CN109690215A - 工业气体场所与液氢生产的一体化 - Google Patents

工业气体场所与液氢生产的一体化 Download PDF

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Publication number
CN109690215A
CN109690215A CN201780055204.7A CN201780055204A CN109690215A CN 109690215 A CN109690215 A CN 109690215A CN 201780055204 A CN201780055204 A CN 201780055204A CN 109690215 A CN109690215 A CN 109690215A
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hydrogen
stream
hydrogen stream
nitrogen
pressure
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CN201780055204.7A
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CN109690215B (zh
Inventor
阿兰·吉亚尔
皮埃尔-艾蒂安·法郎
迈克尔·A·特尼
基里尔·安德列耶夫
亚历山大·勒施
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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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
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0005—Light or noble gases
    • F25J1/001—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • 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
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • 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
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    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0012—Primary atmospheric gases, e.g. air
    • F25J1/0015—Nitrogen
    • 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
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    • 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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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • 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"
    • F25J1/004—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 flash gas recovery
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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"
    • F25J1/0045—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 vaporising a liquid return stream
    • 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
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    • F25J1/0047—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 an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/005—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 an "external" refrigerant stream in a closed vapor compression cycle by expansion of a gaseous refrigerant stream with extraction of work
    • 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
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    • F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/0062—Light or noble gases, mixtures thereof
