CN113776275A - Lng冷能预冷下的氢气液化方法 - Google Patents

Lng冷能预冷下的氢气液化方法 Download PDF

Info

Publication number
CN113776275A
CN113776275A CN202111172623.3A CN202111172623A CN113776275A CN 113776275 A CN113776275 A CN 113776275A CN 202111172623 A CN202111172623 A CN 202111172623A CN 113776275 A CN113776275 A CN 113776275A
Authority
CN
China
Prior art keywords
hydrogen
liquefaction
lng
nitrogen
cold
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111172623.3A
Other languages
English (en)
Other versions
CN113776275B (zh
Inventor
杨兆铭
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.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN202111172623.3A priority Critical patent/CN113776275B/zh
Publication of CN113776275A publication Critical patent/CN113776275A/zh
Application granted granted Critical
Publication of CN113776275B publication Critical patent/CN113776275B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • F25J1/003—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
    • F25J1/0047—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
    • 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
    • F25J1/0047—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
    • F25J1/0052—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 vaporising a liquid refrigerant 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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • 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
    • 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
    • F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/007—Primary atmospheric gases, mixtures thereof
    • F25J1/0072—Nitrogen
    • 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
    • F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/008—Hydrocarbons
    • F25J1/0082—Methane
    • 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
    • F25J1/0203—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
    • F25J1/0205—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
    • 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
    • F25J1/0221—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 the cold stored in an external cryogenic component in an open refrigeration loop
    • 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
    • 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
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0292—Refrigerant compression by cold or cryogenic suction of the refrigerant gas
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/82—Processes or apparatus using other separation and/or other processing means using a reactor with combustion or catalytic reaction
    • 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
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/62—Liquefied natural gas [LNG]; Natural gas liquids [NGL]; Liquefied petroleum gas [LPG]
    • 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
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/02—Separating impurities in general from the feed 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
    • F25J2240/00—Processes or apparatus involving steps for expanding of process streams
    • F25J2240/60—Expansion by ejector or injector, e.g. "Gasstrahlpumpe", "venturi mixing", "jet pumps"
    • 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
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/90—Processes or apparatus involving steps for recycling of process streams the recycled stream being boil-off gas from storage
    • 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
    • F25J2250/00—Details related to the use of reboiler-condensers
    • F25J2250/02—Bath type boiler-condenser using thermo-siphon effect, e.g. with natural or forced circulation or pool boiling, i.e. core-in-kettle heat exchanger
    • 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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/14—External refrigeration with work-producing gas expansion loop
    • F25J2270/16—External refrigeration with work-producing gas expansion loop with mutliple gas expansion loops of the same refrigerant

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

本发明披露了一种充分利用LNG冷能的氢液化技术。主要原料氢气经预冷冷箱和液化冷箱后生产出液态氢气，预冷冷箱由LNG气化冷能和液氮气化冷能提供冷量，液化冷箱由氢气膨胀制冷循环提供冷量。在预冷冷箱内，利用LNG直接气化冷能和氮气制冷循环预冷原料氢气和氢气冷剂，LNG气化冷能还用来直接冷凝氮气制冷循环中压缩机出口氮气，实现LNG冷能的充分利用。在液化冷箱内，利用氢气膨胀制冷原理将预冷后的氢气液化。在板翅换热器原料低温氢气流道内填充正仲氢转化催化剂，实现换热同时正仲氢转化，产品液态氢中仲氢浓度大于95％，达到稳定存储要求。

