CN1330760A - 用于液化天然气的双多组分制冷循环 - Google Patents

用于液化天然气的双多组分制冷循环 Download PDF

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CN1330760A
CN1330760A CN99814621A CN99814621A CN1330760A CN 1330760 A CN1330760 A CN 1330760A CN 99814621 A CN99814621 A CN 99814621A CN 99814621 A CN99814621 A CN 99814621A CN 1330760 A CN1330760 A CN 1330760A
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E·L·金伯尔
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ExxonMobil Upstream Research Co
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Abstract

公开了一种在两个封闭循环中用两种混合制冷剂使天然气液化生产温度高于－112℃的加压液态产品的方法,即用于使天然气冷却并液化的低度制冷剂和用于冷却所述低度制冷剂的高度制冷剂。所述低度制冷剂用于使天然气液化后,(a)通过由换热器(65)与另一低度制冷剂流逆流换热和与第一高度制冷剂流换热而升温,(b)压缩至升高的压力,和(c)用外部冷却流体后冷却。然后由换热器(65)通过与第二高度混合制冷剂流换热和与低度制冷剂换热使所述低度制冷剂冷却。所述高度制冷剂通过与所述低度制冷剂换热而升温,压缩(67)至升高的压力,用外部冷却流体(69)后冷却。

Description

用于液化天然气的双多组分制冷循环
发明领域
本发明涉及天然气或其它富甲烷气流的液化方法。更具体地，本发明涉及生产温度高于-112℃(-170°F)的加压液化天然气的双多组分制冷剂液化工艺。
发明背景
因其清洁的燃烧质量和方便性，近年来已广泛使用天然气。许多天然气源位于边远地区，距离天然气的任何商业市场都很远。有时可用管道将生产的天然气输送至商业市场。管道输送不可行时，通常将生产的天然气加工成液化天然气(称为“LNG”)运输至市场。
LNG厂的特点之一是所需投资很大。用于液化天然气的设备一般很贵。液化厂由几个基本系统组成，包括气体处理以去除杂质、液化、制冷、电力设备、和储存和载运设施。该厂的制冷系统可占总费用的多达30％。
LNG制冷系统很贵，因为使天然气液化需要非常多的制冷。典型的天然气流在约4830kPa(700psia)至7600kPa(1100psia)的压力和约20℃(68°F)至约40℃(104°F)的温度下进入LNG厂。天然气(主要是甲烷)不能象能源用重烃那样通过单纯提高压力液化。甲烷的临界温度为-82.5℃(-116.5°F)。这意味着不管施加多大的压力只能在低于该温度下使甲烷液化。由于天然气是一种混合气，所以它在一定温度范围内液化。天然气的临界温度典型地在约-85℃(-121°F)和-62℃(-80°F)之间。在常压下天然气组合物典型地在约-165℃(-265°F)和-155℃(-247°F)之间的温度范围内液化。由于制冷设备占LNG设备费的如此大部分，所以已付出很多努力以降低制冷成本。
虽然已用许多制冷循环使天然气液化，但目前LNG厂最常用的三类是：(1)“阶式循环”，在顺序排列的换热器中使用多种单组分制冷剂以使气体温度降至液化温度；(2)“膨胀器循环”，使气体从高压膨胀至低压，温度相应地降低；和(3)“多组分制冷循环”，在专门设计的换热器中使用多组分制冷剂。大多数天然气液化循环使用这三种基本类型的变体或组合。
多组分制冷剂系统涉及循环多组分制冷物流，通常在用丙烷预冷至约-35℃(-31°F)之后。典型的多组分体系包含甲烷、乙烷、丙烷和可选地其它轻组分。不用丙烷预冷的情况下，所述多组分制冷剂可包括更重的组分如丁烷和戊烷。多组分制冷剂循环的特点在于该工艺中的换热器通常必须处理两相制冷剂的流动。多组分制冷剂在一定温度范围内表现出理想的冷凝性质，使换热系统的设计在热力学方面比单组分制冷剂系统更有效。
用于降低制冷成本的建议之一是在高于-112℃(-170°F)的温度和足以使所述液体处于或低于其泡点温度的压力下输送液化天然气。对于大多数天然气组合物，所述PLNG的压力在约1380kPa(200psia)和约4500kPa(650psia)之间的范围内。此加压的液化天然气称为PLNG以区别于在或接近常压和在约-160℃的LNG。PLNG需要明显更少的制冷，因为PLNG的温度可比常压下的常规LNG高50℃。
仍需要用多组分制冷剂液化天然气生产PLNG的改进的封闭循环制冷系统。
发明概述
本发明涉及一种使天然气流液化生产有高于-112℃(-170°F)的温度和足以使所述液态产品处于或低于其泡点的压力的加压液态产品的方法，使用两种封闭循环的混合(或多组分)制冷剂，其中高度制冷剂使低度制冷剂冷却，所述低度制冷剂使所述天然气冷却并液化。在第一封闭制冷循环中通过间接与所述低度多组分制冷剂换热使天然气冷却并液化。然后通过与另一低度制冷剂流逆流换热、再与高度制冷剂流换热使所述低度制冷剂升温。然后将升温的低度制冷剂压缩至升高的压力，用外部冷却流体后冷却。然后通过与第二高度多组分制冷剂流换热和与低度制冷剂换热使所述低度制冷剂冷却。所述高度制冷剂通过与所述低度制冷剂换热而升温。将升温的高度制冷剂压缩至升高的压力，用外部冷却流体后冷却。
该制冷方法的优点在于可容易地使两种混合制冷剂的组成相互适合(最佳化)并适合被液化物流的组成、温度和压力以使该方法的总能量需求最小。回收所述液化工艺上游天然气液体的常规装置(NGL回收装置)所需制冷可并入所述液化法中，从而不需单独的制冷系统。
本发明方法还可生产加压的燃料源，可在不进一步压缩的情况下用于燃气涡轮驱动器。对于含N2的原料流，可优化所述制冷剂的流动使N2对燃料流的排斥最大。
本发明方法可使所需总压缩比传统LNG液化法降低多达50％。这是有利的。因为可使更多的待液化天然气用于产品输出，作为所述液化法中所用压缩机动力涡轮燃料的消耗更少。
附图简述
参考以下详述和附图将更好地理解本发明及其优点，该附图为本发明一实施方案的简化流程图，说明按本发明实施的液化法。该流程图示出本发明方法一优选实施方案。此附图不是要从本发明范围中排除根据此具体实施方案正常和可预料地修改的其它实施方案。为清楚和简便，已从附图中删除所需各种子系统如阀门、流动物流混合器、控制系统和传感器。
优选实施方案
本发明涉及用两个封闭的制冷循环生产液化天然气的改进方法，这两个循环均用多组分或混合制冷剂作为冷却介质。低度制冷剂循环为所述天然气液化提供最低温度的制冷剂。所述低度(最低温度)制冷剂又在另一换热循环中被高度(温度较高)制冷剂冷却。
本发明方法特别适用于生产有高于-112℃(-170°F)的温度和足以使所述液态产品处于或低于其泡点温度的压力的加压液态天然气(PLNG)。术语“泡点”意指液体开始转化成气体的温度和压力。例如，如果使一定体积的PLNG保持恒压，但使其温度升高，则在所述PLNG中开始形成气泡的温度为泡点。类似地，如果使一定体积的PLNG保持恒温，但使其压力降低，则开始形成气泡的压力定义为泡点。在泡点下所述液化气为饱和液体。对于大多数天然气组合物，在高于-112℃下PLNG的压力在约1380kPa(200psia)和约4500kPa(650psia)之间。
参见附图，优选先使天然气原料流通过常规的天然气回收装置75(NGL回收装置)。如果所述天然气流包含在液化期间可能冻结的重烃，或者如果PLNG中不希望有重烃如乙烷、丁烷、戊烷、己烷等，则可在天然气液化之前通过天然气NGL回收装置除去所述重烃。所述NGL回收装置75优选包括多个分馏塔(未示出)，如产生乙烷的脱乙烷塔、产生丙烷的脱丙烷塔和产生丁烷的脱丁烷塔。所述NGL回收装置可还包括去除苯的体系。NGL回收装置的一般操作为本领域技术人员公知。换热器65除如后面详述用于低度制冷剂的冷却之外，还可任选地为所述NGL回收装置75提供制冷任务。
所述天然气原料流可包括由原油井获得的气体(伴生气)或由天然气井获得的气体(非伴生气)，或由伴生气和非伴生气源获得的气体。天然气的组成可显著地改变。本文所用天然气流包含甲烷(C1)作为主要组分。所述天然气典型地还包含乙烷(C2)、更高的烃(C3+)、和微量的污染物如水、二氧化碳、硫化氢、氮气、丁烷、6或更多碳原子的烃、污垢、硫化铁、石蜡、和原油。这些污染物的溶解度随温度、压力、和组成改变。在低温下，CO2、水和其它污染物可形成固体，有可能堵塞低温换热器的流动通道。如果预见其纯组分的固相温度-压力相边界条件，则可通过除去这些污染物避免这些潜在的困难。本发明以下描述中，假定所述天然气流在进入所述NGL回收装置75之前已经过适当地预处理除去硫化物和二氧化碳并用常规的公知方法干燥除去水而产生“脱硫干气”天然气流。
从NGL回收装置排出的原料流10分成物流11和12。物流11通过换热器60，如后面所述，使燃料流17加热，使原料流11冷却。离开换热器60后，原料流11再与物流12混合，混合物流13通过换热器61，使所述天然气流至少部分地液化。离开换热器61的至少部分液化的物流14可选地通过一或多个膨胀装置62如焦耳-汤姆逊阀或水轮机产生温度高于约-112℃(-170°F)的PLNG。来自膨胀装置62的膨胀流体流15通入相分离器63。蒸汽流17从相分离器63中排出。蒸汽流17可作为燃料用于提供驱动液化法中所用压缩机和泵所需功率。用作燃料之前，蒸汽流17优选用作制冷源参与如上所述换热器60中部分原料流的冷却。液流16作为有高于约-112℃(-170°F)的温度和足以使所述PLNG处于或低于其泡点的压力的PLNG产品从分离器63中排出。
换热器61的制冷任务由闭环冷却提供。此冷却循环中所用制冷剂称为低度制冷剂，因为它是比为换热器65提供制冷任务的冷却循环中所用较高温度混合制冷剂温度更低的混合制冷剂。压缩的低度混合制冷剂经流送管线40通过换热器61，在管线41中离开换热器61。要求所述低度混合制冷剂在换热器61中被冷却至这样的温度，当其从换热器61通入液流管线41时全为液态。管线41中的低度混合制冷剂通过膨胀阀64，使足量的液态低度混合制冷剂闪蒸以使所述低度混合制冷剂的温度降至要求的温度。制备PLNG所要求的温度典型地低于约-85℃，优选在约-95℃和-110℃之间。经过膨胀阀64使压力降低。所述低度混合制冷剂经管线42进入换热器61，当其通过换热器61时连续汽化。当其排入管线43时，所述低度混合制冷剂为气/液混合物(主要为气态)。所述低度混合制冷剂经管线43通过换热器65，在此(1)通过逆流地与另一低度制冷剂流(物流53)间接换热和(2)通过与高度制冷剂流31间接换热，所述低度混合制冷剂继续升温和汽化。升温的低度混合制冷剂经管线44通入汽-液分离器80，在此将所述制冷剂分成液态部分和气态部分。气态部分经管线45通入压缩机81，液态部分经管线46通入泵82，使液态部分加压。管线47中的压缩的气态低度混合制冷剂与管线48中的加压液体混合，混合的低度混合制冷剂流被后冷却器83冷却。后冷却器83通过与外部冷却介质间接换热使所述低度混合制冷剂冷却，所述外部冷却介质优选为最终用所述环境作为受热器的冷却介质。适用的环境冷却介质可包括大气、淡水、盐水、大地、或上述两或多种。然后将所述冷却的低度混合制冷剂通入第二汽-液分离器84，使之分成液态部分和气态部分。所述气态部分经管线50通入压缩机86，所述液态部分经管线51通入泵87，使液态部分加压。压缩的气态低度混合制冷剂与加压的液态低度混合制冷剂混合，混合的低度混合制冷剂(物流52)被后冷却器88冷却，后冷却器88通过类似于后冷却器83的适合的外部冷却介质使之冷却。离开后冷却器88后，所述低度混合制冷剂经管线53通入换热器65，在此与通过换热器65的低度制冷剂流43间接换热和与高度制冷的制冷剂(物流31)间接换热，使任何残留的气态低度混合制冷剂大部分液化。
参见所述高度制冷循环，压缩的基本上液态的高度混合制冷剂经管线31通过换热器65至排出管线32。要求在换热器65中使管线31中的高度混合制冷剂冷却至这样的温度，在其从换热器65通入管线32之前全为液态。管线32中的制冷剂通过膨胀阀74，使足量的液态高度混合制冷剂闪蒸以使所述高度混合制冷剂的温度降至要求的温度。所述高度混合制冷剂(物流33)通过换热器65时沸腾，从而当其排入管线20时所述高度混合制冷剂基本上为气态。所述基本上气态的高度混合制冷剂经管线20通入制冷剂汽-液分离器66，分成液态部分和气态部分。气态部分经管线22通入压缩机67，液态部分经管线21通入泵68，使液态部分加压。管线23中的压缩的气态高度混合制冷剂与管线24中的加压液体混合，混合的高度混合制冷剂流被后冷却器69冷却。后冷却器69通过与外部冷却介质间接换热使所述高度混合制冷剂冷却，与后冷却器83和88相似，所述外部冷却介质优选为最终用所述环境作为受热器的冷却介质。然后，冷却的高度混合制冷剂通入第二汽-液分离器70，分成液态部分和气态部分。气态部分通入压缩机71，液态部分通入泵72，使液态部分加压。压缩的气态高度混合制冷剂(物流29)与加压的液态高度混合制冷剂(物流28)混合，混合的高度混合制冷剂(物流30)被后冷却器73冷却，后冷却器73通过适合的外部冷却介质冷却。离开后冷却器73后，所述高度混合制冷剂经管线31通入换热器65，使任何残留的气态高度混合制冷剂大部分液化。
换热器61和65不限于任何类型，但因经济性，优选板翅片式、螺旋式、和低温试验箱换热器，均通过间接换热冷却。本文所用术语“间接换热”意指使两流体流在无任何物理接触或流体间不相互混合的情况下进行热交换。本发明中所用换热器为本领域技术人员所公知。优选送入换热器61和65的含液相和汽相的所有物流具有沿其进入通道的横截面均匀分布的液相和汽相。为此，优选为各蒸汽和液体流提供分布装置。需要将物流分成液体和蒸汽流时，可将分离器加入多相流体流中。例如，在紧邻物流42进入换热器61之前在物流42中加入分离器。
实际上完成天然气的冷却和液化任务的低度混合制冷剂可包含多种化合物。虽然任何数量的组分可形成所述制冷剂混合物，但所述低度混合制冷剂优选有约3至约7个组分。例如，所述制冷剂混合物中所用制冷剂可选自公知的卤代烃及其共沸混合物以及各种烃。一些例子是甲烷、乙烯、乙烷、丙烯、丙烷、异丁烷、丁烷、丁烯、三氯一氟甲烷、二氯二氟甲烷、一氯三氟甲烷、一氯二氟甲烷、四氟甲烷、一氯五氟乙烷、和本领域技术人员已知的任何其它烃基制冷剂。非烃类制冷剂如氮、氩、氖、氦、和二氧化碳也可使用。用于所述低度制冷剂的组分的唯一判断标准是它们是相容的且有不同的沸点，优选相差至少约10℃(50°F)。所述低度混合制冷剂必须能在管线41中基本上为液态，还能通过与其本身和待液化天然气换热而汽化以致所述低度制冷剂在管线43中主要为气态。所述低度混合制冷剂必须不含将在换热器61或65中固化的化合物。适用的低度混合制冷剂的例子可预计落入以下摩尔分数百分率范围内：C1：约15％至30％，C2：约45％至60％，C3：约5％至15％，和C4：约3％至7％。可调节所述低度混合制冷剂组分的浓度使之与待液化天然气的冷却和冷凝特性和所述液化方法的低温需要相匹配。
所述高度混合制冷剂也可包含多种化合物。虽然任何数量的组分可形成所述制冷剂混合物，但所述高度混合制冷剂优选有约3至约7种化合物。例如，所述制冷剂混合物中所用高度制冷剂可选自公知的卤代烃及其共沸混合物，以及各种烃。一些例子是甲烷、乙烯、乙烷、丙烯、丙烷、异丁烷、丁烷、丁烯、三氯一氟甲烷、二氯二氟甲烷、一氯三氟甲烷、一氯二氟甲烷、四氟甲烷、一氯五氟乙烷、和本领域技术人员已知的任何其它烃基制冷剂。非烃类制冷剂如氮、氩、氖、氦、和二氧化碳也可使用。用于所述高度制冷剂的组分的唯一判断标准是它们是相容的且有不同的沸点，优选相差至少约10℃(50°F)。所述高度混合制冷剂必须能在管线32中基本上为液态，还能通过与其本身和要在换热器65中升温的低度制冷剂(物流43)换热而全部汽化以致所述高度制冷剂在管线20中主要为气态。所述高度混合制冷剂必须不含将在换热器65中固化的化合物。适用的高度混合制冷剂的例子可预计落入以下摩尔分数百分率范围内：C1：约0％至10％，C2：约60％至85％，C3：约2％至8％，C4：约2％至12％，和C5：约1％至15％。可调节所述高度混合制冷剂组分的浓度使之与待液化天然气的冷却和冷凝特性和所述液化方法的低温需要相匹配。
实施例
进行模拟的质量和能量平衡以说明附图所示实施方案，结果示于下表中。这些数据是用称为HYSYSTM的商购工艺模拟程序(购自Hyprotech Ltd.of Calgary，Canada)获得；但也可用其它商购工艺模拟程序产生数据，例如包括HYSIMTM、PROIITM、和ASPEN PLUSTM，均为本领域技术人员熟悉的。提供表中所示数据是为更好地理解附图中所示实施方案，但不应解释为本发明不必要地限于此。温度和流量不应认为是对本发明的限制，基于本文的教导，温度和流量可有许多改变。
该实施例假定天然气原料流10有以下组成(摩尔％)：C1：94.3％；C2：3.9％；C3：0.3％；C4：1.1％；C5：0.4％。进入换热器61的低度制冷剂的组成(摩尔％)为：C1：33.3％；C2：48.3％；C3：2.1％；C4：2.9％；C5：13.4％。进入换热器65的高度制冷剂的组成(摩尔％)为：C1：11.5％；C2：43.9％；C3：32.1％；C4：1.6％；C5：10.9％。本领域技术人员可制定封闭循环中制冷剂的组成使对于各种不同的原料气组成、压力和温度而言使天然气液化生产PLNG所需制冷能量最小。
表中所示数据表明低度循环中所需最大制冷剂压力不超过2480kPa(360psia)。使天然气液化至约-160℃温度的传统制冷循环典型地需要约6200kPa(900psia)的制冷压力。通过在低度制冷循环中使用显著降低的压力，所述制冷循环所需管道材料明显减少。
如该实施例中所示，本发明的另一优点是所述液化工艺过程中在足够用于常规气轮机的压力下提供燃料流18，而不用辅助的燃料气压缩。
本领域技术人员特别是得益于本专利的教导，将认识到对上述具体实施方案的许多修改和改变。例如，根据体系的总体设计和原料气的组成，可按本发明采用不同的温度和压力。而且，可根据总体设计需要补充或改装原料气冷却序列以获得最佳有效换热需求。此外，可通过加入可与所示装置互换的装置完成某些工艺步骤。如上所述，具体地公开的实施方案和实施例不应用于限制或约束本发明的范围，本发明的范围由后面的权利要求书及其等同物确定。
                                                                   表
温度            压力                          流量                          组成
 物流 相 ℃ °F  kPa  Psia  KgMol/hr  1bmol/hr  C1Mol％ C2Mol％  C3Mol％  C4Mol％  C5Mol％
 10 气 -42.2 -44.6  4800  696  47,673  105,100  94.3  3.9  0.3  1.1  0.4
 11 气 -42.2 -44.6  4758  690  1,906  4,203  94.3  3.9  0.3  1.1  0.4
 12 气 -42.2 -44.6  4758  690  45,768  100,900  94.3  3.9  0.3  1.1  0.4
 13 气/液 -43.3 -46.5  4775  693  47,673  105,100  94.3  3.9  0.3  1.1  0.4
 14 液 -93.4 -136.7  4569  663  47,673  105,100  94.3  3.9  0.3  1.1  0.4
 15 气/液 -95.8 -141.1  2758  400  47,673  105,100  94.3  3.9  0.3  1.1  0.4
 16 液 -95.8 -141.1  2758  400  46,539  102,600  94.1  4.0  0.3  1.1  0.5
 17 气 -95.8 -141.1  2758  400  1,134  2,500  99.4  0.5  0.0  0.0  0.0
 18 气 -45.2 -50.0  2738  397  1,134  2,500  99.4  0.5  0.0  0.0  0.0
 20 气/液 9.1 47.8  345  50  17,609  38,820  11.5  43.7  32.0  1.6  11.2
 21 液 9.1 47.8  345  50  102  225  0.3  6.5  18.7  2.7  71.8
 22 气 9.1 47.8  345  50  17,504  38,590  11.5  43.9  32.1  1.6  10.9
 23 气 62.8 144.4  1034  150  17,504  38,590  11.5  43.9  32.1  1.6  10.9
 24 液 9.5 48.5  1069  155  102  225  0.3  6.5  18.7  2.7  71.8
 25 气/液 13.1 55.0  986  143  17,609  38,820  11.5  43.7  32.0  1.6  11.2
 26 气 13.1 55.0  986  143  13,236  29,180  14.9  51.7  29.5  0.9  3.0
 27 液 13.1 55.0  986  143  4,370  9,635  1.0  19.6  39.8  3.3  36.3
 28 液 14.2 57.0  2462  357  4,370  9,635  1.0  19.6  39.8  3.3  36.3
 29 气 66.2 150.6  2462  357  13,236  29,180  14.9  51.7  29.5  0.9  3.0
 30 气/液 47.7 117.2  2462  357  17,609  38,820  11.5  43.9  32.1  1.6  10.9
 32 液 -48.0 -55.0  2345  340  17,609  38,820  11.5  43.9  32.1  1.6  10.9
 33 气/液 -64.2 -84.1  365  53  17,609  38,820  11.5  43.9  32.1  1.6  10.9
 40 气/液 -48.0 -55.0  2345  340  50,894  112,200  33.3  48.3  2.1  2.9  13.4
                                                            表
温度            压力                         流量                          组成
 物流 相 ℃  °F  kPa  Psia  KgMol/hr  1bmol/hr  C1Mol％  C2Mol％  C3Mol％  C4Mol％  C5Mol％
 41 液 -93.4  -136.7  2138  310  50,894  112,200  33.3  48.3  2.1  2.9  13.4
 42 气/液 -111.2  -168.8  386  56  50,894  112,200  33.3  48.3  2.1  2.9  13.4
 43 气/液 -47.8  -54.7  365  53  50,894  112,200  33.3  48.3  2.1  2.9  13.4
 44 气/液 9.1  47.8  345  50  50,894  112,200  33.3  48.3  2.1  2.9  13.4
 45 气 9.1  47.8  345  50  50,486  111.300  33.6  48.7  2.1  2.8  12.8
 46 液 9.1  47.8  345  50  441  972  0.7  7.0  1.2  5.1  85.8
 47 气 86.1  186.4  1379  200  50,486  111,300  33.6  48.7  2.1  2.8  12.8
 48 液 9.7  48.8  1379  200  441  972  0.7  7.0  1.2  5.1  85.8
 49 气/液 82.1  179.2  1379  200  50,894  112,200  33.3  48.3  2.1  2.9  13.4
 50 气 13.1  55.0  1331  193  42,108  92,830  39.5  53.0  1.9  1.8  3.8
 51 液 13.1  55.0  1331  193  8,800  19,400  3.5  25.5  3.2  8.3  59.5
 52 气/液 36.6  97.3  2462  357  50,894  112,200  33.3  48.3  2.1  2.9  13.4
 53 气/液 13.1  55.0  2414  350  50,894  112,200  33.3  48.3  2.1  2.9  13.4
 89 气/液 7.0  44.0  5400  783  48,036  105,900  93.5  3.9  0.3  0.7  1.6
 90 气/液 -48.0  -55.0  5365  778  48,036  105,900  93.5  3.9  0.3  0.7  1.6

Claims (6)

1.一种使天然气流液化生产有高于-112℃(-170°F)的温度和足以使所述液态产品处于或低于其泡点的压力的加压液态产品的方法，使用两种封闭循环的多组分制冷剂，其中高度制冷剂使低度制冷剂冷却，所述低度制冷剂使所述天然气冷却并液化，所述方法包括以下步骤：
(a)在第一封闭制冷循环中通过间接与所述低度多组分制冷剂换热使天然气流冷却并液化；
(b)通过与另一低度制冷剂流逆流换热和与高度制冷剂流换热使所述低度制冷剂升温；
(c)将步骤(b)所述升温的低度制冷剂压缩至升高的压力，用外部冷却流体后冷却；
(d)通过与第二高度多组分制冷剂流换热和与步骤(b)的低度制冷剂换热使所述低度制冷剂进一步冷却，在此热交换期间所述高度制冷剂升温；和
(e)将步骤(d)所述升温的高度制冷剂压缩至升高的压力，用外部冷却流体后冷却。
2.权利要求1的方法，其中步骤(a)的间接换热由一步组成。
3.权利要求1的方法，其中所述低度多组分制冷剂包含甲烷、乙烷、丁烷和戊烷。
4.权利要求1的方法，其中所述高度多组分制冷剂包含丁烷和戊烷。
5.一种使富甲烷气流液化生产有高于-112℃(-170°F)的温度和是以使所述液态产品处于或低于其泡点的压力的加压液态产品的方法，使用两个封闭的多组分制冷循环，所述制冷循环中的各种制冷剂包含不同挥发度的组分，所述方法包括：
(a)在第一制冷循环中用第一低度混合制冷剂在第一换热器中使所述富甲烷气流液化；
(b)在多个压缩步骤中压缩所述第一低度混合制冷剂，在一或多步中用外部冷却流体使所述压缩的低度混合制冷剂冷却；
(c)在第二换热器中用第二低度混合制冷剂冷却所述压缩冷却的第一低度混合制冷剂以使所述压缩的第一低度混合制冷剂在第一换热器中使所述富甲烷气体液化之前至少部分地液化；和
