CN114087846B - 一种光电制氢储能与冷量回收耦合产干冰装置及使用方法 - Google Patents

一种光电制氢储能与冷量回收耦合产干冰装置及使用方法 Download PDF

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CN114087846B
CN114087846B CN202210046797.3A CN202210046797A CN114087846B CN 114087846 B CN114087846 B CN 114087846B CN 202210046797 A CN202210046797 A CN 202210046797A CN 114087846 B CN114087846 B CN 114087846B
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CN114087846A (zh
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韩一松
谭芳
彭旭东
姚蕾
李良英
王佳伟
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Hang Yang Group Co ltd
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Abstract

一种光电制氢储能与冷量回收耦合产干冰装置及使用方法，包括光电转换液氢储能单元：光电在光电转换液氢储能单元中参与电解水制备氢气，满足下游工艺需求后的富余氢气在此单元中经液化，输出液氢从而将间歇性光电能转换成氢能储存；电解水制氢不足但工业用氢连续时，工业尾气提纯CO2和空分氮气分别回收在此单元中作为冷源的低温液氢高、低品位冷量，输出液氮和液体CO2，分别用于光电转换液氢储能单元和制干冰，液氢复热供入下游工艺。本发明用于解决光伏发电间歇性、工业尾气CO2回收利用低效性、低温液氢能量利用率低以及干冰制备高能耗问题，可实现间歇性光电以液氢形式储存、优化回收液氢冷量用于制液氮和干冰，达到节能减排的目标。

Description

一种光电制氢储能与冷量回收耦合产干冰装置及使用方法
技术领域
本发明涉及能源转化、冷量回收领域，具体涉及一种光电制氢储能与冷量回收耦合产干冰装置及使用方法。
背景技术
近年来，化石燃料的加快消耗已经导致了越来越多的环境问题，各种工业用途排放尾气中CO2的含量相当高，控制温室气体CO2的排放引起全球的关注。除了直接减少CO2的发生量外，更重要的是将工业尾气中CO2进一步回收利用，不仅可以减少环境污染，促进低碳经济发展，而且可为企业增加经济效益，具有非常重要的环境、社会和经济意义。干冰，即固态二氧化碳，因其极易挥发、无毒、无味、相变时不会有液体生成即无残留等优点广泛应用在模具清洗、石油化工、印刷工业、食品冷冻、消防灭火及医药卫生等众多领域。目前，国内外CO2工业液化通常将常压CO2气体经过三级压缩加压至1.6~2.5MPa，采用制冷机组使其降温液化，液化CO2则通过节流膨胀制备干冰。此过程对二氧化碳的压缩和制冷机组的制冷量需要消耗大量的能量，因而如何有效的降低系统能耗是干冰制备工艺的主要改进方向和目标。
随着我国经济高速发展，各行业尤其煤化工对氢气的需求量逐年增大。电解水制氢工艺中无污染性气体排放，产物仅为氢气和氧气，是制备氢气的优选方法。绿色环保的太阳能发电可为电解水制氢提供能量来源，将光电充足时生产的富余氢气液化储存，当光电匮乏时将储存的液氢汽化供入下游工艺管网，从而满足工业连续用氢需求。目前，氢气液化工艺已经非常成熟，然而在液氢释能汽化再利用过程中却存在极大冷量损耗，液氢汽化器一般采用自然通风空浴式，未能实现约20K低温液氢汽化时冷量的优化回收，造成冷量浪费和冷污染。若将约20K低温液氢冷能利用技术与液体CO2和干冰制备技术相结合，不仅可显著降低液体CO2和干冰制备系统的工作压力和制冷设备的负荷，降低液体CO2和干冰制备过程中能耗和成本，促进对工业尾气中CO2的回收，减少碳排放量，还可有效地提高低温液氢的能量利用率，减少传统工艺中利用空气将液氢气化所引起的环境冷污染，有利于促进低温液氢产业的健康发展，具有良好的环境效益和社会效益。
发明内容
本发明要解决的技术问题是：提供一种光电制氢储能与冷量优化回收耦合联产干冰工艺路线，用于解决光伏发电间歇性、工业尾气CO2回收利用低效性、低温液氢能量利用率低以及干冰制备高能耗性问题。
为实现上述目的，本发明采用如下技术：一种光电制氢储能与冷量回收耦合产干冰装置，它包括光电转换液氢储能单元和液氢冷量优化回收制干冰单元，所述光电转换液氢储能单元和液氢冷量优化回收制干冰单元共用氢气-二氧化碳换热器II、氢-氮换热器、氢气-二氧化碳换热器I，其中光电转换液氢储能单元内还设有氢液化单元、空分装置、液氮储罐，所述液氮储罐与氢液化单元连接，氢液化单元通过液氢管道连接至低温液氢储罐，将光伏发电制备的氢气在成熟的氢液化单元中与来自液氮储罐的液氮换热后，再经自身膨胀制冷液化，通过液氢管道送入低温液氢储罐中储存，完成光电转换液氢过程，所述低温液氢储罐通过依次连接至氢-氮换热器、氢气-二氧化碳换热器I、氢气-二氧化碳换热器II，并在低温液氢储罐氢-氮换热器之间设有液氢经低温液氢泵，所述空分装置通过氮气管道依次连接至氢气-二氧化碳换热器I和氢-氮换热器最后将产物液氮存入液氮储罐中循环使用。
作为优选：所述液氢冷量优化回收制干冰单元内还设有CO2储罐、干冰机、液体CO2储罐，其中CO2储罐和干冰机之间通过三通管道依次与氢气-二氧化碳换热器II和氢气-二氧化碳换热器I连接，该氢气-二氧化碳换热器I的一端连接至液体CO2储罐，另一端通过管道与干冰机连接形成一个回路。
作为优选：所述氢-氮换热器、氢气-二氧化碳换热器I、氢气-二氧化碳换热器II为管壳式结构、板翅式结构、绕管式结构等中一种或几种组合。
作为优选：所述的低温液氢储罐、液氮储罐和低温液体CO2储罐可采用杜瓦罐或低温储槽。
作为优选：所述低温液氢泵可以为活塞式或离心式结构。
一种光电制氢储能与冷量回收耦合产干冰装置的使用方法，所述方法包括如下步骤：
步骤1：光伏发电制备的氢气在成熟的氢液化单元中与来自液氮储罐的液氮换热后，再经自身膨胀制冷液化，通过液氢管道送入低温液氢储罐中储存，完成光电转换液氢过程；
步骤2：自空分装置的氮气经氮气管道送入氢气-二氧化碳换热器I换热预冷，预冷氮气通过氢-氮换热器与液氢换热液化储存在液氮储罐中；可给步骤1使用；
步骤3：低温液氢储罐中的液氢经低温液氢泵加压依次送入氢-氮换热器、氢气-二氧化碳换热器I、氢气-二氧化碳换热器II复热后送入下游工艺管网；
步骤4：来自气体CO2储罐的常温CO2与干冰机中低温CO2气体预先混合，混合CO2经CO2压缩机压缩后送入氢气-二氧化碳换热器II进一步换热降温预冷，预冷CO2送入氢气-二氧化碳换热器I中换热液化储存在液体CO2储罐中，储罐中带压液体CO2最后送入干冰机中制备干冰，其中部分液体CO2吸热升温汽化为低温气体进入循环回路，另一部分液体CO2凝固为干冰送入干冰储罐；
所述步骤1发生在光电充足，在光电电解水制备氢气满足下游工艺需求后有富余氢气在所述光电转换液氢储能单元液化，输出液氢从而将间歇性光电能转换成氢能储存；步骤2、步骤3、步骤4同时运行，且氢气-二氧化碳换热器II、氢-氮换热器、氢气-二氧化碳换热器I为光电转换液氢储能单元和液氢冷量优化回收制干冰单元共用换热器。
本发明具有的有益效果如下：
通过将间歇性光电以液氢形式储存，有效解决因光电波动难以为工业持续性供氢问题；冷量优化回收工艺将液氢汽化时的高、低品位冷量分别用于制备液氮和干冰，有效减少设备投资和运行成本。本发明工艺路线中将~20K低温液氢冷能利用技术与液体CO2和干冰制备技术相结合，显著降低液体CO2和干冰制备能耗和成本，促进工业尾气中CO2的回收，减少碳排放量。同时，可有效提高低温液氢的能量利用率，减少传统工艺所引起的环境冷污染，促进低温液氢产业健康发展。
附图说明
图1是本发明结构示意图。
具体实施方式
下面将结合附图对本发明作详细的介绍：如图1所示，一种光电制氢储能与冷量回收耦合产干冰装置，它包括光电转换液氢储能单元和液氢冷量优化回收制干冰单元，所述光电转换液氢储能单元和液氢冷量优化回收制干冰单元共用氢气-二氧化碳换热器II13、氢-氮换热器7、氢气-二氧化碳换热器I11，其中光电转换液氢储能单元内还设有氢液化单元4、空分装置9、液氮储罐8，所述液氮储罐8与氢液化单元4连接，氢液化单元4通过液氢管道3连接至低温液氢储罐5，将光伏发电制备的氢气在成熟的氢液化单元4中与来自液氮储罐8的液氮换热后，再经自身膨胀制冷液化，通过液氢管道3送入低温液氢储罐5中储存，完成光电转换液氢过程，所述低温液氢储罐5通过依次连接至氢-氮换热器7、氢气-二氧化碳换热器I11、氢气-二氧化碳换热器II13，并在低温液氢储罐5与 氢-氮换热器7之间设有低温液氢泵6，所述空分装置9通过氮气管道10依次连接至氢气-二氧化碳换热器I11和氢-氮换热器7最后将产物液氮存入液氮储罐8中循环使用，所述液氢冷量优化回收制干冰单元内还设有CO2储罐12、干冰机15、液体CO2储罐14，其中CO2储罐12和干冰机15之间通过三通管道依次与氢气-二氧化碳换热器II13和氢气-二氧化碳换热器I11连接，该氢气-二氧化碳换热器I11的一端连接至液体CO2储罐14，另一端通过管道与干冰机15连接形成一个回路，所述氢-氮换热器7、氢气-二氧化碳换热器I11、氢气-二氧化碳换热器II13为管壳式结构、板翅式结构、绕管式结构等中一种或几种组合，所述低温液氢储罐5、液氮储罐8和低温液体CO2储罐14可采用杜瓦罐或低温储槽，所述低温液氢泵6可以为活塞式或离心式结构。
一种光电制氢储能与冷量回收耦合产干冰装置的使用方法，所述方法包括如下步骤：
步骤1：光伏发电制备的氢气在成熟的氢液化单元4中与来自液氮储罐8的液氮换热后，再经自身膨胀制冷液化，通过液氢管道3送入低温液氢储罐5中储存，完成光电转换液氢过程；
步骤2：自空分装置9的氮气经氮气管道10送入氢气-二氧化碳换热器I11换热预冷，预冷氮气通过氢-氮换热器7与液氢换热液化储存在液氮储罐8中；可给步骤1使用；
步骤3：低温液氢储罐5中的液氢经低温液氢泵6加压依次送入氢-氮换热器7、氢气-二氧化碳换热器I11、氢气-二氧化碳换热器II13复热后送入下游工艺管网；
步骤4：来自气体CO2储罐12的常温CO2与干冰机中低温CO2气体预先混合，混合CO2经CO2压缩机16压缩后送入氢气-二氧化碳换热器II13进一步换热降温预冷，预冷CO2送入氢气-二氧化碳换热器I11中换热液化储存在液体CO2储罐14中，储罐中带压液体CO2最后送入干冰机15中制备干冰，其中部分液体CO2吸热升温汽化为低温气体进入循环回路，另一部分液体CO2凝固为干冰送入干冰储罐；
所述步骤1发生在光电充足，在光电电解水制备氢气满足下游工艺需求后有富余氢气在所述光电转换液氢储能单元液化，输出液氢从而将间歇性光电能转换成氢能储存；步骤2、步骤3、步骤4同时运行，且氢气-二氧化碳换热器II13、氢-氮换热器7、氢气-二氧化碳换热器I11为光电转换液氢储能单元和液氢冷量优化回收制干冰单元共用换热器。
具体实施例：
例如约0.15MPa，25℃氮气在氢气-二氧化碳换热器I11与低温氢气换热预冷，预冷氮气进一步在氢-氮换热器7与来自低温液氢储罐5经低温液氢泵6加压至约5.5MPa的液氢换热，充分回收约20K液氢高品位冷量后液化，储存在低温液氮储罐8中。来自CO2储罐的常温常压CO2与干冰机中约0.11MPa低温气体CO2混合，混合CO2经CO2压缩机16压缩至约0.6MPa，随后送入氢气-二氧化碳换热器II13与出氢气-二氧化碳换热器I11的约5.5MPa的低温氢气换热预冷，预冷CO2随后送入氢气-二氧化碳换热器I11与来自氢-氮换热器7的低温氢气进一步换热后液化，送入液体CO2储罐14中储存，带压液体CO2送入干冰机16节流膨胀制干冰，其中部分液体CO2吸热汽化为低温CO2气体进入循环回路，另一部分液体CO2凝固为干冰送入干冰储罐供给干冰用户。在此工艺路线中，约20K液氢经氢-氮换热器7、氢气-二氧化碳换热器I11、氢气-二氧化碳换热器II13复热后送入下游工艺管网。
本发明在光伏发电匮乏时，液氢通过液氢冷量优化回收制干冰单元汽化供入下游工艺。在~20K低温液氢汽化过程中，优化回收高、低品位的冷量分别用于氮气制液氮和工业尾气提纯CO2低成本制备干冰。

Claims (1)

1.一种光电制氢储能与冷量回收耦合产干冰装置的使用方法，该装置包括光电转换液氢储能单元和液氢冷量优化回收制干冰单元，其特征在于：所述光电转换液氢储能单元和液氢冷量优化回收制干冰单元共用氢气-二氧化碳换热器II（13）、氢-氮换热器（7）、氢气-二氧化碳换热器I（11），其中光电转换液氢储能单元内还设有氢液化单元（4）、空分装置（9）、液氮储罐（8），所述液氮储罐（8）与氢液化单元（4）连接，氢液化单元（4）通过液氢管道（3）连接至低温液氢储罐（5），将光伏发电制备的氢气在成熟的氢液化单元（4）中与来自液氮储罐（8）的液氮换热后，再经自身膨胀制冷液化，通过液氢管道（3）送入低温液氢储罐（5）中储存，完成光电转换液氢过程，所述低温液氢储罐（5）通过依次连接至氢-氮换热器（7）、氢气-二氧化碳换热器I（11）、氢气-二氧化碳换热器II（13），并在低温液氢储罐（5）氢-氮换热器（7）之间设有液氢经低温液氢泵（6），所述空分装置（9）通过氮气管道（10）依次连接至氢气-二氧化碳换热器I（11）和氢-氮换热器（7）最后将产物液氮存入液氮储罐（8）中循环使用；
所述液氢冷量优化回收制干冰单元内还设有CO2储罐（12）、干冰机（15）、液体CO2储罐（14），其中CO2储罐（12）和干冰机（15）之间通过三通管道依次与氢气-二氧化碳换热器II（13）和氢气-二氧化碳换热器I（11）连接，该氢气-二氧化碳换热器I（11）的一端连接至液体CO2储罐（14），另一端通过管道与干冰机（15）连接形成一个回路；
所述氢-氮换热器（7）、氢气-二氧化碳换热器I（11）、氢气-二氧化碳换热器II（13）为管壳式结构、板翅式结构、绕管式结构中一种或几种组合；
所述低温液氢储罐（5）、液氮储罐（8）和低温液体CO2储罐（14）可采用杜瓦罐或低温储槽；所述低温液氢泵（6）可以为活塞式或离心式结构；
所述使用方法包括如下步骤：
步骤1：光伏发电制备的氢气在成熟的氢液化单元（4）中与来自液氮储罐（8）的液氮换热后，再经自身膨胀制冷液化，通过液氢管道（3）送入低温液氢储罐（5）中储存，完成光电转换液氢过程；
步骤2：自空分装置（9）的氮气经氮气管道（10）送入氢气-二氧化碳换热器I（11）换热预冷，预冷氮气通过氢-氮换热器（7）与液氢换热液化储存在液氮储罐（8）中；可给步骤1使用；
步骤3：低温液氢储罐（5）中的液氢经低温液氢泵（6）加压依次送入氢-氮换热器（7）、氢气-二氧化碳换热器I（11）、氢气-二氧化碳换热器II（13）复热后送入下游工艺管网；
步骤4：来自气体CO2储罐（12）的常温CO2与干冰机中低温CO2气体预先混合，混合CO2经CO2压缩机（16）压缩后送入氢气-二氧化碳换热器II（13）进一步换热降温预冷，预冷CO2送入氢气-二氧化碳换热器I（11）中换热液化储存在液体CO2储罐（14）中，储罐中带压液体CO2最后送入干冰机（15）中制备干冰，其中部分液体CO2吸热升温汽化为低温气体进入循环回路，另一部分液体CO2凝固为干冰送入干冰储罐；
所述步骤1发生在光电充足，在光电电解水制备氢气满足下游工艺需求后有富余氢气在所述光电转换液氢储能单元液化，输出液氢从而将间歇性光电能转换成氢能储存；步骤2、步骤3、步骤4同时运行，且氢气-二氧化碳换热器II（13）、氢-氮换热器（7）、氢气-二氧化碳换热器I（11）为光电转换液氢储能单元和液氢冷量优化回收制干冰单元共用换热器。
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