Description

LNG冷能预冷下的氢气液化方法
技术领域
本发明涉及充分利用LNG气化冷能，最大程度降低氢气液化能耗的液化技术，尤其涉及一种LNG冷能预冷和氮气制冷循环预冷联合氢气多级膨胀的高效氢气液化技术。本液化技术方法有效解决了困扰氢气液化的两大难题，即如何降低单位液化能耗，如何提高单线液化规模。
背景技术
双碳目标下，全球氢能产业有望快速成长，发展空间巨大，氢气的安全高效储运是氢能产业的关键，将氢气低温液化后储运将极大的提高氢气储运的效率和安全性，但氢气液化十分困难，降温过程中正仲氢转化时释放大量的转化热，进一步增加的氢气制冷液化的难度，所以将氢气液化的能耗普遍很高，不同的液化工艺单位能耗约12-25kwh/kg，如何降低液化能耗，直接影响氢气产品的市场竞争力。
氢气产品的高端目标市场在东南沿海，而东南沿海分布着数十个LNG接收站，大量LNG冷能没有有效的利用起来，本发明技术仅需利用LNG接收站部分冷能将氢气液化能耗大幅下降，可以降到4-5kwh/kg以下，而且液态氢气的运输具有很高的灵活性和经济性。
发明内容
在预冷冷箱COLD BOX-1里布置三台换热器，第一台是PCHE换热器或高压板翅换热器，第二、三台是板翅换热器。在第一台换热器HE1-1内，LNG直接气化预冷原料氢气和高压氢气冷剂至114-120K；在第二台换热器HE1-2内，中、低压氢气冷剂将原料氢气高压氢气冷剂冷却至88-92K；在第三台换热器HE1-3内，利用热虹吸换热原理氮气制冷循环联合中压、低压氢气冷剂将原料氢气高压氢气冷剂冷却至80K。
热虹吸换热原理氮气制冷循环。利用LNG冷能将氮气压缩机LN2-C出口氮气冷凝成液氮，再节流至1.1-1.28bar进入液氮分离罐LN2-V，相对于第三台换热器，液氮分离罐应布置在适当相对高度以保证换热效率，液氮分离罐LN2-V底部出来的液氮从进入第三台换热器HE1-3底部进入，换热后利用虹吸效应以两相流动状态从顶部流出至液氮分离罐LN2-V，气相氮气从液氮分离罐顶部流出，进入氮气压缩机N2-C入口。
原料氢气在第三台换热器HE1-3内经液氮冷却至80K后进入吸附器ABSORBER，进一步脱除微量氧氩水等杂质实现纯化，再进入HE1-3充满正仲氢转化催化剂流道，进行催化转化。
氢气液化装置主要包括预冷冷箱COLD BOX-1和液化冷箱COLD BOX-2，除氮气冷凝换热器GN2-CONDENSER外所有的换热器和分离罐放置在冷箱内，预冷冷箱COLD BOX-1采用珠光砂发泡、微正压干燥氮气绝热保冷，液化冷箱COLD BOX-2采取抽真空绝热保冷。压缩机和膨胀机放置在冷箱外部。预冷冷箱与液化冷箱之间的管线采用真空管连接。
