CN114874821A - 脱碳lng生产的方法和系统 - Google Patents

脱碳lng生产的方法和系统 Download PDF

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Publication number
CN114874821A
CN114874821A CN202210106606.8A CN202210106606A CN114874821A CN 114874821 A CN114874821 A CN 114874821A CN 202210106606 A CN202210106606 A CN 202210106606A CN 114874821 A CN114874821 A CN 114874821A
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stream
natural gas
hydrogen
power
power generation
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Inventor
A·O·韦斯特
J·D·伯德
D·R·格拉厄姆
J·E·帕拉马拉
M·J·罗伯茨
D·维斯科维奇
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Air Products and Chemicals Inc
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Air Products and Chemicals Inc
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Publication of CN114874821A publication Critical patent/CN114874821A/zh
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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
    • 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
    • F25J1/0229—Integration with a unit for using hydrocarbons, e.g. consuming hydrocarbons as feed stock
    • F25J1/023—Integration with a unit for using hydrocarbons, e.g. consuming hydrocarbons as feed stock for the combustion as fuels, i.e. integration with the fuel gas system
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/12—Liquefied petroleum gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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Abstract

一种集成天然气液化系统、氢生产系统和功率生成系统，以提高CO2捕获和改善整体工厂效率。主要是甲烷的端部闪蒸被送到氢生产系统，该氢生产系统产生氢气和CO2。CO2可以被捕获或有益地使用。所产生的氢气中的至少一部分用于在功率生成中为燃气轮机提供燃料，而该功率生成又以机械功或电力的形式为天然气液化系统的制冷压缩机提供功率。

Description

脱碳LNG生产的方法和系统
背景技术
减少二氧化碳(“CO2”)排放正成为工业过程日益需要的改进，包含烃加工和电功率生成领域。
天然气的液化是具有较高功率要求(主要对驱动支持液化过程所必需的压缩机)的过程。已经努力通过提高液化过程的效率来减少CO2排放，来减少天然气液化的碳“足迹”。对于使用燃气轮机驱动制冷剂压缩机的天然气液化厂(在此也称为“LNG厂”)，通过从高温烟气中回收热量并有益地使用它，可以实现通过效率提高进行的CO2排放方面的进一步减少。这些热量可以通过生成蒸汽和使用组合循环来生成更多的功率来回收。一些LNG厂通过来自电网的电力获得制冷压缩功率。提供电力的发电厂可以采用带有热量回收蒸汽生成系统的燃气轮机，以获得附加功率和效率。
一些发电厂通过使用氢气作为燃气或燃气添加剂来减少CO2排放。如果这种氢气使用诸如太阳能的绿色能量制造，或者利用包含天然气进料和CO2捕获的过程制造，那么总的CO2排放量被降低。用于将天然气转化为氢气的这种过程包含蒸汽甲烷重整过程，其中从合成气和/或烟气中去除CO2。可选地，这种低碳密度的氢气可以通过自热重整或部分氧化过程或气化过程来制备，其中从流出的合成气中去除CO2。
这种改进通常导致相当高的能量成本，并且需要天然气液化过程外部的能源。因此，需要一种减少归因于天然气液化过程的CO2排放和驱动该过程所需的功率的更有效和独立的方法。
发明内容
提供发明内容是为了以简化的形式介绍将在下面的具体实施方式中进一步描述的一些概念。本发明内容不旨在标识所要求保护的主题的关键特征或必要特征，也不旨在用以限制所要求保护的主题的范围。
系统和方法的几个方面概述如下。
方面1-一种方法，包括：
(a)在天然气液化系统中至少部分地液化天然气进料流以形成LNG流，该天然气液化系统包含至少一个压缩机；
(b)将LNG流分离成闪蒸蒸气流和LNG产物流；
(c)将闪蒸蒸气流中的至少一部分通入氢生产系统；
(d)使闪蒸蒸气流中的至少一部分在氢生产系统中反应，以形成含氢流和第一富CO2流；
(e)使用含氢流中的至少一部分在功率生成系统中生成功率；以及
(f)利用在步骤(e)中生成的功率中的至少一部分向至少一个压缩机提供功率。
方面2-根据方面1的方法，其中闪蒸蒸气流是至少50mol％的甲烷。
方面3-根据方面1至2中任一项的方法，其中含氢流是至少80mol％的氢气。
方面4-根据方面1至3中任一项的方法，还包括：
(g)在执行步骤(a)之前，从天然气进料流中分离第二富CO2流；以及
(h)将第一富CO2流和第二富CO2流组合以形成组合的CO2流。
方面5-根据方面4的方法，还包括：
(i)使用来自天然气液化系统的制冷负荷，液化选自第一富CO2流、第二富CO2流和组合的富CO2流组中一者的至少一部分。
方面6-根据方面1至5中任一项的方法，其中步骤(d)还包括使闪蒸蒸气流中的至少一部分和环境空气流在氢生产系统中反应，以形成含氢流和第一富CO2流。
方面7-根据方面1至6中任一项的方法，其中步骤(d)还包括使闪蒸蒸气流中的至少一部分和含氧流在氢生产系统中反应，以形成含氢流、第一富CO2流、第一蒸汽流和废氮流。
方面8-根据方面7的方法，其中含氧流是环境空气。
方面9-根据方面7的方法，还包括：
(j)使环境空气流通过空气分离单元以产生含氧流和富氮流。
方面10-根据方面9的方法，其中步骤(e)还包括使用含氢流和富氮流中的至少一部分在功率生成系统中生成功率。
方面11-根据方面1至10中任一项的方法，其中步骤(e)还包括使用来自氢生产系统或功率生成系统的含氢流和至少一种蒸汽流在功率生成系统中生成功率。
方面12-根据方面1至11中任一项的方法，其中步骤(e)还包括使用含氢流驱动至少一个燃气轮机和使用第一蒸汽流驱动至少一个蒸汽轮机来在功率生成系统中生成功率。
方面13-根据方面1至12中任一项的方法，其中在步骤(e)中生成的功率包括电功率，并且步骤(f)包括向附接到至少一个压缩机的至少一个电机提供电功率中的至少一部分。
方面14-根据方面1至13中任一项的方法，其中在步骤(e)中生成的功率包括电功率，并且步骤(f)包括向氢生产系统和天然气液化系统中的至少一个提供电功率的至少一部分。
方面15-根据方面1至14中任一项的方法，其中在步骤(e)中生成的功率包括电功率，并且该方法还包括：
(k)将电功率中的至少一部分输出到天然气液化系统、氢生产系统和功率生成系统外部的过程。
方面16-根据方面1至15中任一项的方法，其中步骤(e)还包括使用含氢流和至少一种含甲烷流在功率生成系统中生成功率。
方面17-根据方面16的方法，其中至少一种含甲烷流包括选自天然气进料流和闪蒸蒸气流组中的至少一种。
方面18-根据方面1至17中任一项的方法，还包括：
(l)将步骤(d)中产生的含氢流中的至少一部分输出到天然气液化系统、氢生产系统和功率生成系统外部的用途。
方面19-根据方面1至18中任一项的方法，其中步骤(f)包括通过将功率生成系统的至少一个燃气轮机机械耦接到天然气液化系统的至少一个压缩机来驱动至少一个压缩机。
方面20-根据方面1至19中任一项的方法，还包括：
(m)使用来自天然气生产系统的制冷来冷却氢生产系统。
方面21-根据方面1至20中任一项的方法，还包括：
(n)使用从氢生产系统和功率生成系统中的至少一个生成的热量为干燥器单元提供热负荷，干燥器单元适于从用于天然气液化系统的天然气进料流中分离水分。
方面22-根据方面1至21中任一项的方法，还包括：
(o)将天然气进料流分成第一部分和第二部分，对天然气进料流中的第一部分进行步骤(a)，并在进行步骤(d)之前将天然气进料流的第二部分与闪蒸蒸气流组合。
方面23-根据方面1至22中任一项的方法，其中步骤(a)包括在天然气液化系统中至少部分地液化天然气进料流以形成LNG流，天然气液化系统包含具有至少一个压缩机的闭环制冷系统。
方面24-一种改造现有天然气液化系统的方法，该天然气液化系统在进料温度下至少部分地液化天然气进料流，以在产物温度下形成LNG产物，该天然气液化系统包括至少一个压缩机，该方法包括：
(a)添加氢生产系统，该氢生产系统使由天然气液化系统产生的端部闪蒸中的至少一部分反应以形成含氢流；
(b)使用含氢流在功率生成系统中生成功率；以及
(c)利用在步骤(b)中生成的功率中的至少一部分向至少一个压缩机提供功率。
方面25-根据方面24的方法，还包括：
(d)降低进料温度和产物温度之间的差异，从而每立方英尺所处理的天然气产生比改造前产生的更多的端部闪蒸。
方面26-根据方面24至25中任一项的方法，还包括：
(e)添加功率生成系统。
方面27-根据方面24至26中任一项的方法，其中功率生成系统适于在改造之前向天然气液化系统提供功率，该方法还包括：
(f)修改功率生成系统中的至少一个现有燃气轮机以由含氢流提供燃料。
方面28-根据方面27的方法，还包括：
(g)相比于改造前，在改造后利用至少一个现有燃气轮机生成更多的功率。
方面29-根据方面24至28中任一项的方法，还包括：
(h)在改造后产生进入LNG储罐的第二质量流率的LNG产物，该第二质量流率不低于改造前产生的进入LNG储罐的LNG产物的第一质量流率。
方面30-根据方面24至29中任一项的方法，还包括：
(i)使用氢生产系统分离端部闪蒸中包含的至少80％的二氧化碳。
附图说明
下文将结合附图描述本发明，其中相同的附图标记表示相同的元件。
图1是示出互连的天然气液化系统、氢生产系统和功率生成系统的第一示例性实施例的框图；
图2是更详细地示出图1的天然气液化系统的框图；
图3是更详细地示出图1的氢生产系统的框图；
图4是更详细地示出图1的功率生成系统的框图；
图5是示出图1的天然气液化系统的第一替代实施例的框图；
图6是示出图1的功率生成系统的第一替代实施例的框图；
图7是示出图1至图4中示出的示例性实施例的多个流位置处的流体成分和物理参数的表格；以及
图8是图7中示出的表格的延续。
具体实施方式
随后的详细描述提供了优选示例性实施例，并且不旨在限制本发明的范围、适用性或构型。相反，随后对优选示例性实施例的详细描述将为本领域技术人员提供用于实施本发明的优选示例性实施例的使能描述。应当理解，在不脱离本发明的精神和范围的情况下，可以在元件的功能和布置方面进行各种改变。相反，可以在不脱离本发明的精神和范围的前提下在元件的功能和设置方面做出各种改变。
为了帮助描述本发明，说明书和权利要求书中可以使用方向术语来描述本发明的各部分(例如，上、下、左、右等)。这些方向性术语仅仅是旨在帮助描述和要求保护本发明，而不是旨在以任何方式限制本发明。说明书中结合附图引入的附图标记可以在一个或多个后续附图中重复，而在说明书中没有额外的描述，以便为其他特征提供上下文。
说明书和权利要求书中使用的术语“导管”是指流体可以通过其在系统的两个或更多个部件之间输送的一个或多个结构。例如，导管可包含输送液体、蒸气和/或气体的管道、通道、通路及其组合。
如说明书和权利要求书中所使用的，术语“流动连通”旨在表示两个或更多个元件以使流体能够在元件之间流动的方式连接(直接或间接)，包含可以含有阀、门、三通或可以选择性地限制、合并或分离流体流量的其他设备的连接。
说明书和权利要求书中使用的术语“天然气”是指主要由甲烷组成的烃气体混合物。
说明书和权利要求书中使用的术语“烃”、“烃气体”或“烃流体”是指包括至少一种烃并且对于其烃包括气体/流体总组成的至少80％，更优选地至少90％的气体/流体。
如说明书和权利要求书中所使用的，术语“高-高”、“高”、“中”、“低”和“低-低”旨在表达与这些术语一起使用的元件的性质的相对值。例如，高-高压流旨在指示比本申请中描述或要求保护的相对应的高压流或中压流或低压流具有更高压力的流。类似地，高压流旨在指示具有高于说明书或权利要求书中描述的相对应的中压流或低压流，但低于本申请中描述或要求保护的相对应的高-高压流的压力的流。类似地，中压流旨在指示具有高于说明书或权利要求书中描述的相对应的低压流，但低于本申请中描述或要求保护的相对应的高压流的压力的流。
除非本文中另有说明，否则说明书、附图和权利要求书中标识的任何和所有百分比应理解为基于质量百分比。除非本文中另有说明，否则说明书、附图和权利要求书中标识的任何和所有压力应理解为表压。
如说明书和权利要求书中所使用的，术语“压缩系统”被定义为一个或多个压缩级。例如，压缩系统可以包括单个压缩机内的多个压缩级。在替代性示例中，压缩系统可以包括多个压缩机。
除非本文中另有说明，否则在某一位置引入流旨在是指在该位置引入基本上所有的所述流。说明书中讨论的和附图中示出的所有流(通常由带有箭头的线表示，该箭头示出正常操作期间流体流量的总体方向)应该理解为包含在相对应的导管中。每个导管应该理解为具有至少一个入口和至少一个出口。进一步，每件装备应理解为具有至少一个入口和至少一个出口。
在权利要求书中，字母用于标识要求保护的步骤(例如，(a)、(b)和(c))。这些字母用于帮助指代方法步骤，并且不旨在指示其中执行所要求保护的步骤的顺序，除非并且仅在权利要求书中具体陈述了这种顺序。
本文描述的所有示例性实施例的关键特征包含具有一个或多个制冷压缩机的LNG液化器，该LNG液化器从天然气进料产生LNG和端部闪蒸汽体，端部闪蒸汽体(主要是甲烷)被送到产生氢气和二氧化碳的氢生产系统。CO2可以被捕获或有益地使用。例如，CO2可以被压缩、液化、在另一过程中使用、在LNG厂的预冷部分中液化或者通过其他方式处理。在这些步骤之后，CO2可以用于增强石油采收率、被储存、封存、出售、用于另一过程或用于另一目的。可选地，可以通过酸性气体去除单元从天然气进料中提取CO2，并将其与来自氢生产的CO2流出流组合。所产生的氢气中的至少一部分然后被送到功率生成系统中的燃气轮机，该功率生成系统通过将(多个)燃气轮机机械耦接到压缩机上直接地或者通过由耦接到(多个)燃气轮机的发电机生成电力(该电力由耦接到压缩机上的电动机消耗)间接地为(多个)制冷压缩机提供功率。
应该注意的是，即使本文公开的示例性天然气液化系统实施例全部具有闭环制冷，但本文公开的发明构思同等地适用于使用开环或闭环压缩的天然气液化系统。
向氢生产系统进给主要是来自天然气液化系统的甲烷的端部闪蒸具有几个优点。天然气液化系统的效率得到提高，因为制冷剂不必将LNG冷却到如此低的温度。例如，假设相同的燃气轮机制冷压缩机驱动器，端部闪蒸燃料需求增加10-20％，从而导致主低温热交换器的出口温度方面的2-4℉的增加。这导致制冷压缩机功率需求方面的1-2％的下降。此外，更多的LNG由相同大小的制冷系统生产，或者替代性地对于相同的生产能力，制冷系统中包含压缩机、热交换器和管道的装备的尺寸更小。最后，该系统可以从较高的氮进料气生产具有可接受的氮含量的LNG，因为进料氮将集中在端部闪蒸汽体中，因此降低了LNG的氮含量。此外，甲烷端部闪蒸相对没有杂质，这减少了对用于氢生产系统的甲烷进料气体的纯化步骤的需要。
描述了三个系统之间的其他另外的集成选择，包含使用来自天然气液化系统的制冷来降低与氢生产系统相关联的空气分离单元的功率需求或成本，以及使用来自功率生成系统的蒸汽用于天然气液化系统中的过程加热。
图1示出了三个系统的互连：天然气液化系统103、氢生产系统118和功率生成系统124。天然气进料流100可以被分成被送至氢生产系统的可选流101和被送至天然气液化系统103的流102。天然气液化系统103产生含CO2流106和高压LNG流104。高压LNG流104然后在减压设备108中闪蒸至较低压力，该减压设备可以是阀或作功涡轮机。所得到的两相流110在相分离器142中分离，以形成蒸气流111和LNG流112。在这个实施例中，相分离器142是罐。替代性地，可以使用多级蒸馏塔，特别是在需要氮分离的情况下。由热流125表示的呈蒸汽的形式的热量也优选由功率生成系统124提供给天然气液化系统103。可选地，来自天然气液化系统103的制冷可以用于向氢生产系统118提供冷却，如热流117所示。
在压缩和热交换步骤(标记为113)之后，主要为甲烷的闪蒸蒸气流114被送到氢生产系统118，这将在图2的描述中更全面地描述。
氢生产系统118使用环境空气流116和闪蒸蒸气流114来生产氢气流122和中压蒸汽流138，它们两者与废氮气流144、可选的氢产物流134(其可以被送到管道)和CO2流120一起被送到功率生成系统124，该二氧化碳流与来自天然气液化系统103的含CO2流106组合，然后被压缩(通过压缩机130)并通过经压缩的CO2流132被送到管道或封存在地下储存装置中。在其他实施例中，氢生产系统118可以被配置为仅产生氢气流122，而不产生任何蒸汽流。该过程可以包含排出蒸汽(未示出)，其可以包含来自燃烧加热器、蒸汽排出口和废水蒸汽的排气。
功率生成系统124使用来自氢气系统118的氢气流122和中压蒸汽流138来产生电功率128，用于在整个设施和天然气液化系统103中使用(由线126表示)。可选地，电功率可以通过线136输出到电网。经由线126从天然气液化系统103发送的功率可以采取被发送到附接到压缩机的电机的电力的形式或者通过将功率生成系统124中的燃气轮机机械耦接到天然气液化系统103的制冷压缩机。
图2是图1的天然气液化系统103的更详细的描述，该天然气液化系统在图2中标记为203。在这个示例性实施例中，天然气液化系统203包括两个相同的链，使得每个链中的材料和能量流率是整个系统中总量的一半。在这个示例性实施例中，酸性气体去除单元246设置在预冷系统250的上游。酸性气体去除单元246可以是本领域已知的任何酸性气体去除系统，诸如基于胺的吸收系统。天然气进料流202进入酸性气体去除单元246，该酸性气体去除单元使用呈从功率生成系统提供的蒸汽(由线225表示)的形式的热量来操作基于胺的去除单元的再沸器，来从天然气中分离含CO2流206。离开酸性气体去除单元246的流247被送到干燥器单元248以便进行水分去除，以形成预处理的气体流252。
天然气液化系统203可以使用用于天然气液化的任何已知过程。在这个实施例中，使用丙烷预冷的混合制冷剂过程。将不详细描述该过程，因为它是本领域公知的。预处理的进料气体流252被预冷系统250冷却至约-30摄氏度，随后在主热交换器251中进一步冷却至-140至-150摄氏度，作为流204离开。高压LNG流204然后在减压设备208中闪蒸至1-3巴(绝压)的较低压力，该减压设备可以是阀或作功涡轮机。流256(其通常少于离开预冷系统250的天然气流253的20％)然后在闪蒸交换器258中进一步冷却，同时对闪蒸汽流211进行加温。所得到的两相流210在242中分离，以形成蒸气流211和LNG流212。在压缩机260中被压缩至优选的约40至60巴(绝压)(更优选地约40至50巴(绝压))以形成流214之前，蒸气流211在闪蒸交换器中被加温至约-40至-30摄氏度。蒸气流214可以可选地包含来自LNG储罐(未示出)的附加的含甲烷气体。液化过程的能量主要由三个制冷压缩机262、264和266提供。压缩机262和264在预冷系统250中预冷之前压缩气化的低压混合制冷剂。压缩机266在气化的丙烷在环境冷却器268中冷凝并返回到丙烷系统之前对其进行压缩。在这个实施例中，用于压缩机262、264、266的功率是通过将压缩机262、264、266机械耦接到位于图4的功率生成系统中的两个相同的燃气轮机驱动器来提供的，其中这个机械功输入由工作流226a和226b表示。第一级MR压缩262表示总制冷功率需求的50％，同时第二级MR压缩264表示总制冷功率需求的20％，以及丙烷压缩机消耗总制冷功率需求的大约30％。
在所示的布置中，压缩机264和266连接到由机械工作流226a提供动力的同一轴，而压缩机262由机械工作流226b提供动力，从而允许充分利用由位于图4的功率生成系统中的两个相等的燃气轮机驱动器提供的机械功率。利用来自两个相等的燃气轮机驱动器(未示出)的功率的另一选择是将丙烷和混合的制冷剂流分成两半，从而在并联的压缩机中压缩制冷剂。在这种布置中，工作流226a和226b将为具有各自机械地耦接在两个压缩机轴上的三个压缩机的相同压缩管柱提供动力。
图3是图1的氢生产系统118的示例的更详细的描述。在这个图中，所有元件被格式化为3XX。在图3中具有带有与图1中示出的项编号相同的最后两位数字XX的附图标记的元件旨在表示与图1相同的元件。
环境空气流316在压缩机346中被压缩，然后在环境冷却器374中被冷却。可选地，压缩空气流可以使用来自天然气液化系统203的制冷(由流317表示，其对应于图2的能量流217)进一步冷却，以形成冷却的干燥压缩空气流376。这种冷却可以提高氢生产系统318的效率，同时减小基于吸附的干燥器系统375的大小，而无需添加分离的制冷器。这种冷却的形式可以是通过与LNG制冷剂(由流317表示)的间接热交换，或者通过中间流体(诸如乙二醇)。
冷却的干燥压缩空气流376被进给到低温空气分离单元(ASU)348。可以使用其他类型的空气分离技术(诸如吸附或膜)来代替ASU 348。ASU 348产生优选地具有大于约95摩尔％O2的富氧流350和氮流344。来自ASU 348的其他可选产物流包含气态氩、液态氩、液态氧和液态氮。ASU和LNG厂之间的进一步集成可以包含将压缩空气中的一部分送到主热交换器251以被液化。这种集成可以消除ASU膨胀机，从而降低CAPEX。
氧气流350主要与甲烷流314和蒸汽流354混合，并且然后送到自热重整器(ATR)352。在大多数应用中，蒸汽流354在被引入ATR 352之前会被预热。ATR 352中的反应包含重整反应(其中甲烷和水形成一氧化碳和氢气(1))、变换反应(其中一氧化碳与水反应形成氢气(2))以及涉及甲烷、一氧化碳和氢气的部分氧化反应(3-5)：
CH4+H2O→CO+3H2 (1)
CO+H2O→CO2+H2 (2)
2CH4+O2→2CO+4H2 (3)
CO+1/2O2→CO2 (4)
H2+1/2O2→H2O (5)
此外，这些反应的各种组合也是可能的。
来自ATR 352的热流出物然后在蒸汽发生器356中冷却，该蒸汽发生器气化来自功率生成系统124的再循环的水流340(图4中标记为440)和水进料流319(图1中也标记为流119)。水在其进入锅炉(未示出)之前被处理和预热。在进料流358然后被送到变换反应器360之前，可以添加附加蒸汽，在该变换反应器中一氧化碳和水反应形成二氧化碳和氢气：
CO+H2O→CO2+H2 (6)
此外，这些反应的各种组合也是可能的。例如，变换反应器可以由级之间具有冷却的两级变换组成。
含氢流362然后被冷却(364)并被送到二氧化碳去除单元366，该二氧化碳去除单元从氢产物中去除二氧化碳流320。单元366可以是吸附系统，例如基于胺的二氧化碳去除单元或去除二氧化碳的替代装置，诸如吸附系统、膜系统或部分冷凝系统。可以进行附加的可选处理来去除杂质，诸如一氧化碳。
可选地，氢产物流334可以被去除，然后使用例如变压吸附系统进一步纯化，并通过管道发送、液化或转化为氨以便输送给外部用户。
在压缩之后(通过压缩机368)，来自ASU 348的氮的一部分318可以可选地添加到氢气流370中。压缩机372可以用于在氢气作为流322(在图1中标记为122，在图4中标记为422)被送到功率生成系统之前压缩氢气。
用于氢气产生的ATR系统的附加特征可以包含：预重整器、预热包含氧气的进料的装置、用于进料预热和蒸汽过热的燃烧加热器、变换反应器的各种配置(包含高温变换、中温变换、低温变换、等温变换和/或它们的组合)、纯化进料以去除痕量杂质(诸如硫)、回收重整反应器和/或将一氧化碳转化为甲烷的甲烷转化器。
虽然图3是在自热重整器的背景下描述的，但是也可以使用其他氢生产方法。这些方法包含天然气的部分氧化(POX)、蒸汽甲烷重整器(SMR)、热解反应器、各种固体和液体燃料的气化以及水的电解。
图4是图1的功率生成系统124的示例的更详细描述。在这个图中，所有元件都被格式化为4XX。在图1中具有带有与图4中示出的项编号相同的最后两位数字XX的附图标记的元件旨在表示与图1相同的元件。
氢气进料气流422可以在被送到五个并联的燃气轮机446a-e的燃烧器460a-e之前与蒸汽流438中的一部分混合。涡轮机446a-d中的四个机械地耦接到天然气液化系统的两个并联链(由工作流226a、226b表示)中的四个压缩管柱。426a-d的组合工作流在图1中由线126表示。对于图2中示出的两个并联LNG生产链中的第一个，机械工作流426a、426c表示与图1的工作流226a相同的工作流，而工作流426b、426d表示与图1的工作流226b相同的工作流。第五燃气轮机446e机械耦接到发电机456，该发电机产生电功率458。来自每个涡轮机的热排气流被送到热量回收蒸汽发生器462a-e，该热量回收蒸汽发生器气化水464，从而产生高压蒸汽466。
然后，高压蒸汽流466和中压蒸汽482在做功蒸汽涡轮机468中膨胀，该做功蒸汽涡轮机机械耦接到发电机470，从而产生电功率472。低压蒸汽467可以有利地用于为氢生产系统118和/或天然气液化系统103提供热负荷。蒸汽轮机468和耦接的发电机470在图4中被描绘为单个单元，但是可以各自包括并联的多个单元。由发电机470、456产生的电功率中的一部分可以被送到外部功率用户(由线436表示)。由线428表示的电能被引导到设施内的其他电功率需求，诸如压缩机、泵、风扇驱动的冷却器等。此外，由燃气轮机446a-e中的氢气的燃烧形成的水可以在氢生产系统中被收集和再循环(例如，与流319组合)。
也可以使用由功率生成系统424生成的蒸汽来驱动设施中的大型压缩机的附加蒸汽涡轮机械驱动装置(未示出)，而不是电动机驱动装置。为此，蒸汽涡轮机可以机械地耦接到压缩机130、压缩机260和/或压缩机346。
在一些应用中，可能期望的是使用氢气和甲烷或天然气的混合物来为燃气轮机466a-e提供燃料。在这样的应用中，天然气可以从天然气进料流100添加到氢气进料气流422中(由图1中的线182表示)，和/或端部闪蒸可以从闪蒸蒸气流114添加到氢气进料气流422中(由图1中的线181表示)。此外，可以通过以在氢气进料气流422中留下一些未反应的甲烷的方式操作氢生产系统118来产生到功率生成系统124的混合的甲烷/氢气燃料流。
图5和图6描绘了图1的天然气液化系统103和功率生成系统124的替代实施例。在图5中，附图标记相对于图2增加了300倍。例如，图2的天然气进料流202对应于图5的天然气进料流502。图2中出现的与图5相同的元件可以在图5中编号，但在说明书中没有单独地讨论。类似地，在图6中，附图标记相对于图4增加了200倍。例如，图4的氢气进料流422对应于图6的氢气进料流622。图4中出现的与图6中相同的元件可以在图6中编号，但在说明书中没有单独地讨论。
参考图5，在这个示例性实施例中，用于天然气液化系统103中的制冷压缩机的功率以电能526的形式从功率生成系统124提供。丙烷压缩机566机械耦接到电动机570，而低压和高压混合制冷剂压缩机562、564分别机械耦接到电动机574、572。图5中描绘的天然气液化系统的所有其他方面与前面关于图2描述的相同。
参考图6，图4和图6中描绘的功率生成系统424、624之间的关键区别在于，图6的功率生成系统624仅以电能和蒸汽的形式向天然气液化系统输出功率，而不以机械能的形式向天然气液化系统输出功率(如图4的功率生成系统424所进行的那样)。在图6中，两个燃气轮机646a、646b分别机械耦接到发电机674a、674b。热量回收蒸汽发生器662a、662b通过从燃气轮机排气中回收热量来生成高压蒸汽666。高压蒸汽666在耦接到发电机670的蒸汽轮机668中膨胀。来自三个发电机674a、674b和670的电功率中的一部分可以从设施输出到电网用于其他用途(由线636表示)。能量流626表示由天然气液化系统203中示出的两个压缩链消耗的电功率，而由线628表示的电能被提供给图1的设施中的其他消费者，诸如压缩机、泵、风扇驱动的冷却器等。
替代性地，本文讨论的发明构思可以应用于现有天然气液化厂的改型，以减少碳足迹，而没有LNG生产能力方面的任何降低。事实上，据信本文中公开的发明构思实现了碳排放(主要是CO2)方面的显著减少，同时增加LNG生产能力。现有的燃气轮机446a-d(参见图4)可以被修改为使用氢气或富氢燃料操作。这将增加到制冷压缩机的机械功率输出226a和226b(参见图2)，从而增加产量。由于燃料需求增加，产量可以进一步增加，因为这将允许LNG流204的温度增加，从而降低LNG生产中制冷所需的功率。为了充分利用这个益处，可能需要修改或更换闪蒸压缩机260，以适应增加的流量。对于这个改造实施例，闪蒸流214被送到新的氢生产系统(例如如图3所述)。这个示例性改造实施例也可以应用于任何配置的燃气轮机驱动的LNG厂，或者应用于具有专用功率生成的电动机驱动的LNG厂，例如如图5和图6所述。
示例1
下面的建模的示例是基于由图1-4表示的过程图，其中材料流在图7和图8中示出，功率流或热流在下表1中示出、对应于图1中示出的流编号。流138和140的质量和摩尔流率值将彼此相等，但将取决于氢生产系统的设计的细节。
Figure BDA0003493663020000131
表1
表2示出了这个示例的关键参数，该示例使用五台Baker Hughes/GE燃气轮机进行功率生成和制冷剂压缩。该过程每年生产1300万吨LNG，同时捕获97％的CO2用于封存，并将92.6％的进料天然气转化为LNG。
Figure BDA0003493663020000132
表2
示例2
表3示出了替代实施例的示例的关键建模参数，其中两个GE框架7F燃气轮机用于组合循环功率生成。在本示例中，天然气液化系统每年生产1150万吨LNG，同时捕获97％的CO2用于封存，并将94.3％的进料天然气转化为LNG产物。
Figure BDA0003493663020000133
Figure BDA0003493663020000141
表3
由此，已经根据本发明的优选实施例和替代实施例公开了本发明。当然，在不脱离本发明的精神和范围的情况下，本领域技术人员可以设想对本发明的教导进行各种改变、修改和变更。本发明旨在仅由所附权利要求书的条款来限制。

Claims (30)

1.一种方法，包括：
（a）在天然气液化系统中至少部分地液化天然气进料流以形成LNG流，所述天然气液化系统包含至少一个压缩机；
（b）将所述LNG流分离成闪蒸蒸气流和LNG产物流；
（c）将所述闪蒸蒸气流中的至少一部分通入氢生产系统；
（d）使所述闪蒸蒸气流中的至少一部分在所述氢生产系统中反应，以形成含氢流和第一富CO2流；
（e）使用所述含氢流中的至少一部分在功率生成系统中生成功率；以及
（f）利用在步骤（e）中生成的所述功率中的至少一部分向所述至少一个压缩机提供功率。
2.根据权利要求1所述的方法，其中所述闪蒸蒸气流是至少50 mol %的甲烷。
3.根据权利要求1所述的方法，其中所述含氢流是至少80 mol %的氢气。
4.根据权利要求1所述的方法，还包括：
（g）在执行步骤（a）之前，从所述天然气进料流中分离第二富CO2流；以及
（h）将所述第一富CO2流和所述第二富CO2流组合以形成组合的CO2流。
5.根据权利要求4所述的方法，还包括：
（i）使用来自所述天然气液化系统的制冷负荷，液化选自所述第一富CO2流、所述第二富CO2流和所述组合的富CO2流组中一者的至少一部分。
6.根据权利要求1所述的方法，其中步骤（d）还包括使所述闪蒸蒸气流中的至少一部分和环境空气流在所述氢生产系统中反应，以形成所述含氢流和所述第一富CO2流。
7.根据权利要求1所述的方法，其中步骤（d）还包括使所述闪蒸蒸气流中的至少一部分和含氧流在所述氢生产系统中反应，以形成所述含氢流、所述第一富CO2流、第一蒸汽流和废氮流。
8.根据权利要求7所述的方法，其中所述含氧流是环境空气。
9.根据权利要求7所述的方法，还包括：
（j）使环境空气流通过空气分离单元以产生含氧流和富氮流。
10.根据权利要求9所述的方法，其中步骤（e）还包括使用所述含氢流和所述富氮流中的至少一部分在功率生成系统中生成功率。
11.根据权利要求1所述的方法，其中步骤（e）还包括使用来自所述氢生产系统或功率生成系统的所述含氢流和至少一种蒸汽流在所述功率生成系统中生成功率。
12.根据权利要求1所述的方法，其中步骤（e）还包括使用所述含氢流驱动至少一个燃气轮机和使用第一蒸汽流驱动至少一个蒸汽轮机来在所述功率生成系统中生成功率。
13.根据权利要求1所述的方法，其中在步骤（e）中生成的所述功率包括电功率，并且步骤（f）包括向附接到所述至少一个压缩机的至少一个电机提供所述电功率中的至少一部分。
14.根据权利要求1所述的方法，其中在步骤（e）中生成的所述功率包括电功率，并且步骤（f）包括向所述氢生产系统和所述天然气液化系统中的至少一个提供所述电功率的至少一部分。
15.根据权利要求1所述的方法，其中在步骤（e）中生成的所述功率包括电功率，并且所述方法还包括：
（k）将所述电功率中的至少一部分输出到所述天然气液化系统、所述氢生产系统和所述功率生成系统外部的过程。
16.根据权利要求1所述的方法，其中步骤（e）还包括使用所述含氢流和至少一种含甲烷流在功率生成系统中生成功率。
17.根据权利要求16所述的方法，其中所述至少一种含甲烷流包括选自天然气进料流和所述闪蒸蒸气流组中的至少一种。
18.根据权利要求1所述的方法，还包括：
（l）将步骤（d）中产生的所述含氢流中的至少一部分输出到所述天然气液化系统、所述氢生产系统和所述功率生成系统外部的用途。
19.根据权利要求1所述的方法，其中步骤（f）包括通过将所述功率生成系统的至少一个燃气轮机机械耦接到所述天然气液化系统的所述至少一个压缩机来驱动所述至少一个压缩机。
20.根据权利要求1所述的方法，还包括：
（m）使用来自所述天然气生产系统的制冷来冷却所述氢生产系统。
21.根据权利要求1所述的方法，还包括：
（n）使用从所述氢生产系统和所述功率生成系统中的至少一个生成的热量为干燥器单元提供热负荷，所述干燥器单元适于从用于所述天然气液化系统的天然气进料流中分离水分。
22.根据权利要求1所述的方法，还包括：
（o）将所述天然气进料流分成第一部分和第二部分，对所述天然气进料流中的所述第一部分进行步骤（a），并在进行步骤（d）之前将所述天然气进料流的所述第二部分与所述闪蒸蒸气流组合。
23.根据权利要求1所述的方法，其中步骤（a）包括在所述天然气液化系统中至少部分地液化所述天然气进料流以形成所述LNG流，所述天然气液化系统包含具有至少一个压缩机的闭环制冷系统。
24.一种改造现有天然气液化系统的方法，所述天然气液化系统在进料温度下至少部分地液化天然气进料流，以在产物温度下形成LNG产物，所述天然气液化系统包括至少一个压缩机，所述方法包括：
（a）添加氢生产系统，所述氢生产系统使由所述天然气液化系统产生的端部闪蒸中的至少一部分反应以形成含氢流；
（b）使用所述含氢流在功率生成系统中生成功率；以及
（c）利用在步骤（b）中生成的所述功率中的至少一部分向所述至少一个压缩机提供功率。
25.根据权利要求24所述的方法，还包括：
（d）降低所述进料温度和所述产物温度之间的差异，从而每立方英尺所处理的天然气产生比改造前产生的更多的端部闪蒸。
26.根据权利要求24所述的方法，还包括：
（e）添加所述功率生成系统。
27.根据权利要求24所述的方法，其中所述功率生成系统适于在改造之前向所述天然气液化系统提供功率，所述方法还包括：
（f）修改所述功率生成系统中的至少一个现有燃气轮机以由所述含氢流提供燃料。
28.根据权利要求27所述的方法，还包括：
（g）相比于改造前，在改造后利用至少一个现有燃气轮机生成更多的功率。
29.根据权利要求24所述的方法，还包括：
（h）在改造后产生进入LNG储罐的第二质量流率的LNG产物，所述第二质量流率不低于改造前产生的进入所述LNG储罐的LNG产物的第一质量流率。
30.根据权利要求24所述的方法，还包括：
（i）使用所述氢生产系统分离所述端部闪蒸中包含的至少80%的二氧化碳。
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