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CN1501044A - 组合的空气分离和天然气液化装置 - Google Patents

组合的空气分离和天然气液化装置 Download PDF

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Publication number
CN1501044A
CN1501044A CNA200310103133A CN200310103133A CN1501044A CN 1501044 A CN1501044 A CN 1501044A CN A200310103133 A CNA200310103133 A CN A200310103133A CN 200310103133 A CN200310103133 A CN 200310103133A CN 1501044 A CN1501044 A CN 1501044A
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CN
China
Prior art keywords
heat exchanger
air
natural gas
cryogenic distillation
cold fluid
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Pending
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CNA200310103133A
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English (en)
Inventor
J-P・特拉尼耶
J-P·特拉尼耶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Application filed by LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Publication of CN1501044A publication Critical patent/CN1501044A/zh
Pending legal-status Critical Current

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
    • F25J3/04187—Cooling of the purified feed air by recuperative heat-exchange; Heat-exchange with product streams
    • F25J3/04218—Parallel arrangement of the main heat exchange line in cores having different functions, e.g. in low pressure and high pressure cores
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0022—Hydrocarbons, e.g. natural gas
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
    • F25J1/0042—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by liquid expansion with extraction of work
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    • F25J1/0203—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a single-component refrigerant [SCR] fluid in a closed vapor compression cycle