在液化冷箱COLD BOX-2里，布置六台板翅换热器，从预冷冷箱COLD BOX-1来的80K高压氢气冷剂2-3经第一台换热器HE2-1换热降温至70-71K后流出一分为二，一股高压氢冷剂2-5进行一级膨胀机H2-T1膨胀后进入HE2-2冷却后再进入二级膨胀机H2-T2、三级膨胀机H2-T3膨胀降压至2.6-2.9bar，该股中压氢冷剂物流2-13返流，作为冷流体先后流经HE2-4、HE2-3、HE2-2和HE2-1，为这4台换热器提供冷量，该股中压氢气冷剂物流2-21换热后温度78K，进入预冷冷箱COLD BOX-1，继续为换热器HE1-3、HE1-2提供冷量。另一股高压氢冷剂2-6先后经换热器HE2-2、换热器HE2-3、换热器HE2-4和换热器HE2-5换热后，温度降至29-31K，再经LH2-VALVE进一步节流降压降温，并流进液氢分离罐LH2-V进行气液分离，分离罐底部出来的液氢利用热虹吸原理进入HE2-6进行制冷换热，换热后低压两相流氢气冷剂2-20进入液氢分离罐LH2-V，其中分离出来的气相低压氢冷剂2-22，20-22K，返流相继经过换热器HE2-5、HE2-4、HE2-3、HE2-2和HE2-1换热，为这5台换热器提供冷量。该股低压氢气冷剂物流2-32换热后温度为78K，进入预冷冷箱COLD BOX-1，继续为换热器HE1-3、HE1-2提供冷量。氢气冷剂压缩机分两段压缩，从预冷冷箱COLD BOX-1换热后出来的低压气相氢气冷剂2-36和中压气相氢气冷剂2-25分别进入一段氢气冷剂压缩机入口和二段压缩机入口，压缩至20-30bar。
HE2-5液化后的原料氢气利用喷射器E-J将液氢储罐内来的液氢蒸发气BOH负压吸收，进入下一级换热器HE2-6进一步降温液化，液氢产品经过产品节流阀PRODUCT-VLVE进入储罐。
换热器HE1-3、HE2-1、HE2-2、HE2-3、HE2-4和HE2-5低温原料氢气流道内充填铁基正仲氢转化催化剂。
氢气冷剂压缩机H2-C1、H2-C2和氮气压缩机N2-C为低温压缩机，无需压缩机级间和出口冷却器，装置设备配置简单。
从LNG气化器入口LNG管路上接出分支管路引出LNG，LNG气化冷能利用后，天然气返回气化器出口天然气管路或其它下游天然气管路，通过LNG流量LNG-1、LNG-2调节来控制换热器HE1-1、换热器GN2-CONDENSER出口被冷介质原料氢气1-1和氮气3-1的冷却温度。
附图说明
图1，预冷冷箱内部流程与设备图、氢气冷剂压缩机图、氮气循环制冷系统示意图。
图2，液化冷箱内部流程与设备图、三级透平膨胀机、产品J/T阀、液氢储罐与液氢蒸发气示意图。
图3，LNG冷能预冷下的氢气液化技术方法系统图。
具体实施方式
本实施例，LNG冷能预冷下的氢气液化装置，具有设备数量少、液化能力大、高度集成、LNG冷能利用率高、液化效率优异的特点，装置包括：预冷冷箱、液化冷箱、连接预冷冷箱和液化冷箱间的绝热管道、氢气冷剂压缩机、氮气压缩机、氮气冷凝换热器、液氮节流阀、液氢产品J/T阀和透平膨胀机。
