CN1391646A - 用于多组分原料流的蒸馏方法 - Google Patents

用于多组分原料流的蒸馏方法 Download PDF

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CN1391646A
CN1391646A CN99812434A CN99812434A CN1391646A CN 1391646 A CN1391646 A CN 1391646A CN 99812434 A CN99812434 A CN 99812434A CN 99812434 A CN99812434 A CN 99812434A CN 1391646 A CN1391646 A CN 1391646A
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pressure
stream
liquid
natural gas
gas
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CN1145000C (zh
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E·T·科勒
B·T·斯通
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ExxonMobil Upstream Research Co
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Exxon Production Research Co
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Abstract

本发明公开了一种从富含甲烷的原料流中除去高挥发性组分如氮气以生产基本不含高挥发性组分的产品的方法。将原料流膨胀(53)并加入产生气流(22)和液体流(19)的相分离器(55)中。气流富集挥发性组分；将贫含挥发性组分和富含甲烷的液体流泵抽(56)至更高压力并加热以生产加压液化产品流，此产品流的压力足以使其处于或低于其泡点，其温度大于约－112℃(－170°F)。

Description

用于多组分原料流的蒸馏方法
发明领域
本发明涉及利用分馏分离多组分原料流和生产加压冷冻的液态产品的一种方法。更具体地说，本发明涉及分离含甲烷和至少一种比甲烷挥发性更高的高挥发性组分的多组分流和生产加压液化天然气的一种方法。
发明背景
由于燃烧干净和使用便利，近年来天然气逐渐被广泛使用。许多天然气源在偏远地区，与使用天然气的市场相距很远。有时可利用管道将生产的天然气传输至使用市场。当管道传输不可行时，常常将生产的天然气加工成液化天然气(称为L‘NG’)运输至市场。
天然气常含诸如氮气和氦气之类的稀释剂气体，这些气体的存在降低了天然气的热值，其中的某些气体如果能从天然气中分离出来，本身也有独立的商业用途。因此，从天然气中分离稀释剂气体在经济上可以有双重好处，即增加天然气的热值和生产诸如氦气之类的有商业价值的气体。LNG工厂也从天然气中除去氮气，因为在运输传统的LNG过程中，LNG处于或接近大气压力，氮气不会保留在液相中。
一般而言，大多数已知的天然气分离方法包括至少三个不同的操作步骤。它们包括(1)除去水和诸如二氧化碳和硫化氢之类的酸性气体的初步气体处理步骤；(2)使用低但不是深冷温度分离和回收乙烷和更重烃组分的天然气液体产品分离步骤；(3)氮气分离或排放步骤，常称之为氮气排放单元(NRUs)。氮气的排放一般通过在蒸馏柱中将含氮气天然气冷却并分馏来进行。
近来，人们建议生产温度大于约-112℃(-170°F)和压力足以使其处于或低于其泡点的富含甲烷的液体。加压液化天然气有时称之为PLNG以区别于处于或接近大气压力的LNG。典型地，PLNG的压力大于约1,380kPa(200psia)。生产PLNG方法的一个优点是加压液化天然气可包含高达约10摩尔百分数的氮气，但是，氮气降低了PLNG的热值和增加了PLNG产品的泡点。因此需要一种从天然气流中除去氮气同时生产PLNG的改进方法。
概述
本发明涉及一种液化方法，其中含甲烷和至少一种比甲烷挥发性更高的高挥发性组分如氦气和氮气的原料流生产富含甲烷且基本不含更高挥发性组分的加压液化产品。为了说明的目的，假定更易挥发的组分是氮气。