    • F25J1/0067—Hydrogen
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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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    • F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
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Abstract

用于生产液氢的方法(346)可以包括以下步骤：将来自高压天然气管道(300)的加压天然气(302)引入处于有效产生经纯化氢流(315)的条件下的气体处理单元；并且将该经纯化氢流引入处于有效产生液氢流的条件下的氢液化单元(346)，其中，该氢液化单元对该经纯化氢流提供暖温冷却和冷温冷却，其中，该暖温冷却是通过利用选自下组的加压流的泄放能量来提供的，该组由以下组成：源自氮管道的氮流(320)、源自该高压天然气管道(300)的天然气流(2)、源自空气分离单元(ASU)的空气气体(86)、及其组合，其中，通过利用该经纯化氢流的泄放能量来提供该冷温。

Description

工业气体场所与液氢生产的一体化
相关申请的交叉引用
本申请要求于2016年8月5日提交的美国临时申请号62/371,497和2017年1月24日提交的美国专利申请号15/414,155的非临时申请的权益，这些申请的全部内容通过援引并入本文。
技术领域
本发明涉及一种用于氢的液化的设备和方法。更具体地，本发明的实施例涉及通过使用各种高压流的压力泄放(letdown)进行组合制冷来液化氢气流。
背景技术
在典型的氢液化设施中，将高压氢气(例如，15-70bara)纯化和干燥并送至冷箱，在冷箱中将其冷却至约-190℃。这种冷却水平的制冷典型地通过闭环氮制冷循环提供。除了利用氨或其他制冷剂的机械制冷单元之外，氮制冷循环可以包括单一涡轮机、多个涡轮机、具有增压器的涡轮机。另外，氮制冷循环典型地采用多级氮再循环压缩机来完成闭环。
替代性地，对于一些应用，通过将液氮(LIN)流注入约-190℃的交换器中来提供这种制冷水平(至-190℃)。当氮流与正在冷却的氢流交换冷时，该氮流汽化并升温至接近环境温度。该替代方案的热动力效率较低，并且需要源自单独的氮液化器的液氮，这仍需要循环压缩机和涡轮机增压器。
通过第二制冷循环将冷却的气态氢进一步冷却并在约-252℃下液化。可以通过具有多个涡轮机和氢(或氦)再循环压缩机的氢(或氦)制冷封闭循环来提供用于这种冷却水平的制冷。由于低分子量(MW)或更具体地因为这些分子太小，氢(或氦)压缩非常困难且昂贵。
本领域普通技术人员还将认识到，产生液氢需要其他步骤(例如，吸附系统、邻位-对位转换)，这些步骤在本文中未描述，因为它们不受本发明实施例的影响。
美国专利号2,983,585(史密斯)披露了一种部分氧化过程，在该过程中，用氧将甲烷部分氧化以产生一氧化碳和氢气。该部分氧化过程与氢液化过程集成，在该氢液化过程中通过与液态甲烷的间接热交换来将氢气预冷却、并且随后使用液氮(“LIN”)作为制冷剂在封闭的外部制冷循环中将其进一步冷却。所得甲烷在该液化过程的暖端被压缩、然后被送到部分氧化过程。所得的气态氮在闭合循环的暖端被压缩、然后通过与液态甲烷的间接热交换而冷凝、并再循环。披露了可以用液化天然气(“LNG”)来代替液态甲烷。然而，对于此方案，暖端的制冷负荷简单地从氢液化单元转移到天然气液化单元。在氮与LNG之间需要额外的热交换系统，这将导致额外的热力学损失。并且，由于LNG的液化温度，氢流仅被冷却到约-150℃。
美国专利号3,347,055(布兰卡德等人)披露了一种过程，在该过程中使气态烃原料反应以产生氢气，然后将氢气在一体化的液化循环中液化。在一个实施例中，该液化循环包括两个制冷剂封闭循环，第一个使用氢气作为制冷剂，而第二个使用氮。这两个制冷循环的压缩发生在循环的暖端。还通过与经液化的烃原料气体的间接热交换来冷却待液化的氢，由此产生1atm(例如，约0.1MPa)的气态原料，用于在氢生产设施中使用。披露了烃原料可以是天然气。该方案还将部分制冷负荷从氢液化器转移到天然气液化器。
JP-A-2002/243360披露了一种生产液氢的过程，在该过程中通过与加压LNG流的间接热交换来预冷却氢作为原料气体(与3,347,055布兰卡德中的相似)。将预冷却的氢气送入液化器，在液化器中该氢气通过与LIN以及选自氢或氦的制冷剂的间接热交换被进一步冷却。进一步冷却后的氢接着膨胀而产生部分冷凝的氢，该氢被分离成液氢(被移除并储存)和氢蒸气(在液化器中再循环)。
Quack(夸克)披露了(“Conceptual Design of a High Efficiency LargeCapacity Hydrogen Liquefier(高效大容量氢液化器的概念设计)”；Adv.Cryog.Eng.,Proc.CEC,Madison 2001,AIP,第613卷,255-263)一种氢液化器循环，据发明人所知，这最准确地表示了对氢液化循环的目前最好的技术预测。应注意的是，夸克使用的压缩机和涡轮机的效率数据目前无法实现、但被认为未来是可现实的。
当前的氢液化过程基于在2.5MPa(25巴)的典型压力下的气态氢进料，以大约11kWh/kg(液氢)的速率消耗电力。夸克(“Conceptual Design of a High EfficiencyLarge Capacity Hydrogen Liquefier(高效大容量氢气液化器的概念设计)”；Adv.Cryog.Eng.,Proc.CEC,Madison 2001,AIP,第613卷,255-263)提出，如果采用他提出的改进建议，未来的最佳耗电量将在5至7kWh/kg(液氢)之间。
该方案包括通过与丙烷、氨、碳氟化合物或其他制冷剂的间接热交换将来氢预冷却至大约-53℃。然后通过与氦和氖的混合物的间接热交换，将氢进一步冷却并在两个或更多个步骤中液化。使用氖增大了制冷剂混合物的分子量，从而使再循环压缩机更容易，并且由此降低了压缩能量(通常75％的MW＝4的He和25％的MW＝20的Ne得到MW＝8的混合物)。然而，在混合物中使用氖还可以防止制冷剂的温度水平达到氢液化所需的非常低的温度(-252℃)。此外，必须采购氦和氖，并仔细管理其在氖/氦混合物中的组成。并且，与本发明不同的是，这种制冷剂必须进行特别压缩，且仅用于氢液化能量。
本发明的一个目的是开发一种方案，该方案不需要氖或氦、并且可以在氢液化器的非常冷端(-252℃)有效地提供制冷。
氢的低分子量意味着必须使用大量的压缩级，并且如果指定离心压缩机并且同样地对于给定的膨胀任务，则需要串连操作大量的离心膨胀级。在目前的设施中，氢压缩机通常是往复式单元。多级压缩机加大型回热式热交换器通常在该过程的预冷却步骤中用于除去压缩热。
上述典型过程典型地利用三个氢压缩机和两个氮压缩机(H2入口进料压缩机、H2循环进料压缩机、H2再循环压缩机、N2进料压缩机和N2再循环压缩机)。这样，这些类型的系统和方法需要大量的资金和操作成本(例如，公用设施和维护)，以实现氮和氢制冷循环所需的压缩。
此外，由于其分子量低且分子大小小，氢的压缩非常困难并且因此成本高。因此，希望在不进行氢压缩或减少氢压缩的情况下生产液氢，以降低或减少相关的高资本支出或大量的操作成本。
发明内容
本发明涉及一种满足这些需求中的至少一个的方法。在本发明的某些实施例中，提供了一种通过使用之前浪费的泄放能量来将加压氢气液化的方法。在某些实施例中，该泄放能量可以通过选自下组的高压气体的泄放来提供，该组由以下组成：(1)来自高压天然气管道的天然气流，(2)来自高压氮管道的氮气流，(3)来自附近设施的氢气流，及其组合。
在可选的实施例中，高压气体可以进一步包括来自或源自空气分离设施的干燥且经纯化的空气气体，其中，该干燥且经纯化的空气气体选自下组，该组由以下组成：来自空气主压缩机的加压空气、来自空气增压压缩机的加压空气、来自中压塔或氮压缩机的加压氮、及其组合。
在一个实施例中，用于将源自变压吸附器单元的加压氢气液化的方法可以包括以下步骤：从甲醇生产单元中抽出含氢气体，该含氢气体优选地是含氢吹扫气体；将该含氢气体引入处于有效纯化该含氢气体的条件下的变压吸附器(PSA)单元以产生经纯化的氢流；将该经纯化的氢气送至处于对于氢气液化有效的条件下的氢液化单元，由此产生经液化的氢流，其中，该氢气液化单元被配置用于提供第一制冷源和第二制冷源，其中，该第一制冷源使用高压氮流的膨胀来提供制冷，该高压氮流优选地来自氮管道，其中，该第二制冷源使用高压氢气流的膨胀来提供制冷，以产生暖的氢气流，其中，该高压氢气流是源自选自下组的氢流，该组由以下组成：该经纯化氢流、从第二PSA单元抽出的第二经纯化氢流、及其组合。
在本发明的可选实施例中：
·该PSA单元是甲醇设施的一部分；
·该高压氮在一个或多个涡轮膨胀器中膨胀；
·该一个或多个涡轮膨胀器彼此串联地布置；
·该一个或多个涡轮膨胀器彼此并联地布置；
·该高压氮膨胀到至少4bara的压力并且用作公用事业气体(utility gas)；
·将暖的氢气流在选自下组的单元中被用作燃料气体，该组由以下组成：蒸汽甲烷重整器(SMR)、蒸汽锅炉、火焰加热器、及其组合，其中，优选的是该SMR在该PSA的上游；
·该第二制冷源包括：将该高压氢气流的第一部分在第一膨胀涡轮机中膨胀至第一压力；并且将该高压氢气流的第二部分在第二膨胀涡轮机中膨胀至第二压力，其中，该第一压力高于该第二压力；
·该第一制冷源提供暖温冷却，并且该第二个制冷源提供冷温冷却；
·使用天然气泄放能量来提供第三制冷源；
·该第三制冷源提供暖温冷却；
·使用源自空气分离单元(ASU)的空气气体的泄放能量来提供第四制冷源；
·该源自ASU的空气气体是选自下组的气体流，该组由以下组成：来自空气增压压缩机的被压缩且纯化的空气、可以来自氮管道的氮流、及其组合；
·该PSA单元和该第二PSA单元共用共同的进料流；
·该方法可以不包括以下步骤：使用由在该PSA单元和该氢液化单元下游的马达提供动力的压缩装置来压缩该经纯化氢流或该经膨胀的经纯化氢流，其中，该经压缩的氢将提供冷温制冷；和/或
·该经纯化氢流处于至少15巴的压力。
在一个实施例中，该用于产生液氢的方法可以包括以下步骤：将来自高压天然气管道的加压天然气引入处于有效产生经纯化氢流的条件下的气体处理单元；并且将该经纯化氢流引入处于有效产生液氢流的条件下的氢液化单元，其中，该氢液化单元对该经纯化氢流提供暖温冷却和冷温冷却，其中，该暖温冷却是通过利用选自下组的加压流的泄放能量来提供的，该组由以下组成：源自氮管道的氮流、液氮、源自该高压天然气管道的天然气流、源自空气分离单元的空气气体、及其组合，其中，该冷温制冷是通过利用该经纯化氢流的泄放能量来提供的。
在该方法的可选实施例中：
·该方法可以不包括以下步骤：使用由在该气体处理单元和该氢液化单元下游的马达提供动力的压缩装置来压缩该经纯化氢流或该经膨胀的经纯化氢流，其中，这种经压缩的氢将提供该冷温制冷；
·该气体处理单元包括甲醇生产设施；
·该气体处理单元包括甲醇制丙烯生产设施；
·该气体处理单元包括氨生产设施；
·在共用吸附器单元中从正在液化的经纯化氢流以及提供用于制冷的泄放能量的氢流中去除氩和/或氮；
·该冷温制冷由至少两个以串联布置来操作的涡轮机提供；
·这些氢涡轮机中的一个或多个被配置用于驱动一个或多个增压器，其中，该一个或多个增压器用于对该经纯化氢流、该经膨胀的经加压氢流、或其组合加压；
·通过氢的泄放而提供的冷制冷是由三个涡轮机提供，其中，氢在第一涡轮机中膨胀而产生第一膨胀氢流，该第一膨胀氢流的第一部分在第二涡轮机中进一步膨胀而产生第二膨胀氢流，该第一膨胀氢流的第二部分在第三涡轮机中冷却并膨胀而产生第三膨胀氢流，其中，该第二和第三膨胀氢流通过与正在冷却的氢流进行热交换而升温；
·在该升温步骤之前或期间将该第二和第三膨胀氢流合并；和/或
