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CN114232005B - 一种电解水制氢与低温耦合的储能装置及储能方法 - Google Patents

一种电解水制氢与低温耦合的储能装置及储能方法 Download PDF

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CN114232005B
CN114232005B CN202111286736.6A CN202111286736A CN114232005B CN 114232005 B CN114232005 B CN 114232005B CN 202111286736 A CN202111286736 A CN 202111286736A CN 114232005 B CN114232005 B CN 114232005B
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hydrogen
liquid
secondary refrigerant
energy storage
heat exchanger
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CN114232005A (zh
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韩一松
谭芳
彭旭东
姚蕾
李良英
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Hang Yang Group Co ltd
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Hang Yang Group Co ltd
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Priority to DE102022128800.5A priority patent/DE102022128800A1/de
Priority to US18/051,033 priority patent/US20230138866A1/en
Priority to FR2211357A priority patent/FR3128720A1/fr
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Abstract

一种电解水制氢与低温耦合的储能装置及储能方法，用于解决光电资源不连续与生产用绿氢连续化要求矛盾的问题。所述装置包括液氮预冷氢气液化系统、液氢‑液氮换热系统、冷能储存系统及空气分离装置冷能利用系统，本发明系统间高度耦合，通过储氢的形式，可实现最大限度的利用光电可再生能源，在实现高效储能调峰的同时，能够有效降低绿氢制备利用的能耗成本，达到节能效果，具有良好的推广前景。

Description

一种电解水制氢与低温耦合的储能装置及储能方法
技术领域
本发明涉及太阳能可再生能源发电与绿电水电解制氢、氢气液化储能、氢能领域，具体涉及一种电解水制氢与低温耦合的储能装置及储能方法。
背景技术
以太阳能为代表的可再生能源，因受自然环境因素（季节、天气）的影响极大，其发电过程中能量输入及功率输出无法达到像化石能源那样的精确控制，具有波动大、间断性、随机性、不可控等特点，难以直接接入电网加以利用，导致大规模弃光的现象发生。因此，如何有效平抑光电功率波动、提升光电消纳能力，已经成为限制光电大规模发展的关键技术瓶颈。储能系统作为能量缓冲手段，可以有效平抑光电功率波动，减少弃光弃电，将在推动可再生能源的合理利用进展中扮演越来越重要的角色。
氢能以其优秀的能量密度、能量利用效率和清洁性，以及电能、核能、太阳能、风能、水能等均可转换成氢能加以储存、运输或直接使用，被誉为最佳的碳中和能源载体，将在“脱碳”过程中发挥关键作用。氢气可通过天然气或化石燃料重整、工业副产氢纯化、可再生电电解等大规模方式制备获得，而其中利用太阳能等可再生能源发电电解所制得的“绿氢”，由于其制备过程中没有碳排放或碳排放量很少，更是成为未来能源的“最终目标”。氢作为能源载体用于集中处理可再生资源的使用已在全世界开始推广，有利于可再生资源和氢能的携手发展，利用市场前景广泛。目前氢能大多数用于传统工业领域，如炼油、合成氨、生产甲醇等方面，而采用太阳能等可再生能源发电电解制备的原料氢气流量的不稳定，将直接对下游工艺产生极大的影响。因而如何利用不连续性、波动性大的太阳能等可再生能源制备连续性供应的“绿氢”是当前研究的热点和难点。
为保障“绿氢”的持续性供应，当可再生能源发电系统电量充足，即日照充足时，该阶段发出的绿电通过水电解制氢能够生产足量氢气，作为原料气供应给下游工厂、企业的同时还有部分富余氢气，为进一步充分利用富余氢气，可将富余氢气作为能源储存便于能源短缺阶段的进一步供能。目前的储氢技术主要包括高压气态储氢、低温液态储氢、有机液态储氢以及固态储氢等类型。液氢储能以其存储密度和储运效率高的优点，成为更适用于大规模长距离储运需求的氢储能形式。利用氢气液化系统将这光电绿电解制氢的富余氢气液化后送入液氢储罐进行储存。当可再生能源发电系统因环境变化而导致发电量不足时，如夜晚太阳能发电系统无法提供绿电解制氢所需的电量，为了持续向下游工厂提供稳定的原料氢气，只需将储罐内的液氢汽化为氢气后供入下游工艺管网。但氢液化过程由于氢气沸点（20K）极低，液化制冷带来的能耗较大，如何在工业级大规模储氢应用中降低能耗，成为储氢的关键，也是“绿氢”推动太阳能等可再生资源的合理利用和发展壮大的关键。
发明内容
本发明要解决的技术问题是：提供一种电解水制氢与低温耦合的储能装置及储能方法，用于解决光电资源不连续与生产用氢连续化要求矛盾的问题。通过储液氢的形式，实现最大限度的利用光电可再生能源，并在实现高效储能调峰的同时，有效降低绿氢制备利用的能耗成本，达到节能效果，为实现上述目的，本发明采用的如下技术：一种电解水制氢与低温耦合的储能装置，所述装置包括液氮预冷氢气液化系统、液氢-液氮换热系统、冷能储存系统及空气分离装置冷能利用系统；所述液氮预冷氢气液化系统包括液氮输入系统、氮气输出系统、液氢输出系统和氢气液化系统，各个系统之间通过管道连接和阀门控制；所述液氢-液氮换热系统包括液氢储罐、液氢泵、液氢-液氮换热器、液氮储罐，各个系统之间通过管道连接和阀门控制，用于汽化液氢并液化氮气，其中所述液氢储罐的液氢输入端连接于所述液氮预冷氢气液化系统的液氢输出系统，所述液氢泵的液氢输入端连接于所述液氢储罐的液氢输出端，所述液氢-液氮换热器的液氢输入端连接于所述液氢泵的液氢输出端，所述液氢-液氮换热器的氮气输入端连接于所述空气分离装置冷能利用系统的空气分离装置产品氮气输出系统的氮气输出端，所述液氢-液氮换热器的液氮输出端连接于所述液氮储罐的液氮输入端，所述液氮储罐的液氮输出端连接于所述液氮预冷氢气液化系统的所述液氮输入系统的输入端。
作为优选：所述冷能储存系统包括氢气-载冷剂换热器、载冷剂泵、载冷剂-冷能储存换热器、载冷剂储罐，冷能储罐，各个系统之间通过管道连接和阀门控制，用于复热氢气并储存冷能，其中所述氢气-载冷剂换热器的氢气输入端连接于所述液氢-液氮换热器的氢气输出端，所述氢气-载冷剂换热器的载冷剂输出端连接于所述载冷剂泵的载冷剂输入端，所述载冷剂泵的载冷剂输出端连接于所述载冷剂-冷能储存换热器的载冷剂输入端，所述载冷剂-冷能储存换热器的载冷剂输出端连接于所述氢气-载冷剂换热器的载冷剂输入端，所述载冷剂-冷能储存换热器的水输出端连接于所述冷能储罐的输入端，所述载冷剂储罐通过管道和阀门连接于所述载冷剂泵的载冷剂输入端。
作为优选：所述空气分离装置冷能利用系统包括循环水系统、水冷塔、空气分离装置产品氮气输出系统，空气分离装置冷冻水输入系统，各个系统之间通过管道连接和阀门控制，所述循环水系统的输出端连接于所述载冷剂-冷能储存换热器的水输入端，所述冷能储罐的输出端连接于所述水冷塔的上部输入端，所述氮气输出系统的输出端连接于所述水冷塔的下部输入端，所述水冷塔的底部输出端连接于所述空气分离装置冷冻水输入系统的输入端。
作为优选：所述液氢-液氮换热器、氢气-载冷剂换热器、载冷剂-冷能储存换热器均为绕管式换热器或板面式换热器。