在本发明的方法中，将液化多组分原料流加入诸如一个或多个水轮机之类的液压骤冷器装置中。多组分原料流富含甲烷和至少一种比甲烷挥发性更高的高挥发性组分。原料流处于或低于其泡点，其温度大于约-112℃(-170°F)。骤冷器装置降低原料流的压力并冷却原料流，在压力降低的过程中产生气相和液相。将液相和气相从骤冷器装置中加入分离系统中以使液相和气相分离。将富含挥发性组分的顶部气流从分离系统中排出。优选将一部分顶部气流作为蒸气产品流排出，它们可用作燃料气或进行进一步加工。优选将剩余部分顶部气流冷凝，用于内部或外部冷冻系统。冷凝后，优选将液流加入分离系统的上部区域。将富含甲烷的液流从分离系统回收，泵抽至更高压力并加热，优选间接与原料流进行热交换，由此产生加压液化产品流，此产品流的压力足以使其处于或低于其泡点，其温度大于约-112℃(-170°F)。在优选实施方案中，富含甲烷的高压流与原料流之间的热交换降低了液化方法的冷冻要求。
附图的简要描述
通过参看下列详细描述和附图可以更好地了解本发明及其优点。
图1为本发明的一个实施方案的简要流程图，说明从加压天然气中除去氮气和生产PLNG的低温方法。
图2为本发明的第二个实施方案的简要流程图。
附图中的流程图表现了实践本发明的优选实施方案。这些附图无意将体现对这些特定实施方案进行正常和可预见的修改所得结果的其它实施方案排除在本发明的范围之外。为了简明和表示清楚，所要求的各种子系统如阀门、物流混合机、控制系统和传感器已从附图中删去。
优选实施方案的描述
发现加压液化天然气(PLNG)可由传统的氮气排放单元生产。加压液化天然气流与其它工艺流之间的间接热交换降低了液化方法的冷冻要求。
根据此发现，本发明提供了一种分离含甲烷和至少一种高挥发性组分如氦气和氮气的液化天然气的方法。此分离方法产生一种液化天然气，它基本不含高挥发性组分，其温度大于约-112℃(-170°F)和压力足以使其处于或低于其泡点。在此说明书中，这种富含甲烷的产品有时称之为加压液化天然气(“PLNG”)。
用于此说明书中的术语“泡点”是液体开始蒸发的温度和压力。例如，如果一定体积的PLNG保持在固定压力，但是增加其温度，在PLNG中气泡开始形成的温度为泡点。同样，如果一定体积的PLNG保持固定温度，但是降低其压力，气体开始形成的压力定义为泡点。在泡点时，液化气体为饱和液体。
在低温加工天然气的过程中，首先要考虑的是沾污。适于本发明方法的天然气原料可包括从原油井(伴生气)或气井(非伴生气)得到的天然气。天然气的组成差别很大。用于此处的天然气流包含的主要成分为甲烷(C1)。典型地，天然气也包含乙烷(C2)、更多碳的烃(C3+)和少量杂质如水、二氧化碳、硫化氢、氮气、丁烷、六个或更多碳原子的烃、脏物、硫化铁、蜡和原油。这些杂质的溶解度随温度、压力和组成的变化而变化。在低温时，二氧化碳、水或其它杂质可形成固体，在低温热交换器中会堵塞通道。考虑温度与压力的关系如果预先将温度降至等于或低于其纯组分的固体温度以除去这些杂质，这些潜在困难可避免。在本发明的下列描述中，认为天然气流已使用已知的传统方法经过适当处理除去了硫化物和二氧化碳，并干燥除去了水份，产生“纯净干燥”的天然气流。如果天然气流包含在液化过程中会冻析的重烃或不希望在PLNG中存在重烃，可在生产PLNG之前通过分馏方法将重烃除去。在PLNG的操作压力和温度下，天然气中有适量的氮气是可以接受的，因为氮气会与PLNG一起保持在液相中。在此说明书中，假设根据本发明的分离方法，天然气中包含足以证实氮气除去的氮气含量。
以图1中表示的流程图为参考，对本发明的方法进行描述。天然气原料流10在大于约1,380kPa(200psia)、更优选2,400kPa(350psia)的压力和优选大于约-112℃(-170°F)的温度下进入液化工艺。不过，如有需要，可使用不同的压力和温度，系统可据此进行适当的调整。如果气流10的压力低于1,380kPa(200psia)，可通过合适的压缩装置(未显示)加压，压缩装置可包括一个或多个压缩机。
将原料流10通过热交换器区50使天然气液化。热交换器区50可包括由以丙烷、丙烯、乙烷、二氧化碳或任何其它合适液体作为制冷剂的传统封闭循环冷冻系统51进行冷却的一段或多段。本发明不局限于任何种类的热交换器，但是由于经济原因，优选散热片式、旋绕式和冷箱热交换器，这些热交换器均通过间接热交换冷却。冷冻系统51优选为闭环多组分冷冻系统，这是本领域普通技术人员周知的通过间接热交换进行冷却的方式。用于本发明和权利要求书中的术语“间接热交换”意指两股流体流产生热交换关系而无任何物理接触或流体彼此之间不相混合。