装置外部接口条件，净化后的原料氢气FEED-GH2，压力20-30bar；LNG来流可以是LNG接收站、LNG气化站等气化器入口LNG管路，压力2-90bar，分别接入LNG预冷换热器HE1-1换热器LNG1物流和氮气冷凝器GN2-CONDENSER上LNG2物流，气化后的天然气返回外部气化器出口管路。通过调节LNG流量LNG-1、LNG-2来控制换热器HE1-1、换热器GN2-CONDENSER出口被冷介质原料氢气1-1和氮气3-1的冷却温度。
净化合格的原料氢气1-0，压力20-30bar和高压氢气冷剂2-0，压力20-30bar，在预冷冷箱内，经HE1-1、HE1-2、HE1-3换热器冷却至80K，并在吸附器ABSORBER内进一步纯化，杂质总含量小于4mg/kg，油含量小于10ppbv，氧含量小于2ppbv，水含量小于1ppmv。纯化后的原料氢气返回H1-3原料氢气流道入口，流道中充填铁基正仲氢转化催化剂，实现80K温度下正仲氢转化达到该温度下正仲氢平衡浓度。纯化和正仲氢转化平衡后的80K原料氢气和高压氢冷剂进入液化冷箱COLD BOX-2。
从预冷冷箱COLD BOX-1来的80K原料氢气，经换热器HE1-3、HE2-1、HE2-2、HE2-3、HE2-4和HE2-5低温原料氢气流道，流道内充填铁基正仲氢转化催化剂，降温过程中同时进行正仲氢催化转化，HE2-5液化后的原料氢气温度为29-31K，利用喷射器E-J将液氢储罐内来的液氢蒸发气BOH负压吸收，进入下一级换热器HE2-6进一步降温催化转化，1-12温度为22-23K，液氢产品经过产品节流阀LH2-VLVE节流降压后进入液氢产品储罐。
从预冷冷箱COLD BOX-1来的80K高压氢气冷剂2-3经第一台换热器HE2-1换热降温至70-72K后流出一分为二，一股高压氢冷剂2-5进行一级膨胀机H2-T1膨胀后进入HE2-2冷却后再进入二级膨胀机H2-T2、三级膨胀机H2-T3膨胀降压至2.6-2.9bar，该股中压氢冷剂物流2-13返流，作为冷流体先后流经HE2-4、HE2-3、HE2-2和HE2-1，为这4台换热器提供冷量，该股中压氢气冷剂物流2-21换热后温度为78K，进入预冷冷箱COLD BOX-1，继续为换热器HE1-3、HE1-2提供冷量。另一股高压氢冷剂2-6先后经换热器HE2-2、换热器HE2-3、换热器HE2-4和换热器HE2-5换热后，温度降至29-31K，再经LH2-VALVE进一步节流降压降温，并流进液氢分离罐LH2-V进行气液分离，分离罐底部出来的液氢利用热虹吸原理进入HE2-6进行制冷换热，换热后低压两相流氢气冷剂2-20进入液氢分离罐LH2-V，其中分离出来的气相低压氢冷剂2-22，约20-22K，返流相继经过换热器HE2-5、HE2-4、HE2-3、HE2-2和HE2-1换热，为这5台换热器提供冷量。该股低压氢气冷剂物流2-32换热后温度为78K，进入预冷冷箱COLDBOX-1，继续为换热器HE1-3、HE1-2提供冷量。氢气冷剂压缩机分两段压缩，从预冷冷箱COLDBOX-1换热后出来的低压气相氢气冷剂2-36和中压气相氢气冷剂2-25分别进入一段氢气冷剂压缩机入口和二段压缩机入口，压缩至20-30bar。