作为优选：所述水冷塔为填料塔。
一种应用于上述储能装置的储能方法，包括以下步骤：步骤1：当光电绿色电解水制氢气过量时，过量氢气可经氢气液化系统液化，其中液氮作为氢液化的预冷冷源，液化后的液氢送入液氢储罐进行储存，汽化复热到常温的氮气由氮气输出系统通过管道进入水冷塔的下部后被从冷能储罐过来的低温水进入水冷塔上部后喷淋，低温水被进一步冷却，有利于空气分离装置后续的工艺，节省了空气分离装置的能耗。
步骤2：当光电等可再生能源发电系统因环境变化，如日照减弱而导致绿色电解水制氢不足时，储存于液氢储罐的液氢经液氢泵加压后进入液氢-液氮换热器汽化复热后又进入氢气-载冷剂换热器复热得到常温氢气，用来补充绿色电解水的制氢不足。同时产品氮气输出系统的常温氮气进入液氢-液氮换热器用来提供热源汽化复热液氢，其自身被液化冷凝成液氮后进入液氮储罐，可作为氢气液化时液氮预冷的部分补充。同时载冷剂进入氢气-载冷剂换热器用来提供热源复热氢气，其自身被冷却后经载冷剂泵加压后进入载冷剂-冷能储存换热器，用来冷却从循环水系统过来的常温水，常温水被冷却成低温水后出载冷剂-冷能储存换热器进入冷能储罐，冷能储罐的低温水可通过管道和阀门进入水冷塔上部进行喷淋，进一步降低水温。
作为优选：所述载冷剂为无机、有机化合物或其混合溶液或其水溶液。进一步的，所述载冷剂以有机化合物水溶液为主要优选，如乙二醇水溶液、丙二醇水溶液、甲醇、甲醇水溶液或乙醇水溶液。
作为优选：所述水冷塔装填为填料。
本发明具有的有益效果如下：
本发明利用光电绿色电解水制氢与低温技术耦合储能，当光电可再生能源充足时，绿电水电解制氢生产的富余氢气通过液氮预冷氢气液化系统将氢气液化储存；当光电可再生能源因环境变化发电量减少导致绿电水电解制氢不足时，储存的液氢通过液氢-液氮换热系统和冷能储存系统汽化复热后供入下游工艺管网。与此同时低温换热获得的液氮可为氢液化系统提供部分预冷冷源；冷能储存系统储存的冷能可以为空气分离装置冷能利用系统利用。本发明解决了光电资源不连续生产绿氢与生产用绿氢连续化需求矛盾的问题，通过储氢的形式，可实现最大限度的利用光电可再生能源，在实现高效储能调峰的同时，能够有效降低绿氢制备利用的能耗成本，达到节能效果，具有良好的推广前景。
附图说明
图1是本发明的示意图。
具体实施方式
为使本发明需解决的技术问题、技术方案和有益效果更加清楚，下面结合附图和具体实施方式对本发明作进一步详细说明。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
下面将结合附图对本发明作详细的介绍：如图1所示：一种电解水制氢与低温耦合的储能装置，所述装置包括液氮预冷氢气液化系统、液氢-液氮换热系统、冷能储存系统及空气分离装置冷能利用系统；所述液氮预冷氢气液化系统包括液氮输入系统11、氮气输出系统12、液氢输出系统13和氢气液化系统14，各个系统之间通过管道连接和阀门控制；所述液氢-液氮换热系统包括液氢储罐21、液氢泵22、液氢-液氮换热器23、液氮储罐24，各个系统之间通过管道连接和阀门控制，用于汽化液氢并液化氮气，其中所述液氢储罐21的液氢输入端连接于所述液氮预冷氢气液化系统的液氢输出系统13，所述液氢泵22的液氢输入端连接于所述液氢储罐21的液氢输出端，所述液氢-液氮换热器23的液氢输入端连接于所述液氢泵22的液氢输出端，所述液氢-液氮换热器23的氮气输入端连接于所述空气分离装置冷能利用系统的空气分离装置产品氮气输出系统43的氮气输出端，所述液氢-液氮换热器23的液氮输出端连接于所述液氮储罐24的液氮输入端，所述液氮储罐24的液氮输出端连接于所述液氮预冷氢气液化系统的所述液氮输入系统11的输入端，所述冷能储存系统包括氢气-载冷剂换热器31、载冷剂泵32、载冷剂-冷能储存换热器33、载冷剂储罐34，冷能储罐35，各个系统之间通过管道连接和阀门控制，用于复热氢气并储存冷能，其中所述氢气-载冷剂换热器31的氢气输入端连接于所述液氢-液氮换热器23的氢气输出端，所述氢气-载冷剂换热器31的载冷剂输出端连接于所述载冷剂泵32的载冷剂输入端，所述载冷剂泵32的载冷剂输出端连接于所述载冷剂-冷能储存换热器33的载冷剂输入端，所述载冷剂-冷能储存换热器33的载冷剂输出端连接于所述氢气-载冷剂换热器31的载冷剂输入端，所述载冷剂-冷能储存换热器33的水输出端连接于所述冷能储罐35的输入端，所述载冷剂储罐34通过管道和阀门连接于所述载冷剂泵32的载冷剂输入端，所述空气分离装置冷能利用系统包括循环水系统41、水冷塔42、空气分离装置产品氮气输出系统43，空气分离装置冷冻水输入系统44，各个系统之间通过管道连接和阀门控制，所述循环水系统41的输出端连接于所述载冷剂-冷能储存换热器33的水输入端，所述冷能储罐35的输出端连接于所述水冷塔42的上部输入端，所述氮气输出系统12的输出端连接于所述水冷塔42的下部输入端，所述水冷塔42的底部输出端连接于所述空气分离装置冷冻水输入系统44的输入端，所述液氢-液氮换热器23、氢气-载冷剂换热器31、载冷剂-冷能储存换热器33均为绕管式换热器或板面式换热器，所述水冷塔42为填料塔。
一种应用于上述储能装置的储能方法，包括以下步骤： 步骤1：当光电绿色电解水制氢气过量时，过量氢气可经氢气液化系统液化，其中液氮作为氢液化的预冷冷源，液化后的液氢送入液氢储罐21进行储存，汽化复热到常温的氮气由氮气输出系统12通过管道进入水冷塔42的下部后被从冷能储罐35过来的低温水进入水冷塔42上部后喷淋，低温水被进一步冷却，有利于空气分离装置后续的工艺，节省了空气分离装置的能耗。
步骤2：当光电等可再生能源发电系统因环境变化，如日照减弱而导致绿色电解水制氢不足时，储存于液氢储罐21的液氢经液氢泵22加压后进入液氢-液氮换热器23汽化复热后又进入氢气-载冷剂换热器31复热得到常温氢气，用来补充绿色电解水的制氢不足。同时产品氮气输出系统43的常温氮气进入液氢-液氮换热器23用来提供热源汽化复热液氢，其自身被液化冷凝成液氮后进入液氮储罐24，可作为氢气液化时液氮预冷的部分补充。同时载冷剂进入氢气-载冷剂换热器31用来提供热源复热氢气，其自身被冷却后经载冷剂泵32加压后进入载冷剂-冷能储存换热器33，用来冷却从循环水系统41过来的常温水，常温水被冷却成低温水后出载冷剂-冷能储存换热器33进入冷能储罐35，冷能储罐35的低温水可通过管道和阀门进入水冷塔42上部进行喷淋，进一步降低水温。
所述载冷剂为无机、有机化合物或其混合溶液或其水溶液。进一步的，所述载冷剂以有机化合物水溶液为主要优选，如乙二醇水溶液、丙二醇水溶液、甲醇、甲醇水溶液或乙醇水溶液，所述水冷塔42装填为填料。
当光电绿色电解水制氢气过量时，过量氢气经氢气液化系统14液化，氢气液化系统14一般采用市场上广泛采用的液氮预冷Claude氢循环氢气液化系统或Brayton氦循环氢气液化系统，氢液化的预冷冷源液氮可从液氮储罐24经过液氮输入系统11输入进入氢气液化系统14，汽化的氮气经氮气输出系统12通过管道进入水冷塔42的下部，氮气被从冷能储罐35过来的低温水进入水冷塔42上部后喷淋，低温水被进一步冷却。对于空气分离装置广泛熟知的认知，空气分离装置预冷系统水冷塔的低温水温度合理范围内的降低，有利于节省空气分离装置的整体能耗，降低了空气分离装置产品的单耗。
当光电等可再生能源发电系统因环境变化，如日照减弱而导致绿色电解水制氢不足时，储存于液氢储罐21的液氢经液氢泵22加压到如1.6MPaA后进入液氢-液氮换热器23，同时空气分离装置产品氮气输出系统43的温度约为25℃的氮气进入液氢-液氮换热器23用来提供热源汽化复热液氢，其自身被液化冷凝成液氮后进入液氮储罐24，可作为氢气液化时液氮预冷的部分补充，补充率可达约60%。从液氢-液氮换热器23汽化复热出来的氢气温度还很低，一般在-100℃左右，氢气需再进入氢气-载冷剂换热器31复热得到常温氢气，用来补充绿色电解水的制氢不足。同时载冷剂，如乙二醇水溶液进入氢气-载冷剂换热器31用来提供热源复热氢气，其自身被冷却到约0℃后经载冷剂泵32升压约0.1-0.3MPaA后进入载冷剂-冷能储存换热器33，用来冷却从循环水系统41过来的温度为30℃的常温水，常温水被冷却到约20℃后成低温水，低温水出载冷剂-冷能储存换热器33进入冷能储罐35储存，冷能储罐35的低温水可通过管道和阀门连续进入水冷塔42上部进行喷淋，从而进一步降低低温水的温度成冷冻水。

Claims (6)

1.一种电解水制氢与低温耦合的储能装置，其特征在于：所述装置包括液氮预冷氢气液化系统、液氢-液氮换热系统、冷能储存系统及空气分离装置冷能利用系统；所述液氮预冷氢气液化系统包括液氮输入系统、氮气输出系统、液氢输出系统和氢气液化系统，各个系统之间通过管道连接和阀门控制；所述液氢-液氮换热系统包括液氢储罐、液氢泵、液氢-液氮换热器、液氮储罐，各个系统之间通过管道连接和阀门控制，用于汽化液氢并液化氮气，其中所述液氢储罐的液氢输入端连接于所述液氮预冷氢气液化系统的液氢输出系统，所述液氢泵的液氢输入端连接于所述液氢储罐的液氢输出端，所述液氢-液氮换热器的液氢输入端连接于所述液氢泵的液氢输出端，所述液氢-液氮换热器的氮气输入端连接于所述空气分离装置冷能利用系统的空气分离装置产品氮气输出系统的氮气输出端，所述液氢-液氮换热器的液氮输出端连接于所述液氮储罐的液氮输入端，所述液氮储罐的液氮输出端连接于所述液氮预冷氢气液化系统的所述液氮输入系统的输入端，所述冷能储存系统包括氢气-载冷剂换热器、载冷剂泵、载冷剂-冷能储存换热器、载冷剂储罐，冷能储罐，各个系统之间通过管道连接和阀门控制，用于复热氢气并储存冷能，其中所述氢气-载冷剂换热器的氢气输入端连接于所述液氢-液氮换热器的氢气输出端，所述氢气-载冷剂换热器的载冷剂输出端连接于所述载冷剂泵的载冷剂输入端，所述载冷剂泵的载冷剂输出端连接于所述载冷剂-冷能储存换热器的载冷剂输入端，所述载冷剂-冷能储存换热器的载冷剂输出端连接于所述氢气-载冷剂换热器的载冷剂输入端，所述载冷剂-冷能储存换热器的水输出端连接于所述冷能储罐的输入端，所述载冷剂储罐通过管道和阀门连接于所述载冷剂泵的载冷剂输入端，所述空气分离装置冷能利用系统包括循环水系统、水冷塔、空气分离装置产品氮气输出系统，空气分离装置冷冻水输入系统，各个系统之间通过管道连接和阀门控制，所述循环水系统的输出端连接于所述载冷剂-冷能储存换热器的水输入端，所述冷能储罐的输出端连接于所述水冷塔的上部输入端，所述氮气输出系统的输出端连接于所述水冷塔的下部输入端，所述水冷塔的底部输出端连接于所述空气分离装置冷冻水输入系统的输入端。
2.根据权利要求1所述的电解水制氢与低温耦合的储能装置，其特征在于：所述液氢-液氮换热器、氢气-载冷剂换热器、载冷剂-冷能储存换热器均为绕管式换热器或板面式换热器。
3.根据权利要求1所述的电解水制氢与低温耦合的储能装置，其特征在于：所述水冷塔为填料塔。
4.根据权利要求1-3中任一项所述储能装置的储能方法，其特征在于：包括以下步骤：步骤1：当光电绿色电解水制氢气过量时，过量氢气可经氢气液化系统液化，其中液氮作为氢液化的预冷冷源，液化后的液氢送入液氢储罐进行储存，汽化复热到常温的氮气由氮气输出系统通过管道进入水冷塔的下部后被从冷能储罐过来的低温水进入水冷塔上部后喷淋，低温水被进一步冷却，有利于空气分离装置后续的工艺，节省了空气分离装置的能耗；
步骤2：当可再生能源发电系统因环境变化，如日照减弱而导致绿色电解水制氢不足时，储存于液氢储罐的液氢经液氢泵加压后进入液氢-液氮换热器汽化复热后又进入氢气-载冷剂换热器复热得到常温氢气，用来补充绿色电解水的制氢不足，同时产品氮气输出系统的常温氮气进入液氢-液氮换热器用来提供热源汽化复热液氢，其自身被液化冷凝成液氮后进入液氮储罐，可作为氢气液化时液氮预冷的部分补充，同时载冷剂进入氢气-载冷剂换热器用来提供热源复热氢气，其自身被冷却后经载冷剂泵加压后进入载冷剂-冷能储存换热器，用来冷却从循环水系统过来的常温水，常温水被冷却成低温水后出载冷剂-冷能储存换热器进入冷能储罐，冷能储罐的低温水可通过管道和阀门进入水冷塔上部进行喷淋，进一步降低水温。
5.根据权利要求4所述的电解水制氢与低温耦合的储能方法，其特征在于：所述载冷剂为无机、有机化合物或其混合溶液或其水溶液。
6.根据权利要求4所述的电解水制氢与低温耦合的储能方法，其特征在于：所述水冷塔装填为填料。
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