然后，将从热交换器区域出来的液化天然气流13以适当的膨胀方法如液压骤冷器53和54进行膨胀以减小物流的压力，由此在物流进入分离柱55中部之前对物流进行冷却。分离柱55为蒸馏或分馏柱或区域，其中液相和气相顺流接触以进行流体混合物的分离，例如，在一系列固定在柱内的竖直方向分开的塔盘或板上或在充填柱的填料上通过气相和液相的接触进行流体混合物的分离。分离柱55优选在约-175℃(-283°F)至约-160℃(-256°F)的温度范围内和在接近大气压、更优选在约100kPa至约120kPa的压力范围内操作。在分离柱55内，富含氮气的气体和富含甲烷的液体被分离。液体以流体19离开分离柱55，流体19经过泵56，该泵将液化天然气抽至所希望的储存或运输压力。用于PLNG的压力优选为大于约1,724kPa(250psia)。优选将PLNG通过热交换器65温热至其温度大于约-112℃(-170°F)。
从氮气排放柱55的顶部出来的气流22包含甲烷、氮气和诸如氦气和氢气之类的其它轻组分。典型地，富含甲烷的气流22包含原料流和蒸发气流中90％以上的氮气。气流22中的第一部分从此过程中作为燃料或为了进一步处理以回收氦气和/或氮气而再利用(气流27)。因为气流22处于低温下，为了将气流27作为燃料使用，优选在热交换区(在图1中未显示)中通过空气、淡水或盐水将其温热至适当的温度或通过进入工艺流程的原料流温热。将顶部气流的第二部分(气流32)通过冷却区70，使至少一部分气流32液化，再作为回流返回至柱55，由此至少部分为操作柱55提供必要的冷冻。冷却区70可包括使至少部分气流32液化的任何传统冷却系统。例如，冷却区可包括(1)冷却一或多个热交换段的单个、级联或多组分闭环冷冻系统，(2)利用单级或多级压力循环的开环冷冻系统，给气流32加压，随之通过单级或多级膨胀循环降低压缩气流的压力，由此降低其温度，或(3)与产品流的间接热交换关系，从产品流中抽取含于其中的冷冻作用，或(4)这些冷却系统的组合。考虑气流32的流速、其组成和分离柱55的冷冻需要，本领域的普通技术人员可确定冷却区70所需的最优冷却系统。
图2表示本发明方法的一个优选实施方案，在此实施方案中，与图1中的设备和流体流有相似编号的设备和流体流有基本相同的处理功能且操作方式基本相同。不过，本领域的普通技术人员会认识到从一个实施方案到另一个实施方案中的处理设备和流体流在大小和容量上会有所变化以满足不同的流体流速、温度和组成的要求。
在图2的方法中，将原料流10通过热交换器区域50以使天然气液化，将冷却流13在热交换器区域52中进一步冷却，热交换器区域52被分馏柱55中的液体产品冷却。然后用适当的液压骤冷器53和54将冷却液体流14膨胀以降低压力和进一步冷却此流。将已膨胀的液化冷天然气通过分馏柱55，分馏柱55产生富含氮气的顶部气流22和富含甲烷的液体19。将此液体通过泵56加压至所希望的贮存或运输压力。再将加压液体通过热交换器区域52冷却管道13中的原料流，并将加压液体温热至大于约-112℃(-170°F)的温度，由此从产品流中抽取含于其中的冷冻。与原料流不用PLNG冷却的情况下所需的能量相比，在PLNG流与管道13中的原料流之间的间接热交换降低了冷却所需能量的40％之多。管道21中的压力和温度为温度大于约-112℃(-170°F)和压力足以使液体产品处于或低于其泡点。
气流22通过热交换器57和59将返回柱55的回流物流冷却。从热交换器59中出来的气流用单级或多级压缩机进行压缩。在图2中，气流连续通过两个常规的压缩机60和62。经过每一压缩步骤后，将气流以环境空气或水或以后冷却器进行冷却。经过最后的压缩步骤后，可将一部分气流排出，用作驱动压缩机和泵的气体涡轮的燃料，或将排出的气流进行进一步处理以回收商业用途的氦气和/或氮气。将气流中的余下部分(气流28)通过热交换器59、58和57以进一步冷却气流。热交换器59和57由上述的顶部气流22冷却。通过间接热交换以工艺中衍生的至少一种致冷剂、优选从分馏柱55的较低部位排出的塔底物流(物流33)对热交换器58进行冷却。以适当的膨胀设备如涡轮骤冷器64将从热交换器57中出来的回流气流(物流31)膨胀至等于或接近于分馏柱55的操作压力。以骤冷器64将至少部分气流冷凝成液体。从骤冷器装置中出来的回流气流(物流32)进入分馏柱55的上部。
