CN1616609A - 天然气液化和转化方法 - Google Patents

天然气液化和转化方法 Download PDF

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CN1616609A
CN1616609A CNA2004100855400A CN200410085540A CN1616609A CN 1616609 A CN1616609 A CN 1616609A CN A2004100855400 A CNA2004100855400 A CN A2004100855400A CN 200410085540 A CN200410085540 A CN 200410085540A CN 1616609 A CN1616609 A CN 1616609A
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natural gas
gas
sweet natural
pipeline
fisher
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CN1616609B (zh
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B·菲色尔
A·罗吉
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—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
    • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0235—Heat exchange integration
    • F25J1/0237—Heat exchange integration integrating refrigeration provided for liquefaction and purification/treatment of the gas to be liquefied, e.g. heavy hydrocarbon removal from natural gas
    • F25J1/0238—Purification or treatment step is integrated within one refrigeration cycle only, i.e. the same or single refrigeration cycle provides feed gas cooling (if present) and overhead gas cooling
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
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Abstract

通过管道1流动的天然气冷却，然后在涡轮T1中膨胀。罐D2底部的液体是液化天然气。在罐D2顶部的气体通过压缩机K1压缩，然后送入采用Fisher－Tropsch过程的处理装置，将天然气转化为天然气液体。

Description

天然气液化和转化方法
发明领域
本发明涉及天然气转化为液态产物的方法。更具体地，本发明提供采用Fisher-Tropsch过程的协合作用，通过冷却使天然气液化的方法。
所谓的天然气是一种包含至少50％甲烷以及可能的其他烃和氮的气体、液体或两相的混合物。天然气一般以气体形式，在例如2-15MPa的高压下生产。
天然气通常在远离需使用它的地方生产。常规方法是将气体转化为液体，以便能例如通过LNG载运车长途运输。天然气可以在极低温度下液化。也可以通过Fisher-Tropsch过程重整为合成气，然后转化为液体石蜡。
发明背景
有许多天然气液化的方法。
具体而言，专利US-6,105,389描述了一种采用两个冷却剂循环的液化方法。尽管这种方法是有效的，但是需要大量能量，因此需使用非常贵的气体涡轮。
专利US-6,449,982描述了一种仅使部分处理的气体液化的方法。因此降低了用于液化的能量。然而，该方法的缺陷在于使用过量的气体，因此，液化位置往往远离使用地点。
专利US-6,248,794描述了Fisher-Tropsch过程与天然气液化方法的各种综合。具体地，提出将来自Fisher-Tropsch过程的残余气体用于操作冷冻压缩机的气体涡轮，或使用蒸气涡轮来操作冷冻压缩机，蒸气产生于Fisher-Tropsch单元。
本发明提供一种方法，该方法提出综合低温液化法和Fisher-Tropsch过程，能最好地提高来自油井的所有的天然气质量。
发明概述
一般而言，本发明涉及天然气液化和转化方法，该方法中进行下面步骤：
a)冷却，然后蒸馏天然气，以获得洗涤过的天然气和天然气液体，
b)至少部分液化洗涤的天然气，
c)使步骤b)获得的部分液化的天然气至少一部分膨胀，以获得气体部分和液体部分，
d)压缩步骤c)获得的气体部分的一部分，
e)膨胀，然后蒸馏步骤a)获得的天然气液体，
f)通过Fisher-Tropsch过程，将在步骤d)获得的压缩气体以及来自步骤e)蒸馏的蒸气，转化为每分子包含至少5个碳原子的产物。
根据本发明，可进行下列步骤：
g)至少部分液化步骤a)获得的洗涤的天然气，以获得气相和液相，该气相第一部分通过Fisher-Tropsch过程转化，该气相第二部分形成步骤a)的天然气。
根据本发明，在步骤b)中，天然气通过与步骤c)获得的气体部分热交换被冷却。步骤b)中，也能通过使用压缩机与回路中循环的冷却剂热交换来冷却天然气。压缩机可由电动机电运转，而由蒸气涡轮操作的发电机提供，Fisher-Tropsch过程产生蒸气。