    • F25J1/0204—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a single-component refrigerant [SCR] fluid in a closed vapor compression cycle as a single flow SCR cycle
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    • F25J1/0205—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a single-component refrigerant [SCR] fluid in a closed vapor compression cycle as a dual level SCR refrigeration cascade
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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    • F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
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Abstract

本发明涉及一种低温蒸馏分离空气和液化天然气(NG)的一体化方法，其中液化天然气所需要的至少一部分致冷作用是来自至少一个低温空气蒸馏装置，该装置包括主换热器(7)和蒸馏塔(15，17)，其中天然气(25)通过在换热器(7，32，34)中与冷流体(21，26)的间接热交换而被液化，所述冷流体至少部分以液体形式被送到换热器中并在该换热器中进行至少一部分汽化。

Description

组合的空气分离和天然气液化装置
发明领域和发明背景
天然气通常从远离消费者的地区获得。在这种情况下，可以预见几种可能性：
-通过管道输送，请注意相关的距离非常大；
-用下列装置将轻质烃液化：
●基本负荷设备：这些设备分布在全世界的约15个地点，在任一
地点可以有一个或多个系列，目前一个系列的容量最多为5百万吨
/年；
●甲烷油槽船：它们输送温度为约-160℃的低温液体，目前约有一
百艘这样的油槽船；
●LNG终端站：来自甲烷油槽船的液化天然气被卸载，然后进行
汽化，并输送到管道中。
峰式设备是小型的液化设备，它距离消费区近，该设备可以在需求低时液化并储存天然气，在需求高时将气体汽化。
-将天然气转化成液体或固体产品，这些产品可以采用以下方式容易地输送：
●以两步方式将天然气转化成重质合成烃：
  ■通过部分氧化或自热重整生产氢和一氧化碳的混合物(称为
  合成气)，这两种方法都需要富氧气体
  ■Fischer-Tropsch型催化反应
●将天然气转化成甲醇
●使用天然气生产氨或肥料
-将天然气在热电联产设备中转化成电能，并通过电缆输送电能：当距离大时，这种方式象管道方式一样是不经济的。
天然气的液化或转化都需要大量的投资以使该工艺能产生效益。在两种方法(液化和转化)之间的第一协合作用可以在上流和下流式基础设施中发现。如果两个装置处于同一地点的上游，则它们可以使用相同的天然气田和相同的管道将天然气输送到该地点。在液化或转化成合成气之前，对于这两个装置而言，对天然气的预处理也可以是共同的。下游口的基础设施也可以是共同的。相同的设施(水、蒸汽、仪表气源)对于两个装置可以是共同的。
在WO00/71951中已经提出使用由液氮、液氧或液氩汽化产生的能量来液化天然气。US-A-5390499和FR-A-2122307涉及在汽化液氮和液化天然气之间的热传递。GB-A-2172388描述了一种生产氧气和液氮的空气分离装置。来自空气分离装置的液氮然后被输送到遥远的地点并用于液化天然气。所生产的气态氮然后用于改进油的回收。
关于生产LNG的液化循环，在各种出版物中描述了几种解决方案(例如，“Developments in natural gas liquefaction”，Hydrocarbon ProcessingApril 1999)。最有效的是级联的致冷循环：通过三种不同的致冷剂来提供致冷作用，通常是甲烷、乙烯和丙烷，它们各自在几个压力水平下汽化。最常用的是具有丙烷预冷却的混合致冷循环，其中烃类的多组分混合物(通常是丙烷、乙烷、甲烷和/或氮)进行天然气的最终冷却，同时单独的丙烷循环进行天然气和所述混合致冷剂的预冷却。该循环描述在US-A-3763658中。由于能耗较高而从未在基本负荷设备中使用过的最后一种循环是膨胀剂循环。US-A-5768912显示了改进这种循环的各种可能方式，但是都不能达到经丙烷预冷却的混合致冷循环的效率。
发明概述
本发明的目的是提供一种在空气分离装置和等熵膨胀的组合中液化天然气且没有高能耗的方法。本发明包括使用可以通过空气分离装置经由等熵膨胀产生的冷能，优选与液体汽化操作一起使用，以便液化天然气。基本理念在于使用从蒸馏段取出的液体或气体形式的冷料流，它富含氮气、氧气或氩气，以便通过间接热交换来冷却天然气。由于用于加热这些冷料流的热量不再能完全用于冷却空气，所以等熵膨胀用于直接冷却空气。另一个方案包括对冷料流之一进行等熵膨胀以便增加由冷料流提供的冷却量，所以能冷却天然气和空气。空气膨胀将是优选的方案，这是因为可以避免循环或使其最小化。一般来说，循环增加了换热器的任务，进而增加了它的不可逆性。
在本文使用的术语“循环”表示至少在换热器的给定区段中，在膨胀后将至少一部分流体加热。在同一给定的区段中，在膨胀之前有至少一部分流体。术语“液化”也包括假液化，这种情况在天然气于超过临界压力的压力下被冷却时出现。
与在所有目前基本负荷设备中已使用的级联或混合致冷循环或两者组合的情况相比，本发明的方法将具有以下优点：
-基本消除了在换热器中分布气相和液相的问题；所以，可以使用铜焊铝型换热器，它比常规螺旋缠绕式换热器更有效且更廉价；也允许在换热器中有更多的料流；
-当气体膨胀时，温度控制更容易；
-设备的开动/关闭更简单；
-对进料组成变化的耐受性更高；
-为了在开动之前填充回路或补偿在操作期间的损失而在级联循环中储存致冷流体或混合致冷剂的各种组分的操作是不再需要的。
根据本发明的一个方面，提供一种低温蒸馏分离空气和液化天然气的一体化方法，其中液化天然气所需要的至少一部分致冷作用是来自至少一个低温空气蒸馏装置，该装置包括主换热器和蒸馏塔，其中天然气通过在换热器中与冷流体的间接热交换而被液化，所述冷流体至少部分以液体形式被送到换热器中并在该换热器中进行至少一部分汽化。
根据本发明的进一步任选方面：
-等熵膨胀提供了用于液化天然气的致冷作用；
-空气分离装置包括两个塔，具有以热方式连接的中压塔和低压塔，和其中空气在被送到中压塔之前在汽轮机中膨胀；
-在低温空气蒸馏装置的主换热器内将天然气液化，其中用于低温空气蒸馏装置的进料空气被冷却到适合蒸馏的温度，和所述冷流体是至少一种液体料流，相对于空气而言，它富含氧气、氮气和氩气中的至少一种，并在主换热器中汽化；
-要在低温空气蒸馏装置中分离的所有空气在主换热器中冷却；
-在非主换热器的附加换热器中，天然气通过热交换被先前在至少一个空气分离装置的主换热器中已被汽化液体冷却的至少一种冷流体液化；
-天然气通过其中流动冷流体的封闭回路被液化，所述冷流体被换热器用液化汽化天然气加热，并在主换热器中通过热交换而被冷却；
-冷流体选自氮气、氩气、CF4、HCF3、甲烷、乙烷、乙烯和丙烷；
-来自低温空气蒸馏装置的气态氮被输送到附加换热器；
-低温空气蒸馏装置产生了加压的氧气，用于由天然气供应的GTL装置、甲醇装置或DME装置中的至少一个；
-液化天然气所需要的所有致冷作用都来自单一低温蒸馏装置，该装置的塔、主换热器和其它换热器位于单一低温试验箱中；
-液化天然气所需要的部分致冷作用来自至少两个低温空气蒸馏装置，各自包括主换热器和蒸馏塔，所述主换热器和蒸馏塔位于低温试验箱内，液化天然气所需要的部分致冷作用由至少一种由蒸馏塔之一生产的富含氧气、氮气或氩气的液体料流的汽化来提供，和天然气在另一个换热器中通过热交换被来自各低温空气蒸馏装置的冷流体液化；
-在进行使用所述冷流体的间接热交换之前，天然气至少部分在低于0℃的温度下通过间接热交换被至少一种不来自任何低温空气蒸馏装置的流体预先冷却；
-所述不来自任何低温空气蒸馏装置的流体包括丙烷。
根据本发明的另一方面，提供一种低温蒸馏分离空气和液化天然气的一体化装置，其中液化天然气所需要的至少一部分致冷作用是来自至少一个低温空气蒸馏装置，该装置包括主换热器和蒸馏塔，包括用于将天然气和冷流体至少部分以液体形式输送到换热器中的装置，用于从换热器取出已液化的天然气的装置，和用于从换热器取出至少部分被汽化的冷流体的装置。
根据本发明的进一步任选方面：
-等熵膨胀提供了用于液化天然气的致冷作用；
-空气分离装置包括两个塔，具有以热方式连接的中压塔和低压塔，以及进行空气膨胀的汽轮机，和用于将已膨胀的空气输送到中压塔的装置；
-该装置包括用于将待液化的天然气输送到低温空气蒸馏装置的主换热器中的装置，其中所述冷流体是至少一种液体料流，相对于空气而言，它富含氧气、氮气和氩气中的至少一种，并在主换热器中汽化；
-该装置包括将要分离的所有空气输送到主换热器中的装置；
-该装置包括非主换热器的附加换热器，和用于将待液化的天然气和至少一种已在至少一个空气分离装置的主换热器中被汽化液体冷却的冷流体输送到附加换热器中的装置；
-该装置包括其中流动至少一种冷流体的封闭回路，该回路经过主换热器和附加换热器；
-该装置包括用于将气态氮从至少一个低温空气蒸馏装置输送到附加换热器中的装置；
-该装置包括用于将加压的氧气从低温空气蒸馏装置输送到由天然气供应的GTL装置、甲醇装置或DME装置的至少一个中的装置；
-液化天然气所需要的所有致冷作用都来自单一低温蒸馏装置，该装置的塔、主换热器和其它换热器位于单一低温试验箱中；
-液化天然气所需要的部分致冷作用来自至少两个低温空气蒸馏装置，各自包括主换热器和蒸馏塔，所述主换热器和蒸馏塔位于低温试验箱内，液化天然气所需要的部分致冷作用由至少一种由蒸馏塔之一生产的富含氧气、氮气或氩气的液体料流的汽化来提供，和天然气在另一个换热器中通过热交换被来自各低温空气蒸馏装置的冷流体液化；
-该装置包括在使用所述冷流体进行间接热交换之前将天然气预先冷却的装置；
-所述用于预先冷却的装置包括换热器和用于将丙烷输送到该换热器的装置。
附图简述
图1-5是根据本发明的装置的示意图。图6是现有技术。
本发明的优选实施方式
以下几种选择是可能的：
1)使用图1的装置进行最小规模的LNG生产：在这种情况下，GTL设备通常在现有/未来的LNG基本负荷设备的附近建设，以便从其基础设施中受益。
空气1在主空气压缩器3中被压缩到21.5巴的压力，并使用机械致冷装置或吸收致冷装置冷却到12℃的温度。然后，空气1用通常含有氧化铝和分子筛的吸收器5提纯，并除去杂质例如水和二氧化碳。提纯装置的低温是优选的，这是出于以下几个原因：空气将在较低的温度下进入主换热器，使得LNG产量增加；空气将含有较少的水，吸收更有效，所以将需要较少的氧化铝和分子筛。然后，空气1(基本量＝1000Nm3/h)被引入通常散热片式铜焊铝型主换热器7中(或者可以使用螺旋缠绕式换热器)，并冷却到-145℃的温度，分成两股料流9、11：第一股料流9(848Nm3/h)在膨胀汽轮机13中膨胀到5.6巴的压力、-173.5℃的温度，液体分数大于10％。假设从该膨胀获得的能量在发电机中回收。尽管如此，可以有几种其它的选择，例如：
-在提纯装置之前或之后用增压器制动汽轮机，从而降低主空气压缩器的排料压力；
-将膨胀汽轮机的能量直接或经由齿轮转移到主空气压缩器的的轴或其驱动器；
第二股料流11(152Nm3/h)进一步冷却、冷凝，过冷到-174.8℃的温度。将这两股料流都引入到低温空气分离装置的中压塔15中。从中压塔15取出富含氧气和富含氮气的料流并输送到低压塔17。从该蒸馏塔17取出富含液氧的料流21(200Nm3/h)，并用泵23泵压到53.5巴的压力，两股富含气态氮的料流19、27也被取出，其中来自低压塔17的料流19处于1.25巴(绝对)的低压和-176℃的温度(该料流已经用于将蒸馏段内部料流过冷；流量为720Nm3/h)，另一股来自中压塔15的料流27处于5.5巴(绝对)的中等压力和-177.8℃的温度(流量为80Nm3/h)。这三股料流19、21、27在换热器7内加热。压力为60巴(绝对)和温度接近环境温度且经过预处理的天然气料流GN25(其中已除去Hg、H2S、H2O和CO2)被引入换热器7内的加热端，流量为38Nm3/h。如果料流25含有重质烃，则可以在换热器7的中等温度下取出，以便如美国专利5390499中所示除去那些重质烃，然后再次加入换热器7中进一步冷却到约-165℃的温度，并在GNL流动时通过阀门或液体汽轮机膨胀之后送至储库。从换热器7中位于空气料流9出口位置上游的位置取出已液化的天然气。
2)使用图2的装置进行中等规模液体的生产。
空气1在压缩器3中被压缩到优选5-25巴(绝对)的中等压力，通常约15巴(绝对)，并使用机械致冷装置或吸收致冷装置冷却到12℃的温度。然后，空气1用通常含有氧化铝和分子筛的吸收器5提纯，并除去杂质例如水和二氧化碳。然后，空气1(基本量＝1000Nm3/h)进一步在增压器6中压缩到50巴(绝对)的压力，冷却，然后引入通常散热片式铜焊铝型换热器7中(或者可以使用螺旋缠绕式换热器)，并冷却到-77℃的温度，分成两股料流：第一股料流9(708Nm3/h)在膨胀汽轮机13中膨胀到5.6巴的压力、-163.7℃的温度。第二股料流11(292Nm3/h)进一步冷却、冷凝，过冷到-174.4℃的温度。将这两股料流都引入到低温空气分离装置的中压塔15中。从中压塔15取出富含氧气和富含氮气的料流并输送到低压塔17。从该蒸馏塔17取出富含液氧的料流21(200Nm3/h)，并泵压到53.5巴的压力，两股富含气态氮的料流19、27也被取出，其中料流19处于1.25巴的低压和-175.4℃的温度(该料流已经用于将蒸馏段内部的料流过冷；流量为720Nm3/h)，另一股料流27处于5.5巴的中等压力和-177.8℃的温度(流量为80Nm3/h)。这三股料流都在换热器内加热，氧气21被汽化。压力为60巴(绝对)且经过预处理的天然气料流25GN(其中已除去Hg、H2S、H2O、CO2和任何其它可能会固化的杂质)被预先冷却到-38℃的温度(通常使用与美国专利3 763 658类似的丙烷循环)，引入换热器7内。天然气的流量为134Nm3/h。在该预冷却阶段已经除去了重质烃。然后，再次加入换热器7中进一步冷却到约-165℃的温度，并通过阀门或液体汽轮机膨胀后送至储库，在汽轮机13的上游。
3)使用图3的装置进行大规模液体生产。
空气1在压缩器3中被压缩到中等压力(5.4巴)，并使用机械致冷装置或吸收致冷装置冷却到12℃的温度。然后，空气用通常含有氧化铝和分子筛的吸收器5提纯，并除去杂质例如水和二氧化碳。然后，空气(基本量＝1000Nm3/h)与循环空气31(流量364Nm3/h)混合，进一步在增压器6中压缩到70巴(绝对)的压力，冷却，然后引入通常散热片式铜焊铝型换热器7中(或者可以使用螺旋缠绕式换热器)，并冷却到-36℃的温度，分成两股料流9、11：第一股料流9(1014Nm3/h)在膨胀汽轮机13中膨胀到5.6巴(绝对)的压力、-149.8℃的温度，并分成两股料流31、33，其中料流33被引入中压塔15，料流31循环到换热器7。第二股料流11(350Nm3/h)进一步冷却、冷凝，过冷到-174.2℃的温度。将它引入到中压塔15中。从中压塔15取出富含氧气和富含氮气的料流并输送到低压塔17。从该蒸馏塔17取出富含液氧的料流21(200Nm3/h)，并泵压到53.5巴的压力，两股富含气态氮的料流19、27也被取出，其中料流19处于1.25巴的低压和-175.2℃的温度(该料流已经用于将蒸馏段内部的料流过冷；流量为720Nm3/h)，另一股料流27处于5.5巴的中等压力和-177.8℃的温度(流量为80Nm3/h)。这三股料流都在换热器内加热，氧气被汽化。压力为60巴(绝对)且经过预处理的天然气料流24GN(其中已除去Hg、H2S、H2O和CO2)被预先冷却到-38℃的温度(通常使用与美国专利3 763 658类似的丙烷循环)，引入换热器7内，流量为280Nm3/h。在该预冷却阶段已经除去了重质烃。然后，再次加入换热器中进一步冷却到约-165℃的温度，并在通过阀门或液体汽轮机膨胀之后送至储库。