Claims (10)

1.一种LNG冷能预冷下的氢气液化技术，其特征包括：
S1主要原料氢气经预冷冷箱和液化冷箱后生产出液态氢气，预冷冷箱由LNG气化冷能和氮气气化冷能提供冷量，液化冷箱由氢气膨胀制冷循环提供冷量。
S2在预冷冷箱内，利用LNG直接气化冷能和氮气制冷循环预冷原料氢气和高压氢气冷剂，LNG气化冷能还用来冷凝氮气制冷循环中压缩机出口氮气，实现LNG气化冷能的充分利用。
S3在液化冷箱内，利用氢气三级透平膨胀制冷将预冷后的氢气液化。
S4在板翅换热器低温原料氢气流道内填充正仲氢转化催化剂，实现换热的同时正仲氢转化，产品液态氢中仲氢浓度大于95％，达到稳定存储要求。
S5制冷剂为LNG、氮气和氢气，适用于LNG接收站、LNG气化站、FSRU等LNG气化冷能可利用场景，无需外购其它冷剂，极大降低氢气液化单位能耗。
2.按照权利要求1所述的液化技术，利用LNG气化冷能来直接预冷原料氢气和氢气冷剂，该换热器是PCH E换热器或板翅换热器。
3.按照权利要求2所述的液化技术，利用LNG直接气化冷能来冷凝氮气制冷循环中压缩机出口氮气，高压液氮经节流降压至近常压后进入液氮分离罐，利用热虹吸原理液氮通过气化提供冷量，两相流回至液氮分离罐，气相氮气进入氮气压缩机入口。
4.按照权利要求3所述的液化技术，原料氢气经液氮冷却至80K后进行微量氧氩水等杂质的吸附脱除，纯化后的氢气进入液化冷箱。
5.按照权利要求4所述的液化技术，高压氢气冷剂在液化冷箱内第一段换热器出口后一分为二，一股进行三级膨胀制冷，换热后为中压氢气冷剂，另一股利用节流阀和液氢分离罐热虹吸原理换热制冷，换热后为低压氢气冷剂。
6.按照权利要求5所述的液化技术，在液化冷箱里换热后的中压、低压两股气相氢气冷剂进入预冷冷箱第三段、第二段换热器进一步复温，释放冷量后进入氢气冷剂压缩机压缩。氢气冷剂压缩机分两段压缩，从预冷冷箱换热后出来的低压和中压气相氢气冷剂分别进入一段氢气冷剂压缩机入口和二段压缩机入口进行压缩。
7.按照权利要求6所述的液化技术，液化的原料氢气利用喷射器将液氢储罐内来的液氢蒸发气负压吸收，并进入下一级换热器进一步降温液化，液氢经过产品节流阀降压进入储罐。
8.按照权利要求7所述的液化技术，氢气液化装置分预冷冷箱和液化冷箱，出氮气冷凝换热器外所有的换热器和分离罐放置在冷箱内，预冷冷箱保冷方式是珠光砂发泡和氮气绝热，液化冷箱采取真空绝热。压缩机和膨胀机放置在冷箱外部。
9.按照权利要求8所述的液化技术，氢气冷剂压缩机和氮气压缩机为低温压缩机，无需压缩机级间和出口冷却器，装置设备配置简单，换热器为板翅换热器或PCH E换热器，低温氢气流道内充填正仲氢转化催化剂。
10.按照权利要求9所述的液化技术，LNG冷能利用方法为，从LNG气化器入口LNG管路上接出分支管路引出LNG流体，LNG气化冷能利用后，天然气返回气化器出口天然气管路或其它下游天然气管路，通过LNG流量调节来控制被冷介质原料氢气和氮气的冷却温度。
CN202111172623.3A 2021-10-08 2021-10-08 Lng冷能预冷下的氢气液化方法 Active CN113776275B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111172623.3A CN113776275B (zh) 2021-10-08 2021-10-08 Lng冷能预冷下的氢气液化方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111172623.3A CN113776275B (zh) 2021-10-08 2021-10-08 Lng冷能预冷下的氢气液化方法

Publications (2)

Publication Number Publication Date
CN113776275A true CN113776275A (zh) 2021-12-10
CN113776275B CN113776275B (zh) 2022-12-13

Family

ID=78855058

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111172623.3A Active CN113776275B (zh) 2021-10-08 2021-10-08 Lng冷能预冷下的氢气液化方法

Country Status (1)

Country Link
CN (1) CN113776275B (zh)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114322451A (zh) * 2021-12-20 2022-04-12 江苏国富氢能技术装备股份有限公司 制氢生产用的氢气液化装置
CN114353563A (zh) * 2022-01-10 2022-04-15 浙江大学 一种分温区组合式正仲氢连续转化低温氢气板翅式换热器
CN114439562A (zh) * 2022-01-19 2022-05-06 杨兆铭 Lng冷能高效混合冷剂发电方法
CN114518015A (zh) * 2022-02-14 2022-05-20 杨兆铭 一种采用氮透平膨胀预冷的氢气液化工艺
CN114777349A (zh) * 2022-06-16 2022-07-22 中海油能源发展股份有限公司采油服务分公司 一种制备过冷介质的膨胀制冷循环系统
CN114777411A (zh) * 2022-04-01 2022-07-22 中国科学院理化技术研究所 一种具再生管路的氢气液化装置
CN114777412A (zh) * 2022-04-01 2022-07-22 中国科学院理化技术研究所 一种具有热虹吸式氢过冷器的氢气液化装置
CN115342596A (zh) * 2022-08-08 2022-11-15 中海石油气电集团有限责任公司 一种氢气开式循环制冷系统
CN115371357A (zh) * 2022-08-19 2022-11-22 中国石油天然气集团有限公司 氢气循环制冷液化系统及工艺
CN116697686A (zh) * 2023-07-28 2023-09-05 中太海事技术(上海)有限公司 一种利用低温压缩的氢气制冷系统及其应用

