CN114518015A - 一种采用氮透平膨胀预冷的氢气液化工艺 - Google Patents

一种采用氮透平膨胀预冷的氢气液化工艺 Download PDF

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CN114518015A
CN114518015A CN202210151058.0A CN202210151058A CN114518015A CN 114518015 A CN114518015 A CN 114518015A CN 202210151058 A CN202210151058 A CN 202210151058A CN 114518015 A CN114518015 A CN 114518015A
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杨兆铭
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Abstract

本发明披露了一种采用氮膨胀预冷的氢气液化技术。主要是原料氢气经预冷冷箱和液化冷箱后生产出液态氢气，预冷冷箱由氮气透平膨胀工艺提供冷量，液化冷箱由氢气膨胀制冷循环提供冷量。在预冷冷箱内，利用氮气透平膨胀制冷循环将原料氢气和高压氢气冷剂冷却至80K。在液化冷箱内，利用氢气透平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

一种采用氮透平膨胀预冷的氢气液化工艺
技术领域
本发明涉及采用氮气透平膨胀制冷循环作为预冷方式的氢气液化工艺，流程设计具有独立性强、液化规模大、简洁高效的技术特点。
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，我国大力支持在西北采用风光电进行电解水制氢，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。
2021111726233号发明专利，是本发明人前期针对具有LNG冷能利用条件的氢气液化技术发明，其技术特征为采用LNG气化冷能进行氢气预冷，LNG冷能利用下的氢液化工艺具有液化效率高的特点，但其主要适用于具有LNG冷能利用条件的应用场景，两者20k氢气冷箱技术相同，本发明在预冷技术上进行创新，增加了氢液化技术的适用独立性，扩大了氢液化技术应用场景。
201820802535.4号专利，其技术特征为采用液氮气化冷能进行氢气预冷，其预冷技术路线与本发明完全不同，该氢液化工艺，需要制备和提供液氮进行氢气预冷。
发明内容
在预冷冷箱COLD BOX-1里布置四台PCHE换热器或高压板翅换热器换热器、两套氮气透平膨胀压缩机和氢气低温吸收纯化设备，氮气制冷循环的氮气压缩机和冷却器布置在冷箱外部。
通过一个氮气透平压缩膨胀制冷循环预冷原料氢气和高压氢气冷剂至80k，氮气透平压缩膨胀制冷循环过程中氮气为气相，预冷冷箱内同时实现从20k液化冷箱返回的中低压氢气冷剂的冷量回收。
氮气透平压缩膨胀制冷循环流程设计发明见图1，原料氢气FEED-GH2和高压氢气冷剂2-40先后经HE1-1、HE1-2、HE1-3和HE1-4四个预冷换热器温度降低至约80k，原料氢气连接管道为1-0、1-1、1-2、1-3、1-4，1-5高压氢气冷剂连接管道为2-0、2-1、2-2、2-3，原料氢气在末级换热器HE1-4进行正仲氢催化转化，在ABSORBER吸收纯化；从20k液化冷箱返回的中压氢气冷剂2-21、低压氢气冷剂2-32进入预冷冷箱COLD BOX1返流，先后经HE1-4、HE1-3、HE1-2和HE1-1四个预冷换热器，复温至常温出预冷冷箱COLD BOX1，进入氢气冷剂压缩机增压，中压氢气冷剂连接管道为2-23、2-25、2-27、2-29，低压氢气冷剂连接管道为2-32、2-34、2-36、2-38、2-40。
氮气透平压缩膨胀制冷循环流程设计发明见图1，提供预冷冷量的氮气制冷循环流程包括：换热后的低压氮气3-10从预冷冷箱出来先后经N2-C1压缩，N2-COOLER1冷却、第一级氮气透平膨胀压缩端N2-T1-C压缩、N2-COOLER3冷却、第二级氮气透平膨胀压缩端N2-T2-C压缩、N2-COOLER2冷却后，常温高压氮气冷剂3-2，先后经第一级换热器HE1-1冷却、第一级氮气透平膨胀端N2-T1膨胀降压，物流3-4经第三级换热器HE1-3冷却、第二级氮气透平膨胀端N2-T2再次膨胀降压降温，冷物流3-6，返流先后经HE1-1、HE1-2、HE1-3和HE1-4四个换热器，为预冷冷箱COLD BOX1提供冷量，氮气冷剂复温后，物流3-10流出预冷冷箱再次进入氮气压缩机N2-C1压缩，实现氮气冷剂制冷循环。
氮气压缩膨胀制冷循环流程设计发明见图1，从预冷冷箱COLD BOX1出来的中低压氢气冷剂经低压氢气压缩机H2-C2、高压氢气压缩机H2-C1增压，经氢气冷剂冷却器H2-COOLER1冷却至常温后，高氢冷剂再次进入预冷冷箱COLD BOX1，实现氢冷剂制冷循环。
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，氮气透平膨胀制冷循环作为预冷的氢气液化技术系统图。
具体实施方式
结合附图及本实施例对本发明作以下详细说明，所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本实施例，氮气膨胀制冷循环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、独立性强、液化效率优异的特点，装置包括：预冷冷箱、液化冷箱、冷箱内板翅换热器、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、氮气透平膨胀增压机、液氢产品J/T阀和透平膨胀机等。
净化合格的原料氢气FEED-GH2，压力20-40bar和高压氢气冷剂，压力20-40bar，在预冷冷箱内，经HE1-1、HE1-2、HE1-3、HE1-4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H1-4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1-5和高压氢冷剂2-3进入液化冷箱COLD BOX-2。
换热后的低压氮气3-10从预冷冷箱出来先后经N2-C1压缩，N2-COOLER1冷却、第一级氮气透平膨胀压缩端N2-T1-C压缩、N2-COOLER3冷却、第二级氮气透平膨胀压缩端N2-T2-C压缩、N2-COOLER2冷却后，常温高压氮气冷剂3-2，先后经第一级换热器HE1-1冷却、第一级氮气透平膨胀端N2-T1膨胀降压，物流3-4经第三级换热器HE1-3冷却、第二级氮气透平膨胀端N2-T2再次膨胀降压降温，冷物流3-6，返流先后经HE1-1、HE1-2、HE1-3和HE1-4四个换热器，为预冷冷箱COLD BOX1提供冷量，氮气冷剂复温后，物流3-10流出预冷冷箱再次进入氮气压缩机N2-C1压缩，实现氮气冷剂制冷循环。
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，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，达到液氢产品温度，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，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，进入预冷冷箱COLD BOX-1。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，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，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，进入预冷冷箱COLD BOX-1复温提供冷量。

Claims (2)

1.一种采用氮透平膨胀预冷的氢气液化工艺，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，预冷冷箱由氮气透平膨胀制冷循环提供冷量，液化冷箱由氢气膨胀制冷循环提供冷量。
S2在预冷冷箱内，利用氮气透平膨胀制冷循环预冷原料氢气和高压氢气冷剂，换热器为高压板翅换热器，预冷冷箱内同时实现20k液化冷箱中低压氢气返回冷剂的冷量回收。
S3在液化冷箱内，利用氢气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制冷剂为氮气和氢气，独立性强，流程简洁、效率高，特别适用于风光电电解水制氢和石化产氢的氢气液化。
2.按照权利要求1所述的液化技术，氢气液化装置分预冷冷箱和液化冷箱，板翅换热器和低温氮气透平端放置在冷箱内，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。
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