根据本发明，可进行下列步骤：
h)膨胀步骤c)获得的液体部分，以获得第二气体部分和第二液体部分，
i)步骤c)获得的液体部分通过与用步骤h)获得的第二气体部分热交换而冷却。
根据本发明：
-天然气可处于2-15MPa压力范围，
-在步骤c)中，膨胀可在高至0.1-1MPa绝对压力范围下进行，
-在步骤d)中，压缩可在高至0.5-5MPa绝对压力范围下进行。
一般，天然气在工艺进口的压力高于通过Fisher-Tropsch过程转化的气体的压力。根据本发明，这一压力差能有利地用于通过膨胀冷却天然气。
附图简述
由下面说明书，并参见附图，可理解本发明的其他特征和优点。
图1为本发明方法示意图。
图2、3和4所示为本发明方法的各种变化形式。
详细描述
图1中，通过管道1流动的天然气在热交换器E中冷却。管道R将冷却剂带入交换器E。天然气从交换器E流出，通过管道2部分或全部液化，然后送入膨胀装置T1。膨胀装置T1可以是一个阀，涡轮或涡轮和阀的组合。由装置T1进行的膨胀可进行至充分低压力，例如0.1-1MPa绝对压力范围，使膨胀后的天然气包括气体部分和液体部分。较好地，天然气膨胀至接近大气压的压力。
将来自膨胀装置T1的天然气送入分离装置D2，例如分离罐。分离装置D2可以使气体部分与液体部分分离。
来自分离装置D2的液体部分形成液化天然气，将其通过管道3送入低温储存处。
来自分离装置D2的蒸气部分通过管道4送入压缩机K1，将该部分压缩至足够压力，例如0.5-5MPa范围，供给采用Fisher-Tropsch过程的FT单元。管道5将压缩后的蒸气部分送入单元FT。
Fisher-Tropsch过程首先在30年代在德国使用，自50年代以来，已在南非工业化应用。这种方法看来是最有前景的，特别对提高远离使用地点的地方生产的天然气的质量。然而，该过程是高度放热，且在有限的温度范围内操作。通常的做法是通过产生大量蒸气从反应器放出热量，在往往远离天然气生产的地点是不易利用这些热量。
本说明书中，术语FT或Fisher-Tropsch过程指在大气压和环境温度下从天然气生产液态烃的步骤。本领域技术人员都了解这些步骤。第一步骤是在水存在下于高温转化甲烷，产生由一氧化碳和氢组成的合成气。第二步骤使用合适的催化剂，以从第一步骤获得的合成气制备长链烃。该第二步骤一般称作Fisher-Tropsch合成或Fisher-Tropsch反应。
Fisher-Tropsch过程特别在下列文献中述及：US-6,596,667和US-6,348,510。
图2中，通过管道1流动的天然气在热交换器E1和E2中由第一和第二冷却混合物冷却。
第一冷却混合物较好地由丙烷和乙烷组成，由压缩机K10压缩，然后在热交换器C10中冷凝。然后，该第一混合物在热交换器E1中过冷，膨胀至三个不同压力水平，之后通过热交换器E1完全蒸发。最后，将第一冷却混合物送回到压缩机K10。
第二冷却混合物较好地包括甲烷和乙烷，由压缩机K20压缩，由热交换器C20冷却，在热交换器E1中冷凝，在热交换器E2中过冷，在膨胀机T3(阀和/或涡轮)中膨胀。然后，第二冷却混合物通过热交换器E2蒸发，再送回到压缩机K20。
部分或全部液化的天然气通过管道2离开热交换器E2，然后送入膨胀装置T1。膨胀天然气以产生液体部分和气体部分。液体部分和气体部分在分离器D2中分离。
来自罐D2的气体部分通过管道111可用作热交换器E1和/或E2的冷却剂，然后通过管道4送入压缩机K1进行压缩。
来自罐D2的液态部分通过管道3在热交换器E3中冷却，然后通过膨胀装置T2膨胀，产生气体部分和液体部分。该气体部分和液体部分在分离器D3中分离。
通过管道5排出的液体部分形成液化天然气。
从分离器D3排出的气体部分用作热交换器E3中的冷却剂，然后通过管道6送入压缩机K1进行压缩。
来自压缩机K1的压缩天然气通过管道7送入采用Fisher-Tropsch过程的单元FT。
结合图3描述的方法提出，通过洗涤天然气并回收天然气液体来进行本发明。
图3中，通过管道1流动的天然气在热交换器E1中较好冷却至0℃至-50℃范围。热交换器E1通过冷却回路R1冷却。
将冷却的气体通过管道2送入蒸馏塔C1底部。比气体更冷的液体通过管道13送到塔C1的顶部，以冷凝天然气所含的重化合物。这些冷凝物通过管道14从塔C1底部排出。
洗涤的天然气(即至少部分无重组分)通过管道3从塔C1顶部排出，然后送入热交换器E1被再次冷却。天然气通过管道4从热交换器E1排出，部分冷凝。
部分冷凝的天然气通过管道4送入分离器D1，分离液体部分和气体部分。
来自分离器D1底部的液体部分通过泵P1用管道13送到塔C1的顶部。
来自D1的气体部分通过管道5送到热交换器E2，进行冷凝。热交换器E2由冷却回路R2冷却。
天然气通过管道10流出热交换器E2，至少部分液化，较好完全液化。天然气通过管道10被带到膨胀装置T1，以进行膨胀，产生气体部分和液体部分。膨胀后，液体和气体部分送到分离罐D2，D2的压力较好接近大气压。
罐D2底部的液体部分形成液化天然气，并可通过管道11送到低温储存处。
罐D2顶部的气体部分通过管道12送到压缩机K1。压缩的气体部分通过管道15从压缩机K1排出。
通过管道14在蒸馏塔C1底部获得的冷凝物通过阀V10膨胀，然后送入蒸馏塔C2进行稳定。热交换器E3可在塔C2底部提供热量。
主要包含丙烷和丁烷的天然气液体通过管道18从塔C2底部排出。
主要包含甲烷的再蒸发天然气通过管道19从塔C2顶部排出。
在管道15和19中循环的气体送到采用Fisher-Tropsch过程的单元FT。
天然气冷却期间，一般分离出天然气中所含的重组分，特别是包含丙烷和丁烷的LPG，以及包含5个以上碳原子(C5+)烃的部分。这些部分分开精练。在结合图4描述的方法中给出这样的流程，并由一些实施例加以说明。
压力为5.5MPa，温度为30℃的天然气通过管道1送入热交换器E1。天然气的组成按照摩尔％计如下：
氮                0.2％
甲烷              85％
乙烷              7％
丙烷              4％
异丁烷            2％
正丁烷            1％
C5+               0.8％
天然气在热交换器E1中冷却至-25℃。然后，通过管道2送到蒸馏塔C1底部。天然气在塔C1中，重化合物被通过管道13送入塔C1顶部的-50℃的液体吸收。在塔C1底部获得的液体通过管道14送到阀V10进行膨胀，然后到冷凝物稳定塔C2。
从塔C1顶部通过管道3流动的洗涤后气体送入热交换器E1，被冷却到-50℃。在此温度，气体被部分液化。该气-液混合物通过管道4送入罐D1，液体和气体部分分离。在罐D1底部获得的液体分成两部分。
一部分液体通过泵P1和管道13送入塔C1，洗涤在管道2流动的天然气。另一部分液体通过管道30排出，通过阀V1膨胀，然后送入冷凝物稳定塔C2。
在罐D1顶部获得的气体部分包含93％甲烷，5.2％乙烷和小于1.7％的丙烷以及重于丙烷的产物。该气体分成两部分。第一部分气体经管道5送到热交换器E2进行冷却和液化。在热交换器E2出口获得的液化天然气通过管道10送入膨胀涡轮T1，然后送入压力接近大气压的罐D2。在罐D2底部收集的液体部分形成液化天然气，可通过管道11送到储存处。在罐D2顶部获得的气体部分通过管道21送入压缩机K1。压缩后的气体通过管道22排出。
来自罐D1气体的第二部分通过管道15送入涡轮T2，膨胀至2.71MPa压力。膨胀过程中形成液体部分。在涡轮T2出口获得的混合物通过管道16送入罐D3，分离液体和气体部分。在罐D3底部获得的液体部分用泵P2和管道17送入塔C2。
热交换器E3使塔C2底部的液相再沸，并蒸发塔C2内的甲烷。在塔C2底部，天然气液体通过管道24排出。该天然气液体由28.4摩尔％乙烷，33.1摩尔％丙烷，29.8摩尔％丁烷，8.4摩尔％戊烷和重化合物组成。
在塔C2顶部收集的蒸气通过管道19与通过管道18来自罐D3的气体部分混合。该气体混合物的温度为-77℃，压力为2.7MPa。它在热交换器E2中加热，然后在E1中加热至25℃。随后通过管道20送入压缩机K2，该压缩机由膨胀涡轮T2回收的能量运行。来自压缩机K2的压缩气体与通过管道22来自压缩机K1的气体混合。该气体混合物通过管道23送入采用Fisher-Tropsch过程的单元FT。
天然气在热交换器E1和E2中一方面由通过管道18和19流动的冷气体冷却，另一方面由回路R1和R2冷却，这两个回路分别冷却热交换器E1和E2。
根据结合图4描述的方法，天然气在管道1的流速为27000Kmol/h，液化气体通过管道11排出的流速为11930Kmol/h，送入单元FT的气体的流速为12525Kmol/h，通过管道24排出的天然气液体的流速为2545Kmol/h。两个冷却回路R1和R2所需功率为49.93MW。压缩机K1功率为6.5MW。高总功率对应于由处理12525Kmol/h流速气体的单元FT产生的汽化水形式的可得到的功率。因此，两个冷却回路R1和R2以及压缩机K1所需能量来自于单元FT。因此，根据本发明，无需外部提供能量，或仅提供很少能量，就能产生1.8百万吨液体天然气和1百万吨天然气液体。
根据本发明，需处理的第一部分天然气通过冷却液化，第二部分通过Fisher-Tropsch过程液化。第一部分的组成不同于第二部分：在本发明方法期间，第一部分富含重化合物，主要是重于甲烷的烃类，而第二部分富含轻化合物，主要是甲烷和氮。
例如，结合图1，通过管道3排出的液体部分主要包含重于甲烷的烃类，而通过管道5排出的气体部分主要包含甲烷和氮。
结合图2，通过管道5排出的液体部分主要包含重于甲烷的烃类，而通过管道7排出的气体部分主要包含甲烷和氮。
结合图3，通过管道11排出的液体部分主要包含甲烷和乙烷，通过管道18排出的液体部分主要包含丙烷和丁烷，而通过管道15和19排出的气体部分主要包含甲烷和氮。
结合图4，通过管道11排出的液体部分主要包含甲烷和乙烷，通过管道24排出的液体部分主要包含丙烷和丁烷，而通过管道20和22排出的气体部分主要包含甲烷和氮。
有利的事实是，气体第二部分通过Fisher-Tropsch过程液化，富含轻组分如甲烷和氮。实际上，通过冷却液化的天然气中存在的氮必须受到严格限制，但是存在适量的氮不阻碍Fisher-Tropsch转化过程。而且，第一部分气体富含重化合物事实给冷却液化的天然气比主要包含甲烷的液化天然气高的卡路里值。
一般，进行Fisher-Tropsch过程的压力低于操作液化单元操作的压力。该压力差得益于本发明方法，例如，在结合图4所述的方法，通过涡轮膨胀部分液化天然气。这样的设计允许在轻组分如甲烷和氮与重组分间的连续分离。
膨胀和蒸发后，图1冷却回路R中循环的冷却剂，图3和4的冷却回路R1和R2中循环冷却的冷却剂被压缩。同样，在结合图2所述方法中所用的第一和第二冷却剂在膨胀和蒸发后通过压缩机K10和K20压缩。
有利的是，根据本发明，冷却剂再压缩所需的能量至少部分来自于Fisher-Tropsch过程。事实上，该过程是一放热过程，反应期间产生的热量可用于产生蒸气。
由此产生的蒸气在涡轮中膨胀，涡轮驱动用于压缩冷却剂的压缩机。
蒸气还可以在驱动交流发电机的涡轮内膨胀。由此产生的电能可用于向压缩冷却剂用的压缩机提供动力的电动机供电。
尽管以具体实施例描述了本发明，但应理解，本发明不限于这些实施例，在不偏离本发明范围下可以进行修改或变动。

Claims (8)

1.一种天然气液化和转化方法，其特征在于，进行下列步骤：
a)冷却，然后蒸馏天然气，以获得洗涤过的天然气和天然气液体，
b)至少部分液化洗涤的天然气，
c)使步骤b)获得的部分液化的天然气至少一部分膨胀，以获得气体部分和液体部分，
d)压缩步骤c)获得的气体部分的一部分，
e)膨胀，然后蒸馏步骤a)获得的天然气液体，
f)通过Fisher-Tropsch过程，将在步骤d)获得的压缩气体以及来自步骤e)蒸馏的蒸气，转化为每分子包含至少5个碳原子的产物。
2.如权利要求1所述的方法，其特征在于，还进行下列步骤：
g)至少部分液化步骤a)获得的洗涤的天然气，以获得气相和液相，该气相第一部分通过Fisher-Tropseh过程转化，该气相第二部分形成步骤a)的天然气。
3.如权利要求1或2所述的方法，其特征在于，在步骤b)，天然气通过与步骤c)获得的气体部分热交换被冷却。
4.如前述权利要求中任一项所述的方法，其特征在于，在步骤b)，天然气通过使用压缩机与回路中循环的冷却剂热交换被冷却。
5.如权利要求4所述的方法，其特征在于，所述压缩机由蒸气涡轮运转，由Fisher-Tropsch过程产生蒸气。
6.如权利要求4所述的方法，其特征在于，所述压缩机由电动机运转，而电由蒸气涡轮运转的发电机提供，由Fisher-Tropsch过程产生蒸气。
7.如前述权利要求中任一项所述的方法，其特征在于，还进行下列步骤：
h)膨胀步骤c)获得的液体部分，以获得第二气体部分和第二液体部分，
i)步骤c)获得的液体部分通过与步骤h)获得的第二气体部分热交换而冷却。
8.如前述权利要求中任一项所述的方法，其特征在于，
-天然气可处于2-15MPa压力范围，
-在步骤c)中，膨胀可在高至0.1-1MPa绝对压力范围下进行，
-在步骤d)中，压缩可在高至0.5-5MPa绝对压力范围下进行。
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