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180038638A1 (en) * 2016-08-05 2018-02-08 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Integration of industrial gas site with liquid hydrogen production
CN109059419A (zh) * 2018-05-28 2018-12-21 张家港富瑞氢能装备有限公司 氢气液化预冷工艺
US20200141637A1 (en) * 2018-11-07 2020-05-07 L'Air Liquide, Société Anonyme pour I'Etude et I'Exploitation des Procédés Georges Claude Integration of hydrogen liquefaction with gas processing units
EP3676529A1 (de) * 2017-08-31 2020-07-08 Messer Group GmbH Vorrichtung und verfahren zum befüllen eines mobilen kältemitteltanks mit einem kryogenen kältemittel
KR20200109054A (ko) * 2019-03-12 2020-09-22 주식회사 한국초저온 액화 천연 가스의 냉열을 이용하는 수소 액화 장치
CN112361713A (zh) * 2020-10-30 2021-02-12 北京航天试验技术研究所 一种设置有并联透平膨胀机机组的氢气液化设备
CN112361711A (zh) * 2020-10-30 2021-02-12 北京航天试验技术研究所 一种设置有三个串联的透平膨胀机机组的氢气液化设备
KR20210072985A (ko) * 2019-12-10 2021-06-18 오성연료전지 주식회사 수소 액화 장치
CN113446815A (zh) * 2021-09-01 2021-09-28 杭州制氧机集团股份有限公司 一种采用混合制冷氢气液化设备及其使用方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180038638A1 (en) * 2016-08-05 2018-02-08 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Integration of industrial gas site with liquid hydrogen production
EP3676529A1 (de) * 2017-08-31 2020-07-08 Messer Group GmbH Vorrichtung und verfahren zum befüllen eines mobilen kältemitteltanks mit einem kryogenen kältemittel
CN109059419A (zh) * 2018-05-28 2018-12-21 张家港富瑞氢能装备有限公司 氢气液化预冷工艺
US20200141637A1 (en) * 2018-11-07 2020-05-07 L'Air Liquide, Société Anonyme pour I'Etude et I'Exploitation des Procédés Georges Claude Integration of hydrogen liquefaction with gas processing units
KR20200109054A (ko) * 2019-03-12 2020-09-22 주식회사 한국초저온 액화 천연 가스의 냉열을 이용하는 수소 액화 장치
KR20210072985A (ko) * 2019-12-10 2021-06-18 오성연료전지 주식회사 수소 액화 장치
CN112361713A (zh) * 2020-10-30 2021-02-12 北京航天试验技术研究所 一种设置有并联透平膨胀机机组的氢气液化设备
CN112361711A (zh) * 2020-10-30 2021-02-12 北京航天试验技术研究所 一种设置有三个串联的透平膨胀机机组的氢气液化设备
CN113446815A (zh) * 2021-09-01 2021-09-28 杭州制氧机集团股份有限公司 一种采用混合制冷氢气液化设备及其使用方法