在贮存、运输和处理液化天然气的过程中，可能有一定量的蒸发。本发明的方法可任选地再液化这些蒸发气体，也可除去包含在蒸发气体中的氮气。蒸发气体中氮气杂质的主要来源是包含在液化天然气中的氮气，液化天然气是蒸发气体的来源。比液化天然气更具挥发性的氮气优先闪蒸出来，集中在蒸发气体中。例如，含0.3摩尔％N2的液化天然气可生产含约3摩尔％N2的气体。在PLNG的更高温度和压力下，氮气甚至比处于或接近大气压的传统液化天然气更优先闪蒸出来。
参见图2，可将蒸发气体通过气流34引入本发明的方法中。虽然图1说明了将蒸发气体34引入处于在骤冷器53与54之间的工艺流中，但是根据本发明的原理，可将蒸发气体引入本方法中在将原料流引入柱55中之前的任一位置，也可将蒸发气体直接引入柱55中，这对于本领域的普通技术人员是显而易见的。引入本发明分离过程中的蒸发气体应处于或接近于将蒸发气体引入其中的气流的压力。取决于蒸发气体的压力，也许需要压缩机65对蒸发气体进行压力调整或使蒸发气体膨胀(未在图中显示)以便与蒸发气体进入流程中所在位置的压力相匹配。
实施例
实行模拟物料和能量平衡以说明列于图2中的实施方案，这些结果列于下表中。列于表中的数据用于更好了解图2中所示的实施方案，并无意局限本发明的范围。
这些数据通过使用可购得的工艺模拟程序HYSYSTM得到，不过，也可使用其它可购得的工艺模拟程序得到这些数据，包括例如HYSIMTM、PROIITM和ASPEN PLUSTM，这些已为本领域的普通技术人员所熟悉。
本领域的普通技术人员，特别是了解本发明原理益处的人，会认识到可对上述具体方法进行调整和改变。例如，取决于系统的整体设计和原料气的组成，可根据本发明使用不同的温度和压力。取决于整体设计要求，也可补充或重新配置原料冷却机以得到最优且有效的热交换要求。如上所述，公开的具体实施方案和实施例不应该用于局限或限制本发明的范围，本发明的范围由以下的权利要求书和其同等物决定。
                                                                    表1
    组成，摩尔％
物流 气相/液   压力psia   压力kPa   温度°F    温度℃   流量lbmole/hr    流量kgmole/hr    C1    C2    C3+    CO2   He     N2
    10     V   1300   8960    50     10    79610    36110   95.53    0.10    0.0    0.04   0.02    4.31
    11     V/L   390   2690    55     13   137520    62380   29.00    48.0    23.0    0.0   0.0    0.0
    12     V   155   1070    52     11   137520    62380   29.00    48.0    23.0    0.0   0.0    0.0
    13     L   1250   8620   -120    -84   79610    36110   95.53    0.10    0.0    0.04   0.02    4.31
    14     L   1240   8550   -242    -152   79610    36110   95.53    0.10    0.0    0.04   0.02    4.31
    15     L   445   3070   -244    -153   79610    36110   95.53    0.10    0.0    0.04   0.02    4.31
    17     L   445   3070   -223    -142   86200    39100   95.72    0.09    0.0    0.04   0.02    4.13
    18     V/L   16   110   -262    -164   86200    39100   95.72    0.09    0.0    0.04   0.02    4.13