·通过仅来自在该第一氢涡轮机之前的氢流的制冷来部分地冷却到该第一涡轮机的氢，其中，提供该冷却的氢流由该第一、第二和第三膨胀氢流、第四膨胀氢流、储罐汽化流(boil off)、及其组合组成。
附图说明
参考以下描述、权利要求和附图，本发明的这些和其他的特征、方面和优点将变得更好理解。然而，应注意的是，附图仅展示了本发明的若干实施例并且因此不应被认为是对本发明范围的限制，因为本发明可以允许其他等效实施例。
图1示出了根据现有技术实施例的甲醇生产设施的实施例。
图2示出了根据本发明实施例的具有ASU和液化器的一体式甲醇生产设施的实施例。
图3示出了根据本发明实施例的具有ASU和液化器的一体式甲醇生产设施的另一个实施例。
图4示出了根据本发明实施例的氢液化器的实施例。
图5示出了根据本发明实施例的氢液化器的另一个实施例。
图6示出了根据本发明实施例的氢液化器的另一个实施例。
图7提供了根据本发明实施例的空气分离单元的示意图。
具体实施方式
虽然将结合若干实施例来描述本发明，但是应理解的是，不旨在将本发明限制于那些实施例。相反，本发明旨在覆盖可以包含在由所附权利要求限定的本发明的精神和范围内的所有替代、修改和等同物。
在其最简单的形式中，本发明的实施例包括气体处理单元与氢液化单元的整合，其中气体处理单元使用可获得的泄放能量(否则将被浪费)来提供一部分制冷，以将氢液化。
在某些实施例中，气体处理单元可以包含甲醇(MeOH)设施，并且在一些情况下可以包含甲醇制丙烯设施。在另一个实施例中，来自空气分离单元的加压空气和/或氮也可以为氢液化器提供泄放能量。在某些实施例中，提出了将气体处理单元的未充分利用的泄放能量整合到液化单元中来以降低的操作成本生产液体。
在某些实施例中，气体处理单元包含一种或多种高压供应气体流，其向中压消耗器提供气体。一些系统还具有未充分利用的压缩能力，该压缩能力可以被利用来使得气体可以泄压至大气压力并排出或再循环。从压力泄放流中提取的能量可以用于提供制冷，以与待冷却和液化的氢气进行逆流热交换。
在许多气体处理单元的典型操作中，通常将较高压气体流泄压而不回收在气体膨胀期间产生的任何所得制冷。
例如，甲醇设施需要来自高压输送网络的大量天然气进料。该天然气进料的一部分的压力通过控制阀减小至低压、并在以下中的一者或多者中作为燃料燃烧：蒸汽甲烷重整器(SMR)、火焰加热器、燃气涡轮机、辅助锅炉、蒸汽锅炉、以及辅助燃烧器。
天然气进料的其余部分(并且是大部分)在脱硫单元中进行处理、并在SMR和/或自热重整器(ATR)中反应而产生合成气。在甲醇设施中，合成气(含有二氧化碳、一氧化碳、甲烷和氢气，并且具有约为11的组合分子量)被进一步压缩至约50-150bara并发生反应，以产生甲醇和富含氢的经加压的副产物流。该副产物流可以分成两个分量，其中第一分量去往变压吸附器(PSA)以产生纯化的氢产物，而其余的第二分量(称为吹扫气体)典型地通过控制阀将压力减小至约0.3-7bara、并且在甲醇设施内用作燃料。
该压缩能量是生产甲醇所需的、但是可以在本发明的某些实施例中使用，通过利用吹扫气体的泄压能量而无需任何额外的能量输入来达到氢液化器的极冷制冷水平。与现有技术中制冷压缩能量必须专门且单独分配给氢液化不同，本发明的实施例可以通过使用来自甲醇设施的加压氢来减少甚至消除压缩待液化的氢流的需要。此外，本发明某些实施例的经压缩流的分子量(MW＝11)高于夸克所说的现有技术液化器的8和常规氢液化器对于氢而言的2或对于氦而言的4。
在另一个实施例中，该气体处理单元可以包括公共设施氮使用器。这些使用器将大量处于约4-8bara压力下的氮用作公共设施气体。这典型地是通过附近高压(～37bara)氮管道的压力泄放来提供的。在一个实施例中，气体处理单元可以包括甲醇制丙烯(MMTP)设施，该设施还需要约4-8bara压力下的大量气态氮作为公共设施气体。
因此，在某些实施例中，可以存在具有未充分利用的压力泄放能量的至少三种流：针对公共设施气体所吸附的高压氮、针对用作燃料泄放或泄放到低压分配网络的高压天然气、以及作为燃料被泄放的富氢吹扫，其通常不利用压力控制阀的可获得高压能量。另外，甲醇过程还产生高压氢产物流。该设备(诸如PSA)可以被设计用于增大流量并用于实现制冷膨胀的目的。
在某些实施例中，可以通过这些流的膨胀与从高压氮管道到低压或排气口的加压氮气流的膨胀的结合来利用这些流的潜在高压能量。
可以通过膨胀来自ASU的加压气体流、诸如从空气增压压缩机(BAC)排出的空气、来自管道或氮压缩机的加压氮、及其组合来提供额外的制冷来源。出于本文的目的，源自管道的氮被认为是源自ASU的经加压气体流。
在ASU的正常操作中，BAC典型地低于其最大设计条件来操作。这是因为最大设计条件通常是基于最坏情况的条件(例如，最大液体产物、最大高压气态氧、夏季条件等)，这可能是偶尔需要的、但很少是实际操作点。另外，诸如MAC和BAC的主要设备的设计容量可以最大化到资本成本的阶梯式变化的极限，例如基于压缩机机架大小的极限。因此，在典型的空气分离单元中，通常从BAC、MAC和预处理可获得过剩的容量，使得可以从ASU中抽出约15-100bara的高压空气，而有额外的资本成本极少或为零并且仅略微增加运营成本。通过整合甲醇设施，通过使用从甲醇设施可获得的蒸汽的蒸汽涡轮机来驱动MAC和BAC，可以实现额外的节约。
在另一个实施例中，高压空气的未送至ASU冷箱的一部分可以与来自氮管道的为约30-70bara的可用高压氮气(HPN2)混合。这可以实现约30-70bara的可用于液化器中的膨胀制冷的低成本、精益合成的高压空气(或不纯的N2)流。在一个实施例中，空气注入可能受限于甲烷中的O2(约12％)或H2中的O2(约6％)的可燃性限制、或由于潜在泄露对这些限制所应用的设计余量。
因此，本发明的某些实施例提供了一种用于氢液化的改进方法，该方法以有效的方式结合了上述方法的可用的浪费能量。在另一个实施例中，该方法还可以包括天然气的液化和/或氮的液化。
图1提供了典型甲醇设施301的示意性概览。从天然气管道300中抽出天然气，其中将天然气的第一部分302送至加氢脱硫单元以除去硫，从而形成脱硫天然气304。然后将该流送至蒸汽甲烷重整器(SMR)以产生合成气306，然后在压缩机310中将其加压至约50-70bara，然后将其送至处于有效生产甲醇和吹扫气体311的条件下的甲醇生产设施。然后将吹扫气体的第一部分314送至变压吸附器(PSA)，以回收经纯化的氢。在典型的甲醇设施中，吹扫气体的第二部分312(处于仅标称地小于压缩机310的排出压力的增大压力(～50-70bara)下)典型地跨过阀而膨胀至非常低的压力(例如，大约大气压)并且接着被送至SMR以用作吹扫气体燃料316。类似地，典型地使用天然气的第二部分1在阀穿通管线308中膨胀之后作为SMR的燃料来补充上述燃料。
图2提供了根据本发明实施例的整合的甲醇设施、液化器和ASU的示意性概览。在本发明的一个可选实施例中，代替天然气1膨胀跨过阀而浪费其膨胀能量，可以将天然气2送至液化器，如图6所描述的，以提供用于将天然气冷却和液化的制冷的一部分。
另外，代替将吹扫气体的第二部分312膨胀并送至SMR作为燃料316，将额外的吹扫气体311送至PSA，以产生额外的高压经纯化氢。因此，在本发明的某些实施例中，用于纯化吹扫气体311的PSA优选地大于正常值，以适应吹扫气体311到PSA的增大的体积流量。在另一个实施例中，可以将在PSA的吸附阶段被吸附并且在PSA的再生阶段被解吸附的杂质313从PSA送至SMR。在操作中，这些从PSA中解吸附的杂质处于低压、并且补偿了不将吹扫气体送至SMR作为燃料。燃料净平衡只受作为液态产物346被除去的氢分子的少量减少的影响，而天然气燃料流1的少量增加则弥补了这一影响。
如上所述，在本发明的某些实施例中，与正常操作相比，可以增大经纯化氢的体积流量。这允许将经纯化氢的第一部分315送至液化器，这将在图3至图5中更详细地讨论。由于该经纯化氢流已经处于升高的压力(例如，通常大于50bara)，因此本发明的某些实施例不要求使用氢进料压缩机或制冷循环压缩机来实现该循环的极低温度水平。
可以通过将来自氮管道的高压氮320泄压来提供制冷能量的其他来源。图3至图5中示出了制冷循环的细节。氢液化器在有效产生液氢产物346和低压氢62、64的条件下操作。在某些实施例中，液化器还可以产生LNG(或液氮)46以及中压氮66，该中压氮可以在附近设施、例如甲醇设施301中用作公用事业气体。
虽然图2未示出吹扫气体的第二部分312，但是本发明的某些实施例可以包括使用吹扫气体的第二部分312作为获得泄放制冷能量的潜在来源。吹扫气体的第二部分(从甲醇设施接收的高压富氢流)可以部分地被冷却(例如，从热交换器的中间区段去除吹扫气体)、在涡轮机(或一组串联或并联布置的涡轮机)中膨胀(这可以与发生器、增压器或用于耗散到大气中的其他系统关联)以形成经膨胀的吹扫气体，然后在液化器的主换热器中升温、并且被送回至甲醇设施作为低压燃料(例如与图2的316混合)。因此，经膨胀的吹扫气体可以提供用于冷却并且最终液化该氢的暖端制冷的额外来源。这减小了PSA的大小，并且因此减少了可用于泄放以提供冷端制冷的氢，但由于吹扫气体中各组分的凝固点的限制，提供更多的暖端制冷。
在未示出的另一个实施例中，在经膨胀的富氢吹扫气体被再加热之后，它可以被增压(在由膨胀器驱动的增压器中)、在主交换器中再冷却、在第二组涡轮机中再次膨胀、并且在主交换器中再加热。这种布置通过利用吹扫气体泄放的较高压力比率提供了增加的暖端制冷产量，而这至少部分地被额外的循环复杂性和资本成本抵消。这是这种应用特别感兴趣的地方，因为氢的膨胀比率高于典型的氢液化器，因为它是从PSA出口的高压到燃料进口的极低压力。典型的氢液化器具有较低的压力比，因为它们必须尽量减少循环压缩机的压缩级数。
与独立的氢液化器相比，甲醇设施、液化器和可选的ASU的集成提供了显著的能量节省。在一个实施例中，用于氢气流液化的所有制冷均由来自氮管道的氮的膨胀和来自PSA的经纯化氢产物流的至少一部分的膨胀所提供的冷却能量提供。在另外的实施例中，额外的制冷源可以包括由来自天然气管道的经加压天然气和来自ASU的空气气体提供的膨胀能量。替代性地，为了增加液化，该液化能量可以用一个或多个另外的液化能源补充，诸如由电动涡轮机、燃气涡轮机或蒸汽涡轮机驱动器或液氮注入所驱动的循环压缩机。
图3提供了图2中所示的整合的甲醇设施、液化器和ASU的替代实施例。在图2中，来自甲醇单元MEOH的所有吹扫气体311被送至PSA进行纯化。但是，在图3的实施例中，与图1所示的实施例类似，抽出吹扫气体的一部分312。然而，为了产生高压富氢气体315，该流并没有被送到SMR用作燃料，而是被送到第二PSA 317进行处理。低压杂质313、313a在与低压氢62合并后被再次送至SMR作为燃料。如图3所示的实施例尤其适用于存在已有甲醇设施并且氢液化器是作为附加设备构建的情况。由于增加了第二PSA 317，原来的PSA不需要更换成更大的单元。这允许以一种更简单且更经济的方式升级现有场所，同时停机时间最少。
在其他实施例中，流315a、315b都可以是非常高纯度的氢，使得两者都可以被带到冷端温度(～-250℃)而不冻结微量组分。替代性地，其中一个PSA可以设计有更高量的微量组分(例如，为了降低PSA成本和/或从PSA获得更高的氢回收)并用于略微更暖的制冷温度水平(例如-200℃至240℃)。另一个PSA优选以非常高纯度的氢操作以提供液氢产物和非常冷的冷端(-230℃至-252℃)制冷。类似地，这些PSA可以在不同压力下操作，以优化PSA成本、氢回收和液化器制冷。
图4提供了利用(1)来自被泄放到低压排气口的管道的高压氮气320和(2)泄放以用作燃料或低压气态产物62和63以及液氢产物346的高压富氢气体315的高压能量的实施例的示意图。
氮制冷循环340提供暖温冷却，而氢膨胀350提供冷温冷却。在氮制冷循环340中，高压氮320(其优选源自在30bara以上操作的氮管道)可以在氮增压器322中进一步压缩并在后冷却器324中冷却以形成增压氮326。该增压氮的第一部分然后可以在第一热交换器345中膨胀、之后在氮涡轮机328中膨胀、在第一热交换器345中再次冷却(或取决于特定氮条件，诸如氮供应压力，被加热)、在第二氮涡轮机332中再次膨胀到大约大气压以形成完全膨胀的氮334，其接着被重新加热并排放到大气中、或选择性地用于在蒸发冷却塔中冷却。氮涡轮机328提供氮增压器322使用的动力。在所示的实施例中，第二氮涡轮机332与发电机G连接，从而产生电力，该电力可以返回电网。本领域普通技术人员还将认识到，第二氮涡轮机332可以与第二氮增压器(参见图5)连接，这取决于系统的操作条件(例如，流速、压力、膨胀比率、热力学等)。
在所示的实施例中，增压氮的第二部分在第一热交换器345内被至少部分冷凝、并且在比第一部分更冷的位置被抽出，之后跨过阀将压力降低到大气压并引入液/气分离器336之前。气态部分337在第一热交换器345中被再加热并最终排放到大气中。液氮(LIN)338从液/气分离器336的底部抽出，其中部分339被加热并部分蒸发、之后再循环回到液/气分离器336。部分339用作热虹吸管。在另一个实施例中，该热传递可以没有热虹吸管。
经纯化氢的第一部分315可在阀(未示出)中膨胀、之后在第一热交换器345中冷却，优选地冷却至足以通过吸附除去杂质的温度，其中所述杂质可以包括氩、氮等。然后在氢纯化单元365中除去这些杂质，使得它们在第二热交换器355内的冷温冷却期间不会冻结。由于氢制冷是开式循环，因此优选的是使正在液化的流和正在膨胀的流的杂质都在冷吸附器中被去除。该冷吸附器可以是共用的冷吸附器，如图4所示。对于典型的氢(或He)制冷封闭循环，只有进入循环的流体和正在液化的流体必须具有这个吸附步骤。
在所示的实施例中，经纯化氢被分成两部分，其中一部分369在第二热交换器355中液化，而另一部分用于通过氢膨胀350提供冷温冷却。液化后的部分369接着可以在阀中膨胀、并被引入分离器371。来自分离器371的蒸汽返回到交换器355以进行冷端制冷，并且液氢346作为产物被抽出。
在所示的实施例中，经纯化氢的另一部分370可以在第二热交换器355中稍微冷却、之后在氢涡轮机375a、375b、375c中经历一系列膨胀步骤以产生冷的中压氢流，该冷的中压氢流然后在第二热交换器355和第一热交换器345中被再加热以形成暖的中压氢62，该暖的中压氢可以被送回至SMR用作燃料、或用于某些其他目的(参见图2和3中的64)。
与氮制冷循环340一样，该氢的第二分量在第二热交换器355内被至少部分冷凝、并且在比氢的其余部分370更冷的位置被抽出、然后跨过阀将压力减小至约大气压并被引入液/气分离器366。气态部分367在第二热交换器355和第一热交换器345中被再加热以形成低压氢。液氢368从液/气分离器366的底部被抽出、并且然后再循环回到液/气分离器366而再次用作热虹吸管。替代性地，这种热传递可以没有热虹吸。
在所示的实施例中，通过提供约57mtd的65bara氢(流315)和约390mtd的36bara的氮(流320)，该方法可以提供约11mtd液氢(流346)、42mtd中压氢(流62)、4mtd低压氢(流63)，同时还从第二氮涡轮机332产生约160kW的能量。
图5提供了第二实施例的示意图，该第二实施例利用(1)来自被泄放到低压排气口的管道的高压氮气320a和(2)被泄放以用作燃料或低压产物的高压富氢气体315的高压能量。在该实施例中，不是使用串联连接的第一和第二膨胀器328、332将所有氮膨胀到大气压，而是氮部分329、334在并联连接的第一和第二膨胀器328、332中膨胀到中压。如果附近有氮公共设施气体的使用器，这是特别有利的，因为该使用器很可能只是将来自该管道的高压氮气快速泄压至中压，而没有捕捉该气流的任何制冷能量潜力。取决于所需的中压氮330的流量，如果氮部分329、334不足，则可以通过旁路管线321提供额外的氮。
另外，该实施例示出了将初始高压氢315在第一热交换器345上游分成两个流315a、315b的实例。在这样做时，还使用另外的纯化单元365b。在所示的实施例中，氢流315a被液化，并且氢流315b提供冷温冷却。将冷吸附器分成如图5所示的365和365b允许其各自在不同的压力下操作，这在某些情况下可以提供更优化的传热成本和冷吸附器成本。例如，365可以在约15-25巴下操作，而365b在更高的50-70巴下操作。
在所示的实施例中，通过提供约57mtd的65bara氢(流315)和约626mtd的37.5bara氮(流320a)，该方法可以提供约11mtd液氢(流346)、42mtd中压氢(流62)、4mtd低压氢(流63)和543mtd的8.5bara中压氮(流329和334)。
在图4所示的实施例中，该过程利用了在氮管道上游任何未充分利用的氮压缩设备的可用容量。这种氮管道压缩设备可能没有得到充分利用，因为典型的设计要求在最恶劣的操作条件(例如，夏季、催化剂寿命终止、最大消耗器操作条件)下的容量，这种情况很少发生。在一个实施例中，氢液化器可以配置成周期性地操作(即，不连续)，使得在某些实施例中，提出氢液化器仅在可获得额外的氮压缩容量时才操作。在某些实施例中，结果是通常使用的氮再循环压缩机可以被去除，从而降低液化器的操作支出(运营成本)并且显著降低其资本支出(资本成本)。这在由于与氢泄压的整合而得到的资本支出和运营成本的节省之外。
图5与图4的不同之处在于，图5的实施例将高压氮气的至少一部分膨胀至中压以用作公共设施气体。另外，图5所示的实施例不需要未充分利用的氮压缩设备容量，而是包含了用于中压氮的消耗器。如果附近的工业场所(例如，MeOH设施)需要大量中压氮作为公共设施气体，这是特别有用的。在这种情况下，原本通过阀而浪费能量来泄放至中压消耗器的氮现在通过膨胀涡轮机来泄放至中压消耗器，以回收该能量，从而产生接近“零能量”的操作成本并显著降低液化器的资本支出。
这些高压氮流和氢流的至少一部分被转向至交换器，在交换器中它们被冷却、然后在它们各自的涡轮机中膨胀以提取能量并产生更冷的工艺流，所述工艺流然后在该交换器中被再加热以冷却涡轮机入口流和待液化的流体(例如，氢)。涡轮增压器的其他布置是可能的。
冷吸附器365、365b用于从进入该过程的非常冷的区段355中的氢流115a、115b中去除氮和氩，在这里这些组分将冻结并损坏设备。可以如下使用单个大型冷吸附器系统：将正在膨胀的氢流与待液化的氢流合并为产物、在暖区段中冷却、纯化并且然后从待膨胀的流中分离待液化的流(图4)。替代性地，可以对待液化的流和待膨胀的流使用单独的冷吸附器单元(图4和5)。替代性地，可以在组合的暖端上的纯化系统中除去氮和氩，从而可以去除冷吸附器。该吸附步骤的位置是独立的、并且不受图3与4之间的氮制冷循环差异的影响。
虽然与现有技术的PSA相比，本发明的某些实施例的PSA的大小可能明显增加(或添加了额外的PSA)，以产生用于在液化器中膨胀的氢，但是此成本被氢循环压缩机的去除和能量节省所抵消。
在一个实施例中，仅使用氢泄放来提供二次冷却(例如，低于-190℃的温度)，从而去除氢再循环压缩。在一个实施例中，离开液化单元的被加热的中压氢可以用作中压氢产物或被送回至工业场所(MeOH设施)，其中它与PSA出口气体混合并作为燃料被消耗。为氢液化器的冷端提供的这种制冷与对于暖(例如，>-190℃)区段氮循环的各种选择是独立的。结果是至少部分地减少了运营支出并降低了资本支出。
图6呈现了一个实施例的示意图，在该实施例中天然气流的泄放能量被用于生产LNG和另外的液化氮(LIN)二者。本实施例对于一体化的甲醇设施尤其有用，因为甲醇设施需要大流量的天然气，该天然气是从高压天然气管道(30至60bara)供应的并且被泄压至中压(2-5bara)并作为燃料气体被消耗。该高压天然气可以在涡轮膨胀器中膨胀，从而对氢液化器供冷以联合生产LNG和/或LIN。
天然气2在纯化单元510中被纯化掉二氧化碳和水而形成流512，该流接着在压缩机520中压缩而形成加压天然气522。加压天然气522然后被后冷却器525冷却，以去除压缩机520的压缩热。
对于暖端制冷(即，温度高于约-100℃)，加压天然气522然后在热交换器345内冷却，其中加压天然气的第一部分524在热交换器的第一中间点处被抽出，其中其在涡轮机530中膨胀至低压以形成第一膨胀部分532、然后在热交换器345中被加热并随后送至甲醇设施以用作燃料(参见图2的管线32和308)。替代性地，在离开后冷却器525后，加压天然气可以通过管线527被直接输送到涡轮机530的入口，而不是在交换器50将该气体冷却，以限制涡轮机的排出口的温度。第一膨胀部分532提供用于冷却并最终液化该天然气、以及冷却该氢的制冷的一部分。涡轮机530可以驱动发电机或增压器对如图所示的天然气总进料、仅对待液化的天然气、仅对待膨胀的天然气进行预增压，或对已膨胀的天然气进行后增压。
在一个可选的实施例中，如果待液化为产物LNG的天然气流含有重烃，诸如丁烷和更重的烃，则它可以在热交换器的第二个中间点处被抽出、并引入到液/气分离器或精馏塔(未示出)中，以除去重烃，留下的顶部气体中不含重烃。将顶部气体重新引入热交换器的中间和/或冷端，其在这里将其进一步冷却和液化以形成液化天然气(LNG)46。
图7提供了根据本发明实施例的可选空气分离单元的示意图。空气在主空气压缩机(MAC)210中被压缩，该主空气压缩机可以由马达(未示出)或蒸汽涡轮机215驱动(特别是如果可获得过量蒸汽的话)以产生压缩空气212。然后在纯化单元220中纯化压缩空气212，以去除将在低温下冻结的组分(例如，二氧化碳和水)。从那里，压缩空气212可以分成第一部分222和第二部分224，第二部分224在热交换器225中被冷却、并且然后被引入双蒸馏塔。第一部分222在空气增压压缩机(BAC)80中被进一步压缩，其中第一分量82在ASU热交换器225中被冷却、之后被引入中压塔230。剩余的增压空气流84单独或与来自氮管道100的氮流102组合(例如氮-空气混合物86)地被送至液化器，如图2所示。
所示的双蒸馏塔是空气分离单元中的典型双蒸馏塔，其包括低压塔240、共用冷凝器/再沸器250、以及高压塔230。富含氧的底部液体232跨过阀而膨胀、之后被引入低压塔240中进行进一步分离。氮流234也作为回流物被引入。液氧流244在低压塔240的底部区段作为产物产生、或在ASU热交换器225中汽化以产生气态氧。在低压塔240的顶部产生低压氮流242，并且在高压塔230的顶部产生中压氮流236。
在一个实施例中，低压氮流242可以被压缩机250进一步压缩并与中压氮流236合并、然后被压缩机260压缩以形成高压氮262，该高压氮然后可以将其引入氮管道100。替代性地，也可以将高压氮的一部分262直接输送到图1的液化器中，无需先进入氮管道100。
下表I给出了在现有技术中已知的一种方法中使用的各种压缩机与本发明的某些实施例的比较。如清楚示出的，本发明的某些实施例不需要氢再循环压缩机、氮再循环压缩机、或氢工艺入口压缩机。这样可以大大节省设备成本。
表I：标准氢液化器和本发明实施例的资本支出比较
在典型的独立氢液化器中，生产液氢的功率要求约为12kWh/kg液氢。理论上的夸克Ne/He方案被估计为5-7kWh/kg液氢。然而，本发明的实施例提供了远远更好的结果。例如，图4中所示的实施例得到约4.2kWh/kg液氢。使用的主要功率是来自未充分利用的氮管道容量的氮压缩。图5所示的实施例使用约0.9kWh/kg液氢，其功耗归因于低压氮闪蒸损失。图6所示的实施例可以使用“零能量”(例如，0kWh/kg所产生液氢)和约0.2kWh/kg LNG来将氢液化，而典型的小LNG单元使用0.5-0.7kWh/kg LNG。
在此所使用的暖温冷却被定义为在比待液化的氢流中的在氢纯化单元内除去的任何杂质的冰点更高的温度下进行的冷却。同样地，冷温冷却被定义为在比待液化的氢流中的在氢纯化单元中除去的任何杂质的冰点更低的温度下进行的冷却。对于氢的液化还应理解的是，暖制冷是在接近大气压下的液氮(即～-190℃)之上的温度，这是不同的，因为该水平的氮制冷可以以比更低温度-190℃至-252℃(这需要来自诸如氢、氦、氖/氦等制冷剂系统的更昂贵制冷)时更低的成本提供。
虽然已经结合其具体实施例描述了本发明，但显然鉴于前述说明，许多替代方案、修改、和变化对于本领域技术人员将是清楚的。因此，旨在包含如落入所附权利要求的精神和宽范围内的所有此类替代方案、修改、和变化。本发明可以适当地包括所披露的要素、由所披露的要素组成或基本由其组成，并且可以在不存在未披露要素的情况下实践。此外，提及顺序的语言，例如第一和第二，应在示例性意义上并且不在限制性意义上进行理解。例如，本领域技术人员可以认识到可以将某些步骤或装置组合成单一步骤/装置。
单数形式“一个/种(a/an)”和“该(the)”包括复数指示物，除非上下文另外清楚地指出。除非上下文另有明确规定，否则术语“约/大致”某个具体值包括该特定值加或减10％。
可选的或可选地是指，随后描述的事件或情况可能发生或可能不发生。本说明包括在其中该事件或情况发生的实例以及在其中该事件或情况不发生的实例。
本文的范围可以表述为从约一个具体值、和/或到约另一个具体值。当表述此种范围时，应理解的是另一个实施例是从该一个具体值和/或到该另一个具体值、连同在所述范围内的所有组合。

Claims (18)

1.一种用于将源自变压吸附器单元的加压氢气液化的方法，该方法包括以下步骤：
从甲醇生产单元中抽出含氢气体(311)；
将该含氢气体引入处于有效纯化该含氢气体的条件下的变压吸附器(PSA)单元以产生经纯化氢流(315)，其中，该经纯化氢流优选在至少15bara的压力下；
将该经纯化氢气送至处于对该氢气液化有效的条件下的氢液化单元，由此产生经液化的氢流(346)，
其中，该氢气液化单元被配置用于提供第一制冷源(340)和第二制冷源(350)，其中，该第一制冷源使用高压氮流(326)的膨胀(332)来提供制冷，其中，该第二制冷源使用高压氢气流(370)的膨胀来提供制冷，以产生暖的氢气流(62)，
其中，该高压氢气流是源自选自下组的氢流，该组由以下组成：该经纯化氢流(315a)、从第二PSA单元(317)抽出的第二经纯化氢流(315b)、及其组合，
其中，该PSA单元和该第二PSA单元优选地共用共同的进料流(311)。
2.如权利要求1所述的方法，其中，该PSA单元是甲醇设施的一部分。
3.如前述权利要求中任一项所述的方法，其中，该高压氮在一个或多个涡轮膨胀器(328，332)中膨胀、优选膨胀到至少4bara的压力并且用作公用事业气体。
4.如前述权利要求中任一项所述的方法，其中，将暖的氢气流在选自下组的单元中用作燃料气体(62，316)，该组由以下组成：在该PSA的上游的蒸汽甲烷重整器(SMR)、蒸汽锅炉、火焰加热器、及其组合。
5.如前述权利要求中任一项所述的方法，其中，该第二制冷源包括：
将该高压氢气流的第一部分在第一膨胀涡轮机(375a)中膨胀至第一压力；并且
将该高压氢气流的第二部分在第二膨胀涡轮机(375b)中膨胀至第二压力，
其中，该第一压力高于该第二压力。
6.如前述权利要求中任一项所述的方法，其中，该第一制冷源提供暖温冷却，并且该第二制冷源提供冷温冷却。
7.如前述权利要求中任一项所述的方法，其中，使用天然气泄放能量来提供第三制冷源(524，530，532)，其中，该第三制冷源提供暖温冷却。
8.如前述权利要求中任一项所述的方法，其中，使用源自空气分离单元(ASU)的空气气体(86)的泄放能量来提供第四制冷源，其中，源自ASU的空气气体是选自下组的气体流，该组由以下组成：来自空气增压压缩机(85)的被压缩且纯化的空气、氮流(102，262)、及其组合。
9.如前述权利要求中任一项所述的方法，进一步不包括以下步骤：使用由在该PSA单元和该氢液化单元下游的马达提供动力的压缩装置来压缩该经纯化氢流或该经膨胀的经纯化氢流，其中，这种经压缩的氢将提供该冷温制冷。
10.一种用于生产液氢的方法，该方法包括以下步骤：
将来自高压天然气管道(300)的加压天然气(302)引入处于有效产生经纯化氢流(315)的条件下的气体处理单元(HDS，SMR，MEOH，PSA)；并且
将该经纯化氢流引入处于有效产生液氢流的条件下的氢液化单元(346)，
其中，该氢液化单元对该经纯化氢流提供暖温冷却和冷温冷却，
其中，该暖温冷却是通过利用选自下组的加压流的泄放能量来提供的，该组由以下组成：源自氮管道的氮流(320)、液氮、源自该高压天然气管道(300)的天然气流(2)、源自空气分离单元(ASU)的空气气体(86)、及其组合，
其中，通过利用该经纯化氢流(315)的泄放能量来提供该冷温制冷。
11.如权利要求10所述的方法，进一步不包括以下步骤：使用由在该气体处理单元和该氢液化单元下游的马达提供动力的压缩装置来压缩该经纯化氢流或该经膨胀的经纯化氢流，其中，该经压缩的氢将提供该冷温制冷。
12.如权利要求10至11中任一项所述的方法，其中，该气体处理单元包括甲醇生产设施。
13.如权利要求10至12中任一项所述的方法，其中，该气体处理单元包括氨生产设施。
14.如权利要求10至13中任一项所述的方法，其中，在共用吸附器单元(365)中从正在液化的经纯化氢流和提供用于制冷的泄放能量的氢流中去除氩和/或氮。
15.如权利要求10至14中任一项所述的方法，其中，该冷温制冷由至少两个以串联布置来操作的涡轮机(375a，375b)提供。
16.如权利要求15所述的方法，其中，这些氢涡轮机中的一个或多个被配置用于驱动一个或多个增压器，其中，该一个或多个增压器用于对该经纯化氢流、该经膨胀的经加压氢流、或其组合加压。
17.如权利要求10至16中任一项所述的方法，其中，通过氢的泄放而提供的冷制冷由三个涡轮机提供，其中，氢在第一涡轮机(375a)中膨胀而产生第一膨胀氢流，该第一膨胀氢流的第一部分在第二涡轮机(375b)中进一步膨胀而产生第二膨胀氢流，该第一膨胀氢流的第二部分在第三涡轮机(375c)中冷却并膨胀而产生第三膨胀氢流，其中，该第二和第三膨胀氢流通过与正在冷却的氢流进行热交换而被加热。
18.如权利要求17所述的方法，其中，通过仅来自在该第一氢涡轮机之前的氢流的制冷来部分地冷却到该第一涡轮机的氢，其中，提供该冷却的氢流是由该第一、第二和第三膨胀氢流、第四膨胀氢流、储罐汽化流、及其组合组成。
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