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114322451A (zh) * 2021-12-20 2022-04-12 江苏国富氢能技术装备股份有限公司 制氢生产用的氢气液化装置
CN114322451B (zh) * 2021-12-20 2024-04-30 江苏国富氢能技术装备股份有限公司 制氢生产用的氢气液化装置
CN114353563A (zh) * 2022-01-10 2022-04-15 浙江大学 一种分温区组合式正仲氢连续转化低温氢气板翅式换热器
CN114353563B (zh) * 2022-01-10 2022-10-04 浙江大学 一种分温区组合式正仲氢连续转化低温氢气板翅式换热器
CN114439562A (zh) * 2022-01-19 2022-05-06 杨兆铭 Lng冷能高效混合冷剂发电方法
CN114518015A (zh) * 2022-02-14 2022-05-20 杨兆铭 一种采用氮透平膨胀预冷的氢气液化工艺
CN114777412A (zh) * 2022-04-01 2022-07-22 中国科学院理化技术研究所 一种具有热虹吸式氢过冷器的氢气液化装置
CN114777411A (zh) * 2022-04-01 2022-07-22 中国科学院理化技术研究所 一种具再生管路的氢气液化装置
CN114777349B (zh) * 2022-06-16 2022-09-06 中海油能源发展股份有限公司采油服务分公司 一种制备过冷介质的膨胀制冷循环系统
CN114777349A (zh) * 2022-06-16 2022-07-22 中海油能源发展股份有限公司采油服务分公司 一种制备过冷介质的膨胀制冷循环系统
CN115342596A (zh) * 2022-08-08 2022-11-15 中海石油气电集团有限责任公司 一种氢气开式循环制冷系统
CN115342596B (zh) * 2022-08-08 2023-12-01 中海石油气电集团有限责任公司 一种氢气开式循环制冷系统
CN115371357A (zh) * 2022-08-19 2022-11-22 中国石油天然气集团有限公司 氢气循环制冷液化系统及工艺
CN115371357B (zh) * 2022-08-19 2024-05-14 中国石油天然气集团有限公司 氢气循环制冷液化系统及工艺
CN116697686A (zh) * 2023-07-28 2023-09-05 中太海事技术(上海)有限公司 一种利用低温压缩的氢气制冷系统及其应用

Also Published As

Publication number Publication date
CN113776275B (zh) 2022-12-13

Similar Documents

Publication Publication Date Title
CN113776275B (zh) Lng冷能预冷下的氢气液化方法
CN113446815B (zh) 一种采用混合制冷氢气液化设备及其使用方法
CN104520660B (zh) 用于天然气液化的系统和方法
CN112361711A (zh) 一种设置有三个串联的透平膨胀机机组的氢气液化设备
CN112361712A (zh) 一种采用氦气制冷循环系统的氢气液化设备
CN110701870A (zh) 一种利用lng冷能的空分装置和方法
CN113503692A (zh) 氢液化系统
CN216620451U (zh) 一种lng重整制氢和lng冷能液化氢气一体化系统
CN214095167U (zh) 一种采用氦气制冷循环系统的氢气液化设备
CN102628634B (zh) 三循环复叠式制冷天然气液化系统及方法
CN113959176A (zh) 一种液化天然气闪蒸气中氦气的分离系统和方法
CN114518015A (zh) 一种采用氮透平膨胀预冷的氢气液化工艺
CN114777418B (zh) 一种冷凝法天然气bog提氦的系统
CN216204684U (zh) 基于双回路循环氢气制冷的氢气液化系统
CN113959175B (zh) 一种用于大规模制备液氢的方法与系统
CN216384787U (zh) 一种氢气液化设备及系统
CN114963688B (zh) 采用低温透平压缩循环的氢液化系统
CN110627609B (zh) 一种结合混合冷剂和丙烷辅助制冷的乙烷回收方法
CN110160315B (zh) 一种利用夜间廉价电力的液体空分装置及生产方法
JP2023531232A (ja) 水素冷却のための設備及び方法
US20230392859A1 (en) Cryogenic Gas Cooling System and Method
CN110186251A (zh) 一种适用于超大规模的三循环天然气液化装置及方法
CN212481844U (zh) 空分装置
CN216522650U (zh) 一种液氧液化空分装置
CN216845327U (zh) 一种利用液化天然气进行高纯甲烷提取液化的系统

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant