CN112197505A - 生产液态氢的方法和设备 - Google Patents

生产液态氢的方法和设备 Download PDF

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CN112197505A
CN112197505A CN202010654172.6A CN202010654172A CN112197505A CN 112197505 A CN112197505 A CN 112197505A CN 202010654172 A CN202010654172 A CN 202010654172A CN 112197505 A CN112197505 A CN 112197505A
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liquefier
power
level
hydrogen
liquid hydrogen
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L·阿利迪耶斯
G·里戈特
P·巴嘉奥克斯
P-G·马里耶
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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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Abstract

本发明涉及一种通过液化器(2)生产液态氢的方法和设备，所述液化器是电动类型的，并且具有取决于所消耗的电功率的可变冷却功率，所述液化器(2)由第一电源(4)供电，并与提供一定量的间歇的或随时间变化的电力的至少一个附加电源(5、6)连接，其特征在于，当以预定的标称电能水平向液化器(2)供电时，所述液化器在第一热力学条件下生产液态氢，并且当以超过所述标称水平的能量水平向液化器(2)供电时，由所述液化器(2)生产的氢相对于第一热力学条件过冷。

Description

生产液态氢的方法和设备
技术领域
本发明涉及一种生产液态氢的方法和设备。
具体而言，本发明涉及一种通过由气态氢源供料的液化器生产液态氢的方法，该液化器为电动型，其冷却功率随消耗的电功率而变化，该液化器由第一电源供电，并连接到至少一个附加电源，该附加电源提供一定量的间歇的或随时间变化的电力。
背景技术
当需要远距离大量运输产品时，因其密度，液态氢较气态氢更适合。液态氢的另一个优点与其密度和为燃料电池汽车填充燃料箱的服务站的高存储容量有关。
例如，液态氢的密度比水低，这就限制了流体静压高度可提供的压力。在低温下，这会在转移过程中因蒸发造成相当大的损失。
在氢液化工厂，用于装载罐车和储罐的系统会造成高达产量的15％的损失(0.2％的损失源于储罐，5％源于储罐填充阀中的闪蒸，10％源于充装罐车的过程)。
当然，这些蒸发造成的损失可以被回收、再加热、再压缩并重新注入液化器中。这需要对损失再循环系统进行投资，并对液化系统进行冗余工程设计。
对于某些类型的液化器(特别是那些以氦为基础的循环运行的液化器)，另一种可能的解决方案是将液态氢过冷至其饱和温度以下。这使得可以通过在储罐中使用冷氢来重新冷凝闪蒸气体，以弥补在充装阶段期间蒸发造成的损失。这种过冷处理通过消耗液化器的特定能量来实现(因为在液体饱和温度下液化所需能量基础上，有必要进一步增加用于过冷的特定能量)。
氢的液化需要相当高的电能：每千克液化氢需要大约6至14kWh的电能(取决于液化技术和工厂规模)。为了减少液化过程的碳排放，最好将液化器与可再生能源联接，该可再生能源可以为间歇性的，诸如太阳能或风能。
可再生能源的间歇性使液化器的操作极其困难，因为要维持工艺的稳定性。因此，液化设备通常不采用间歇性能源供能。这是因为液化器通常物理地集成在生产气态氢(大部分时间是通过天然气重整)的工厂中，为使设备耐用，气态氢的生产也必须在稳定的条件下进行。
发明内容
本发明的目的之一是克服现有技术的前述全部或部分缺陷。
为此，除了按照上述序言给出的一般定义之外，根据本发明的方法的主要特征在于，当以预定的标称电能水平向液化器供电时，液化器生产第一热力学条件下的液态氢，并且当以超过所述标称水平的能量水平向液化器供电时，液化器生产的氢相对于第一热力学条件过冷。
这使得可以在间歇能量可用时使用间歇能量不时地(如果合适的话)过冷却氦循环液化器的产物，该氦循环液化器在稳定的液化功率下以稳定的液化流速运行。被添加到液化功率中的这种过冷功率随着可用的可再生能源的供应而波动。