(d)在多个压缩步骤中压缩所述第二多组分制冷剂，在一或多步中用外部冷却流体使所述压缩的第二多组分制冷剂冷却，使所述压缩冷却的第二多组分制冷剂在第二换热器中热交换产生冷却的至少部分液化的第二多组分制冷剂，使所述冷却的至少部分液化的第二多组分制冷剂膨胀产生低温冷却剂，通入所述低温冷却剂与所述压缩冷却的第二多组分制冷剂逆流换热使所述第一多组分制冷剂至少部分液化并使所述第二多组分制冷剂至少部分汽化，将所述第二多组分制冷剂循环至第一压缩步骤。
6.一种使富甲烷气体液化产生温度高于约-112℃的加压液态产品的方法，包括以下步骤：
(a)在第一换热器中通过与第一封闭制冷循环中的第一多组分制冷剂换热使所述气体冷却并液化；
(b)在第二换热器中用第二封闭制冷循环中的第二多组分制冷剂使所述第一多组分制冷剂冷却；
(c)所述第一制冷循环包括：
在至少一个压缩冷却步骤中使步骤(b)的冷却的第一制冷剂加压和冷却，所述压缩冷却步骤包括使升温的第一制冷剂相分离成为汽相和液相，分别使所述汽相和液相加压，使所述加压的液相和加压的汽相混合，用外部冷却流体使所述混合相后冷却；
使所述加压的第一制冷剂通过第二换热器用所述第二制冷剂冷却所述第一制冷剂；
使所述加压的第一制冷剂通过第一换热器；
使所述加压的第一制冷剂膨胀使所述第一制冷剂转化成更低温度的混合制冷剂，使所述膨胀的第一制冷剂与膨胀前的第一制冷剂和富甲烷气逆流通过所述第一换热器，从而使所述膨胀的第一制冷剂升温并产生温度高于约-112℃的加压液体，使所述升温膨胀的第一制冷剂循环至第二换热器；和
(d)所述第二制冷循环包括：
在至少一个压缩冷却步骤中使所述升温的第二制冷剂加压和冷却，所述压缩冷却步骤包括使所述升温的第二制冷剂相分离成为汽相和液相，分别使所述汽相和液相加压，使所述加压的液相和加压的汽相混合，用外部冷却流体使所述混合相后冷却；
使所述加压的第二制冷剂通过第二换热器用所述第二制冷剂冷却所述第一制冷剂；
使所述加压的第二制冷剂膨胀至更低温度，使所述膨胀的第二制冷剂与膨胀前的第二制冷剂和所述第一制冷剂逆流通过所述第二换热器，从而使所述膨胀的第二制冷剂升温。
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CN1703606B (zh) * 2002-10-07 2010-10-27 科诺科菲利浦公司 用于使天然气液化的工艺和装置
CN100565059C (zh) * 2003-03-18 2009-12-02 气体产品与化学公司 用于气体液化的集成式多回路制冷工艺及系统
CN100504262C (zh) * 2004-06-23 2009-06-24 埃克森美孚上游研究公司 混合冷却剂液化方法
CN101392983B (zh) * 2008-11-10 2012-12-05 陈文煜 一种液化富甲烷气的过程
CN101392982B (zh) * 2008-11-10 2012-12-05 陈文煜 一种液化富甲烷气的工艺流程
CN105716369A (zh) * 2010-03-17 2016-06-29 查特股份有限公司 整体式预冷却混合制冷系统和方法
CN102506298A (zh) * 2011-09-30 2012-06-20 中国寰球工程公司 用于液化天然气装车系统的冷循环系统和方法
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CN102748918A (zh) * 2012-07-03 2012-10-24 中国海洋石油总公司 双级混合冷剂循环天然气液化系统
CN103216998A (zh) * 2013-04-12 2013-07-24 北京安珂罗工程技术有限公司 一种单循环混合冷剂压缩与输送的方法和系统
CN106796081A (zh) * 2014-10-09 2017-05-31 林德股份公司 控制耦合的换热器系统的方法和换热器系统
CN107166871A (zh) * 2017-06-01 2017-09-15 西安交通大学 采用双级混合制冷剂循环的液化天然气蒸发气再液化系统

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