    19     L   16   110   -260    -162   79330    35990   99.36    0.10    0.0    0.04   0.00    0.50
    20     L   475   3280   -256    -160   79330    35990   99.36    0.10    0.0    0.04   0.00    0.50
    21     L   465   3210   -140    -96   79330    35990   99.36    0.10    0.0    0.04   0.00    0.50
    22     V   16   110   -270    -168   33120    15020   53.66    0.00    0.0    0.00   0.23    46.11
    23     V   16   110   -150    -101   33120    15020   53.66    0.00    0.0    0.0   0.23    46.11
    24     V   16   110    58     14   33120    15020   53.66    0.00    0.0    0.0   0.23    46.11
    25     V   65   450    344     173   33120    15020   53.66    0.00    0.0    0.0   0.23    46.11
    26     V   60   410    55     13   33120    15020   53.66    0.00    0.0    0.0   0.23    46.11
    27     V   410   2830    453     234   6860    3110   53.66    0.00    0.0    0.0   0.23    46.11
    28     V   400   2760    136     58   26260    11910   53.66    0.00    0.0    0.0   0.23    46.11
    29     V   390   2690   -101    -74   26260    11910   53.66    0.00    0.0    0.0   0.23    46.11
    30     V   380   2620   -140    -96   26260    11910   53.66    0.00    0.0    0.0   0.23    46.11
    31     V/L   370   2550   -191    -124   26260    11910   53.66    0.00    0.0    0.0   0.23    46.11
    32     V/L   16   110   -277    -172   26260    11910   53.66    0.00    0.0    0.0   0.23    46.11
    33     L   16   110   -261    -163   81640    37030   99.06    0.10    0.0    0.04   0.00    0.80
    34     V   445   3070   -130    -90   6590    2990   98.00    0.00    0.0    0.0   0.0    2.0
功率                   功率，kW       功率，hp
冷冻系统51          45,040         60,410
压缩机
60                  22,780         30,550
62                  32,460         43,530
泵
56                  1,600          2,140