此外，本发明的实施例可以包括以下一个或多个特征：
-当以标称电能水平向液化器供电时，液化器生产的液态氢处于饱和状态，
-当以超过所述标称水平的能量水平向液化器供电时，液化器生产的液态氢相对于其饱和状态过冷，
-被提供给液化器的超过所述标称水平的电能的至少一部分被液化器用来将所生产的液态氢过冷至低于其饱和温度的温度，
-被提供给液化器的超过所述标称水平的电能的至少一部分由所述至少一个附加电源提供，
-液化器被配置为生产一定量的液态氢，该液态氢随着时间被预定为具有零或非零的过冷度/过冷水平，该过冷度是超过提供给所述液化器的所述标称水平的电能水平的函数。
-液化器生产的过冷氢的温度比第一热力学条件下降0.01K至几乎7K，特别是在0.001K至4K之间，特别是降低至可达到氢的三相点温度水平的温度，即13.8K，
-超过所述标称水平的电能水平可在标称电能水平的0％至25％之间、特别是在0％至15％之间变化，
-第一电源包括与液化器连接的电网，
-所述至少一个附加电源包括如下至少一个：风力发电机、太阳能发电机，
-液化器生产的液态氢被转移到液体存储设施，
-当以预定的标称电能水平向液化器供电时，液化器生产的液态氢在对应于储罐中的存储压力下的氢泡点的第一热力学条件下被转移到储罐中，并且当以超过所述标称水平的能量水平向液化器供电时，液化器生产的氢以相同的流速在低于储罐中的存储压力下的氢泡点的温度下被转移到储罐中，
-液化器以稳定或不变的流速生产液态氢。
本发明还涉及一种生产液态氢的设备，其包括液化器、连接到液化器的气态氢源，液化器为电动型，并且具有取决于所消耗的电功率的可变冷却功率，所述设备包括连接至液化器以向后者供电的第一电源、和至少一个附加电源，所述至少一个附加电源提供一定量的间歇的或随时间变化的电力并且连接至液化器以向后者供电，所述设备还包括电子控制器，所述电子控制器配置为管理所述液化器的制冷功率，以便当以预定的标称电能水平向所述液化器供电时生产处于第一热力学条件下的液态氢，或者当以超过所述标称水平的能量水平向液化器供电时生产相对于第一热力学条件过冷的液态氢。
根据其他可能的实施例：
-电子控制器电连接至第一电源、至少一个附加电源以及液化器，电子控制器被配置为由第一电源向液化器提供预定的标称电能水平的电力，并且通过采用由所述至少一个附加电源提供的可用的附加电能补充由第一电源提供的电能，以大于预定的标称电能水平的电能水平供电。
本发明还涉及包括上述及以下权利要求的任意特征组合的任意替代方法或装置。
附图说明
通过阅读以下参照附图所做的描述，其他区别特征和优点将显而易见。
其中：
图1表示根据本发明的设备的结构和操作的示例的局部示意图。
图2表示设备的液化器的电力、供应和液化功率的变化的示例的局部示意图。
具体实施方式
生产液态氢的设备1包括连接到气态氢源3的液化器2。气态氢源3包括例如天然气重整(SMR)单元，该单元生产被供应至液化器2的气态氢。可以具有一个或多个其它气体源。因此，源3可以包括氢网络和/或用于生产氢的单元(例如蒸汽重整和/或通过电解或任何其他合适的源)。因此，源3还可以包括从不纯的源(炼厂残余气体，来自氯碱电解槽的不可避免的氢，等等)回收的氢。
氢源3提供例如稳定的待液化的(优选为纯的)氢气流速，其压力可以在7至150barabs(绝对压力)之间，并且处于环境温度下。
在SMR的情况下，后者生产的不变的氢气流速优选在液化器可接受的最大流速和液化器2功能降低的最小流速之间(通常最小流速为最大流速的30％至40％)。流速的变化率优选大致为每分钟瞬时流速的百分之几。
液化器2是电动型的，其冷却功率随消耗的电力变化。例如，但不限于此，液化器2可以是使用包含氦的工作流体的液化器(“氦循环液化器”，但是可以设想使用另一种工作气体：氮气或任何其他混合物等)，其提供压缩(压缩机)、冷却、降压(一个或多个涡轮)以及再加热。特别地，液化功率可以通过管理驱动压缩机的一个或多个马达的转速来控制。这些马达可以是电动机(特别是磁性轴承上的同步高速电动机)。压缩机优选为直接驱动离心式压缩机，以实现高输出。有利地，一个或多个涡轮的功率可以被回收并用于减少一个或多个马达的消耗。因此，通过增加马达的速度(从而增加工作气体循环中的流速)，产生的制冷功率以及从而液化器的电力消耗增加(反之亦然)。
例如，液化器2可以在从气态氢源3供给的压力减去所述液化器的热交换器中的气体的压头损失(大约几百毫巴)的情况下在其泡点和其凝固点之间产生稳定的液态氢流速。