下表显示了LNG的产量和使用20000吨/天氧气的GTL设备的能耗。
   LNG，106吨/年MW     能耗
仅有ASU(图6)    0     339
最小规模(图1)    0.8     362
中等规模(图2)    2.7     448
大规模(图3)    5.7     562
在比较最小规模LNG产量与仅有ASU的情况时，可见空气分离装置更简单，与空气压缩器和增压空气压缩器相比的单一空气压缩器、在较高压力下操作的预冷却系统和提纯装置使得这些设备的尺寸显著减少，这是因为体积流量更小，吸收的效率更好。所以，最小规模液体生产对于负性投资是可行的。
或者，可以使用图4所显示的方法。该方案的优点是天然气仅仅与惰性气体进行间接热交换。在这种情况下，空气1在主空气压缩器3中压缩到21.5巴的压力，并使用机械致冷装置或吸收致冷装置冷却到12℃的温度。然后，空气1用通常含有氧化铝和分子筛的吸收器5提纯，并除去杂质例如水和二氧化碳。然后，空气1(基本量＝1000Nm3/h)被引入到通常散热片式铜焊铝型主换热器7中(或者可以使用螺旋缠绕式换热器)，并冷却到-145℃的温度，分成两股料流9、11：第一股料流9(848Nm3/h)在膨胀汽轮机13中膨胀到5.6巴的压力、-173.5℃的温度，液体分数大于10摩尔％。第二股料流11(152Nm3/h)进一步冷却、冷凝，过冷到-174.8℃的温度。将这两股料流都引入到低温空气分离装置的中压塔15中，但水平不同。从中压塔15取出富含氧气和富含氮气的料流并输送到低压塔17。从该蒸馏塔17也取出富含气态氮的料流27(流量为80Nm3/h)。从该蒸馏塔17取出富含液氧的料流21(200Nm3/h)，并用泵23泵压到53.5巴的压力，从该蒸馏塔17也取出富含气态氮的料流19，其中料流19处于1.25巴的低压和-176℃的温度(该料流已经用于将蒸馏段内部的料流过冷；流量为720Nm3/h)。这两股料流19、21都在换热器7内加热。
压力为60巴(绝对)且温度接近环境温度的经过预处理的天然气料流GN25(其中已除去Hg、H2S、H2O和CO2)被引入附加换热器32内，流量为38Nm3/h。如果料流25含有重质烃，则可以在附加换热器32的中等温度下取出，以便如美国专利5390499中所示除去那些重质烃，然后再次加入附加换热器32中进一步冷却到约-165℃的温度，并在GNL流动时通过阀门或液体汽轮机膨胀之后送至储库。在附加换热器32中，天然气与与富含氮的气态料流27和在封闭回路26内流动的流体进行热交换。在该回路内的流体通常是惰性气体，例如氩气、氮气、CF4、HCF3或任何其它致冷剂。将其在其中发生至少部分汽化(或如果在超临界压力之上，假汽化)的换热器32内加热，并在其中发生至少部分冷凝(或如果在超临界压力之上，假冷凝)的换热器7内冷却。从换热器32取出已液化的天然气。
目前，基本上由于塔尺寸的限制，在单一系列中不能建立20000吨/天氧气的空气分离装置。通常需要3-5个系列。相反，可以建立5百万吨/年的单一液化系列。所以，图1-4的方案在建立整个装置方面的最优化可以包括将一种(或几种)冷流体(通常是富含氮气的流体，是液体或蒸气形式)从各空气分离系列送到单一天然气液化系列(参见图5，其中使用三个系列。ASU系列1、ASU系列2和ASU系列3)，而不是将天然气料流输送到每个空气分离系列中。与图4的方法相似，氮气27从所有三个系列中取出(对于至少一个系列)，混合形成单一料流，并输送到第一换热器，然后输送到第二换热器。回路流体26在每个系列的换热器7中冷却，混合形成单一料流，并输送到换热器32，在那里在被分离之间进行加热，并返回到该系列中。天然气25在换热器34中用丙烷和氮气27预冷却。丙烷通常在不同的压力水平下汽化。或者，混合的致冷剂循环可以用于进行该预冷却过程。然后，在换热器32中，天然气用在回路中的氮气27和惰性气体26冷却。
另一种最优化方式是基于这样的事实，即其中氧气在30-60巴下被汽化的空气分离装置能提供低温的冷能(-130℃至-110℃)。所以，可以在10-20巴(绝对)的低压下冷凝天然气(取决于其组成)。有两种选择：
-如果天然气可以在40-60巴(绝对)压力下原位获得，则可以将该天然气在环境温度下或在丙烷预冷却之后(优选的方案)进行等熵膨胀；当对图1和2采用这种优化方案时，LNG的产量分别为1.0Mt/y和3.1Mt/y，能耗分别是361MW和441MW；
-减少原位输送天然气所用的压缩器的数目和/或能耗。
在图1-3中，料流27可以省略。在图4中，部分料流19可以代替料流27。
在所有这些图中，可以按照常规方式使用料流18生产氩气。还可以将部分料流11输送到低压塔。此外，从中压塔提取的液体可以用料流19间接热交换来冷却，然后将它们在阀门中膨胀并引入低压塔。还可以用液体汽轮机代替料流11和LNG上的膨胀阀。如果任一压缩器可以用气体汽轮机驱动，则还可以从该气体汽轮机中提取空气，供应到至少部分空气分离装置中。
图6显示现有技术已知的空气分离装置，其中没有任何天然气液化装置。
空气1在压缩器3中被压缩至中等压力(5.8巴)，并使用机械致冷装置或吸收致冷装置冷却到12℃的温度。然后，空气用通常含有氧化铝和分子筛的吸收器5提纯，并除去杂质例如水和二氧化碳。然后，空气(基本量＝1000Nm3/h)分成两股料流。第一股空气料流(流量455Nm3/h)进一步在增压器6中被压缩到66巴(绝对)的压力，冷却，然后引入通常散热片式铜焊铝型换热器7中(或者可以使用螺旋缠绕式换热器)，并冷却到-98℃的温度，分成两股料流9、11：第一股料流9(65Nm3/h)在膨胀汽轮机13中膨胀到5.6巴(绝对)的压力、-173.4℃的温度，并引入中压塔15。第二股料流11(390Nm3/h)进一步冷却、冷凝，过冷到-168.2℃的温度。将它引入到中压塔15中。第二空气料流(流量545Nm3/h)在换热器7中冷却，也引入到中压塔中。从中压塔15取出富含氧气和富含氮气的料流并输送到低压塔17。从该蒸馏塔17取出富含液氧的料流21(200Nm3/h)，并泵压到53.5巴的压力，两股富含气态氮的料流19、27也被取出，其中料流19处于1.25巴的低压和-175.2℃的温度(该料流已经用于将蒸馏段内部的料流过冷；流量为720Nm3/h)，另一股料流27处于5.5巴的中等压力和-177.8℃的温度(流量为80Nm3/h)。这三股料流都在换热器内加热，氧气被汽化。
尽管已经参考特定的优选实施方案详细描述了本发明，但是本领域技术人员将认识到在权利要求的精神和范围内还有其它本发明的实施方案。特别是，可以使用已经描述的任何关于天然气液化的预冷却循环，和可以使用具有等熵膨胀的任何空气分离装置循环来提供致冷作用，从而液化天然气。

Claims (27)

1.一种低温蒸馏分离空气和液化天然气(NG)的一体化方法，其中液化天然气所需要的至少一部分致冷作用是来自至少一个低温空气蒸馏装置，该装置包括主换热器(7)和蒸馏塔(15，17)，其中天然气通过在换热器(7，32)中与冷流体的间接热交换而被液化，所述冷流体(21，26)至少部分以液体形式被送到换热器中并在该换热器中进行至少一部分汽化。
2.根据权利要求1的方法，其中等熵膨胀提供了用于液化天然气的致冷作用。
3.根据权利要求1或2的方法，其中空气分离装置包括两个塔(15，17)，具有以热方式连接的中压塔和低压塔，和其中空气在被送到中压塔之前在汽轮机(13)中膨胀。
4.根据前述权利要求中任一项的方法，其中在低温空气蒸馏装置的主换热器(7)内将天然气液化，其中用于低温空气蒸馏装置的进料空气(1)被冷却到适合蒸馏的温度，和所述冷流体是至少一种液体料流(21)，相对于空气而言，它富含氧气、氮气和氩气中的至少一种，并在主换热器中汽化。
5.根据权利要求4的方法，其中要在低温空气蒸馏装置中分离的所有空气(1)在主换热器中冷却。
6.根据权利要求5的方法，其中在非主换热器(7)的附加换热器(32)中，天然气(NG)通过热交换被先前在至少一个空气分离装置的主换热器中已被汽化液体(23)冷却的至少一种冷流体(26)液化。
7.根据权利要求6的方法，其中天然气通过其中流动冷流体(26)的封闭回路被液化，所述冷流体被换热器用液化汽化天然气加热，并在主换热器(7)中通过热交换而被冷却。
8.根据权利要求6或7的方法，其中冷流体选自氮气、氩气、CF4、HCF3、甲烷、乙烷、乙烯和丙烷。
9.根据权利要求6、7或8的方法，其中来自低温空气蒸馏装置的气态氮(27)被输送到附加换热器(32)。
10.根据前述权利要求任一项的方法，其中低温空气蒸馏装置产生了加压的氧气(21)，用于由天然气供应的GTL装置、甲醇装置或DME装置中的至少一个。
11.根据前述权利要求任一项的方法，其中液化天然气(NG，25)所需要的所有致冷作用都来自单一低温空气蒸馏装置，该装置的塔、主换热器和其它换热器位于单一低温试验箱中。
12.根据前述权利要求任一项的方法，其中液化天然气所需要的部分致冷作用来自至少两个低温空气蒸馏装置(ASU)，各自包括主换热器(7)和蒸馏塔(15，17)，所述主换热器和蒸馏塔位于低温试验箱内，液化天然气(25)所需要的部分致冷作用由至少一种由蒸馏塔之一生产的富含氧气、氮气或氩气的液体料流的汽化来提供，和天然气在另一个换热器中通过热交换被来自各低温空气蒸馏装置的冷流体(26)液化。
13.根据权利要求12的方法，其中在进行使用所述冷流体(26)的间接热交换之前，天然气至少部分在低于0℃的温度下通过间接热交换被至少一种不来自任何低温空气蒸馏装置的流体(40)预先冷却。
14.根据权利要求13的方法，其中所述不来自任何低温空气蒸馏装置的流体(40)包括丙烷。
15.一种低温蒸馏分离空气和液化天然气的一体化装置，其中液化天然气所需要的至少一部分致冷作用是来自至少一个低温空气蒸馏装置，该装置包括主换热器(7)和蒸馏塔(15，17)，包括用于将天然气(25，NG)和冷流体(21，26)至少部分以液体形式输送到换热器(7，32)中的装置，用于从换热器取出已液化的天然气(LNG)的装置，和用于从换热器取出至少部分被汽化的冷流体的装置。
16.根据权利要求15的装置，其中等熵膨胀提供了用于液化天然气的致冷作用。
17.根据权利要求15或16的装置，其中空气分离装置包括两个塔(15，17)，具有以热方式连接的中压塔和低压塔，以及进行空气膨胀的汽轮机(13)，和用于将已膨胀的空气输送到中压塔(15)的装置。
18.根据权利要求15-17中任一项的装置，它包括用于将待液化的天然气输送到低温空气蒸馏装置的主换热器(7)中的装置，其中所述冷流体是至少一种液体料流(21)，相对于空气而言，它富含氧气、氮气和氩气中的至少一种，并在主换热器中汽化。
19.根据权利要求15-18中任一项的装置，它包括将要分离的所有空气(1)输送到主换热器(7)中的装置。
20.根据权利要求15或16的装置，它包括非主换热器(7)的附加换热器(32)，和用于将待液化的天然气和至少一种已在至少一个空气分离装置的主换热器(7)中被汽化液体(21)冷却的冷流体(26)输送到附加换热器中的装置。
21.根据权利要求20的装置，它包括其中流动至少一种冷流体(26)的封闭回路，该回路经过主换热器和附加换热器(7，32)。
22.根据权利要求20或21的装置，它包括用于将气态氮(27)从至少一个低温空气蒸馏装置输送到附加换热器(32)中的装置。
23.根据权利要求15-22中任一项的装置，它包括用于将加压的氧气(21)从低温空气蒸馏装置输送到由天然气供应的GTL装置、甲醇装置或DME装置的至少一个中的装置。
24.根据权利要求15-23中任一项的装置，其中液化天然气所需要的所有致冷作用都来自单一低温蒸馏装置，该装置的塔、主换热器和其它换热器位于单一低温试验箱中。
25.根据权利要求15-23中任一项的装置，其中液化天然气所需要的部分致冷作用来自至少两个低温空气蒸馏装置，各自包括主换热器和蒸馏塔，所述主换热器和蒸馏塔位于低温试验箱内，液化天然气所需要的部分致冷作用由至少一种由蒸馏塔之一生产的富含氧气、氮气或氩气的液体料流的汽化来提供，和天然气在另一个换热器(32)中通过热交换被来自各低温空气蒸馏装置的冷流体(26)液化。
26.根据权利要求25的装置，它包括在与所述冷流体进行间接热交换之前将天然气预先冷却的装置(34)。
27.根据权利要求26的装置，其中所述用于预先冷却的装置包括换热器(34)和用于将丙烷(40)输送到该换热器的装置。
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