             小计   101,880        136,630
骤冷器
53                  -1,410         -1,890
54                  -1,880         -2,520
64                  -4,680         -6,280
小计                -7,970         -10,690
            总计    93,910         125,940

Claims (12)

1.一种从含挥发性组分的加压液化天然气物流中排放比甲烷更易挥发的组分的方法，包括步骤：
(a)将液化天然气物流膨胀至较低压力；
(b)将膨胀的气流通过分馏系统，产生贫含挥发性组分的液流和富含挥发性组分的蒸气流；和
(c)将液流加压至大于约1,380kPa(200psia)的压力，并将液流温热至大于约-112℃的温度，以便液流的温度和压力处于或低于其泡点。
2.权利要求1的方法，它进一步包括以下步骤：从分馏系统提取部分蒸气流，将提取的部分蒸气流冷却至此提取的部分蒸气流至少部分冷凝，并将至少部分被冷却的提取的部分蒸气流作为回流物流返回分馏系统，由此给分馏系统提供冷却。
3.权利要求1的方法，其中在步骤(a)中液化天然气在膨胀前的温度大于约-112℃和压力使其处于或低于其泡点。
4.权利要求1的方法，其中挥发性组分为氮气。
5.权利要求1的方法，其中分馏系统的操作压力接近大气压。
6.权利要求1的方法，其中挥发性组分为氦气。
7.权利要求1的方法，其中在将膨胀气流通入分馏系统前，将从液化气蒸发得到的蒸发气体引入该膨胀气流中。
8.权利要求1的方法，其中步骤(c)中液流的温热至少部分是通过与步骤(a)的膨胀之前的液化天然气进行间接热交换进行的。
9.权利要求1的方法，其中在步骤(a)中加压液化天然气在膨胀前的压力大于约1,380kPa(200psia)。
10.权利要求9的方法，其中液化天然气的压力大于2,400kPa(350psia)。
11.一种从含氮气的加压天然气物流中排放氮气的方法，包括步骤：
(a)将加压天然气物流进行冷却以产生第一液体，该液体的温度大于约-112℃(-170°F)，其压力足以使第一液体处于或低于其泡点；
(b)使第一液体膨胀至更低压力，由此产生两相气体物流；
(c)将所说的两相气体物流通过分馏系统，产生贫含氮气的第二液体和富含氮气的蒸气；
(d)将富含氮气的蒸气的第一部分从分馏系统中作为产品流排出；
(e)冷却富含氮气的蒸气的第二部分，由此所说的第二部分至少部分被冷凝；
(f)将所说已冷却的、至少部分冷凝的第二部分作为回流物流返回至分馏系统，由此给分馏系统提供冷却；
(g)从分馏系统中排出第二液体；和
(h)将第二液体加压至约1,724kPa(250psia)以上的压力，并将第二液体温热至约-112℃以上的温度，以便使第二液体的压力和温度处于或低于其泡点。
12.一种分离方法，包括步骤：
(a)将加压液化多组分原料流送入液压骤冷器装置中，以降低原料流压力和冷却原料流，原料流至少包含甲烷和至少一种挥发性比甲烷更高的高挥发性组分，所说的骤冷器在降压过程中形成气相和液相；
(b)将由骤冷器装置产生的液相和气相送入分离系统，产生贫含高挥发性组分的液体馏分和富含高挥发性组分的蒸气馏分；
(c)将蒸气馏分从分离系统的上部排出；
(d)将所说的蒸气馏分压缩至成更高压力物流；
(e)将压缩蒸气馏分的第一部分作为富含高挥发性组分的压缩蒸气物流排出；
(f)使用步骤(c)中蒸气馏分可得到的冷却，对压缩蒸气物流的第二部分进行冷却；
(g)将步骤(f)的已冷却的压缩蒸气物流膨胀，以进一步冷却所说的压缩物流并至少冷凝部分该蒸气物流；
(h)将步骤(g)的膨胀的物流送入分离系统的上部；
(i)从分离系统的较低部位回收贫含高挥发性组分的液流；和
(j)将液体馏分加压并对其进行温热从而产生液体产品，液体产品的压力足以使其处于或低于其泡点，并且温度大于约-112℃。
CNB998124346A 1998-10-22 1999-10-22 用于多组分原料流的蒸馏方法 Expired - Fee Related CN1145000C (zh)

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