例如，液化器2每天可以生产100kg至每天超过100吨的氢。该产量根据其过冷功率和可用电力进行调整。
该液化器可以是申请人出售的“Turbo Brayton”型液化器，其可以特别地提供15K至20K的制冷和液化。
因此，液化器2是与向液化器供电的第一电源4连接的电动机器。第一电源(主电源)优选是稳定的，并且是或者包括例如电网。
液化器2也电连接(优选并联)到至少一个附加的电源5、6。这个或这些附加的一个或多个电源5、6是提供间歇的或随时间变化的电力的类型，特别是可再生类型的电源(风能、太阳能等)。
设备1还包括电子控制器7，该电子控制器7被配置为管理液化器2的制冷功率，以便当(通过第一电源4)以预定的标称电能水平向液化器供电时生产第一热力学条件下的液态氢，或者(通过第一电源4辅以至少一个附加电源5、6)以超过所述标称水平的能量水平向液化器2供电时生产相对于第一热力学条件过冷的液态氢。
电子控制器7包括例如微处理器、计算机或任何其他适当的装置。
电子控制器7优选地被配置为使得能够根据对饱和液态氢的需求来管理氢液化所需的能量，并且管理过多的可再生电能以提供过冷。
第一电源4提供例如在其泡点液化预定量的氢所需的电能。
因此，由液化器2生产的饱和液体的流速可以保持不变，但是过冷的程度可以仅由可变的且间歇的一个或多个过量可再生能量的源5、6(如果适当的话)所贡献的能量来实现。
图2中示出这种变化的示例。带有十字和圆形的曲线分别表示各自由太阳能源和风能源生产的能量随时间t在预定量的0％到100％之间的变化。第三条曲线表示由液化器2生产的氢的过冷度(ΔT)随时间t(以K为单位)的变化。可见，当可用的可再生能源总量较高时，过冷度成比例地增大。
具有可变冷却能力的液化器使得可以在间歇能量可用时使用间歇能量。这样可以享受优惠的电价(通常白天使用多余的太阳能或暴风雨时使用多余的风能)。在某些情况下，这些价格甚至可能为负。
该构造使得能够以降低的成本生产过冷氢，该过冷氢对于减少蒸发损失是必要的，同时使用诸如SMR之类的稳定生产氢的系统作为源，并且同时液化稳定的流速。
如图所示，液化器2生产的液态氢可以通过管道9转移到液体存储设施8中。该存储设施可以是真空绝热的，其尺寸可以与液化器数天(例如五天)的生产量相匹配。
通常，存储设施8中的压力可调节，例如可调为固定值(例如绝对压力在1.05至11bar之间，例如在1.1至5bar之间，特别是2.5bar)。该压力还可以由热力学平衡的饱和的液相和气体之间的平衡形成。在过冷氢存储设施的情况下，将有利地使用存储设施的大容量，以将过冷氢在容器底部注入，促进液体中氢的温度垂直分层，使得在液/气界面处的处于平衡状态的氢比容器底部的液态氢要热。同样，气相也将温度垂直分层。
存储设施8的压力应理解为是指例如存储设施或存储设施的底部或上部(气体顶部空间中)的平均压力。这是由于氢的密度低，存储设施下部的压力基本等于上部的压力。
由此，设备1成为存储过冷氢形式的可再生能量的系统。与存储液态氢的常规系统相比，其优点是其操作简单。这是因为任何用于氢液化的工厂——其具有可用的适应性氢液化工艺且能够进行过冷处理——都可以转换为这种储能系统。
该液体存储设施8可用于填充(例如通过至少一个管道10)移动储罐11，诸如半挂车运载的液体储罐(例如容量为1000至4000kg)。该管道10可以设置有阀，例如先导阀，和/或泵或其他。
这些储罐11可以被填充接近饱和的液态氢，特别是以例如每小时1000至2000kg的流速。可以设置回收管12，以便在填充储罐期间(例如在1至12bar的压力下且每小时100至200kg的流速下)将储罐11中蒸发的气体回收。由于液态氢是以非零的过冷度注入，故可以进一步减少由待填充储罐或管道中液体蒸发引起的这些损失。
为将存储设施8中产生的蒸发气体(由于热量进入)返回到回收系统14中，可以设置回流管13。该冷却的气体具有例如1至12bar之间的压力，和约为存储设施8的容量的0.1％至1％的日流速。该回收系统14可以包括加热器、存储设施和再循环压缩机。
回收的气体可以通过管道15返回液化器2中重新液化。
这样，可以通过过量间歇能量与基础能量的成本比率来降低过冷处理的附加成本。
例如，液化电能的0％至10％可以用于氢的过冷。
该方案可以应用于除氢气以外的其他气体，特别是天然气。
设备1还可以包括输送管，该输送管的一端连接到液化器2的出口，另一端用于直接连接到储罐11(不经过储存设施8)。该输送管可以配备有阀(优选为先导阀)，以便将液态氢从液化器2输送到储罐11。
储存设施8和储罐11可以为夹套式且真空隔热。

Claims (15)

1.一种通过液化器(2)生产液态氢的方法，所述液化器(2)由气态氢源(3)供料，所述液化器(2)是电动类型的，并且具有取决于所消耗的电功率的可变冷却功率，所述液化器(2)由第一电源(4)供电，并与提供一定量的间歇的或随时间变化的电力的至少一个附加电源(5、6)连接，其特征在于，当以预定的标称电能水平向液化器(2)供电时，所述液化器在第一热力学条件下生产液态氢，并且当以超过所述标称水平的能量水平向液化器(2)供电时，由所述液化器生产的氢相对于第一热力学条件过冷。
2.根据权利要求1所述的方法，其特征在于，当以标称电能水平向所述液化器(2)供电时，所述液化器(2)生产的液态氢处于饱和状态。
3.根据权利要求1或2所述的方法，其特征在于，当以超过所述标称水平的能量水平向所述液化器(2)供电时，所述液化器(2)生产的液态氢相对于其饱和状态过冷。
4.根据权利要求3所述的方法，其特征在于，被提供给所述液化器(2)的超过所述标称水平的电能的至少一部分被所述液化器(2)用来将所生产的液态氢过冷至低于其饱和温度的温度。
5.根据权利要求1至4中任一项所述的方法，其特征在于，被提供给所述液化器(2)的超过所述标称水平的电能的至少一部分由所述至少一个附加电源(5、6)提供。
6.根据权利要求1至5中任一项所述的方法，其特征在于，液化器(2)被配置为生产一定量的液态氢，该液态氢随着时间被预定为具有零或非零的过冷度，该过冷度是超过提供给所述液化器的所述标称水平的电能水平的函数。
7.根据权利要求1至6中任一项所述的方法，其特征在于，液化器(2)生产的过冷氢的温度比第一热力学条件降低0.01K至几乎7K，特别是在0.001K至4K之间，特别是降低至能达到氢的三相点温度水平的温度，即13.8K。
8.根据权利要求1至7中任一项所述的方法，其特征在于，超出所述标称水平的电能水平能在标称电能水平的0％至25％之间、特别是在0％至15％之间变化。
9.根据权利要求1至8中任一项所述的方法，其特征在于，所述第一电源(4)包括与液化器(2)连接的电网。
10.根据权利要求1至9中任一项所述的方法，其特征在于，所述至少一个附加电源(5、6)包括风力发电机(5)、太阳能发电机(6)中的至少一者。
11.根据权利要求1至10中任一项所述的方法，其特征在于，液化器(2)生产的液态氢被转移到液体存储设施(8)。
12.根据权利要求11所述的方法，其特征在于，当以预定的标称电能水平向液化器(2)供电时，液化器(2)生产的液态氢在对应于储罐(8)中的存储压力下的氢泡点的第一热力学条件下被转移到储罐(8)中，并且当以超过所述标称水平的能量水平向液化器(2)供电时，液化器(2)生产的氢以相同的流速在低于储罐(8)中的存储压力下的氢泡点的温度下被转移到储罐(8)中。
13.根据权利要求1至12中任一项所述的方法，其特征在于，液化器(2)以稳定或不变的流速生产液态氢。
14.一种用于生产液态氢的设备，包括液化器(2)、连接到液化器(2)的气态氢源(3)，所述液化器(2)是电动类型的，并且具有取决于所消耗的电功率的可变冷却功率，所述设备包括连接至液化器(2)以向后者供电的第一电源(4)、和至少一个附加电源(5、6)，所述至少一个附加电源提供一定量的间歇的或随时间变化的电力并且连接至液化器(2)以向后者供电，所述设备(1)还包括电子控制器(7)，所述电子控制器配置为管理所述液化器的制冷功率，以便当以预定的标称电能水平向所述液化器供电时生产处于第一热力学条件下的液态氢，或者当以超过所述标称水平的能量水平向液化器(2)供电时生产相对于第一热力学条件过冷的液态氢。
15.根据权利要求14所述的设备，其特征在于，电子控制器(7)电连接至第一电源(4)、所述至少一个附加电源(5、6)以及液化器(2)，电子控制器(7)被配置为由第一电源(4)向液化器(2)提供处于预定的标称电能水平的电力，并且通过采用由所述至少一个附加电源(5、6)提供的可用的附加电能补充由第一电源(4)提供的电能，以大于预定的标称电能水平的电能水平供电。
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