CN115930096A - 加氢站气态氢回收系统和方法 - Google Patents

加氢站气态氢回收系统和方法 Download PDF

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CN115930096A
CN115930096A CN202211198915.9A CN202211198915A CN115930096A CN 115930096 A CN115930096 A CN 115930096A CN 202211198915 A CN202211198915 A CN 202211198915A CN 115930096 A CN115930096 A CN 115930096A
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hydrogen
compression unit
refueling station
electrochemical compression
electrochemical
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D·J·查尔克
J·P·科恩
D·J·法瑞斯
B·H·S·托尔达
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Air Products and Chemicals Inc
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    • F17C5/00Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures
    • F17C5/06Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures for filling with compressed gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B01D53/326Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
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    • BPERFORMING OPERATIONS; TRANSPORTING
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Abstract

本发明涉及一种用于向车辆罐加氢的集成式加氢站,其特征在于包括电化学压缩单元,来自一个或多个燃料站操作单元中含氢气体的泄漏、汽化或排放的次级氢在所述电化学压缩单元中被压缩,其中所述次级氢含有氢和其它气态成分,并且涉及一种此类加氢站的操作方法。

Description

加氢站气态氢回收系统和方法
技术领域
本发明涉及一种用于向车辆罐加氢的集成式加氢站,其中回收来自一个或多个燃料站操作单元中含氢气体的泄漏、汽化(boiling-off)或排放的次级氢中,并且涉及一种操作此类加氢站的工艺。
背景技术
用于在加氢站中为氢驱动车辆加燃料的若干中配置和系统在本领域中是已知的。例如,US 2004/163731(A1)公开了一种自足式移动燃料站。在此类加氢站中,在高压下以气态分配到车辆罐之前,氢以压缩或液体形式存储并被进一步处理。在这些操作的一些操作期间,氢可能会泄漏、汽化和/或被排放,这意味着这部分氢“损失”而无法用于向车辆加燃料。如下文所解释的,这些泄漏、汽化和/或排放的氢通常含有其它成分,在本文中也被称为“次级氢”。
例如,加氢站通常包括一个或多个机械式氢压缩机。此类机械式压缩机在操作期间具有固有的氢泄漏率。泄漏的氢来自多个来源,包含窜漏、蒸汽回流和/或压缩机的出口。传统的机械式氢压缩机因泄漏而损失1%至5%的氢,这当然是不期望的并且代表着经济损失。到目前为止,重点是减少此类泄漏,例如通过在压缩机内使用油密封,然而,这经常导致压缩气体流中的污染物。此外,出于安全原因,机械式压缩机中氢从其泄漏或泄漏到其中的部件(诸如封装箱和/或曲柄箱)必须使用惰性气体(通常为氮)进行吹扫,惰性气体与氢混合,从而对氢进行稀释。
泄漏、汽化和/或排放的氢通常具有降低的压力,并且由于与惰性气体的混合和/或空气中含有其它气态成分,诸如氮,这需要分离所述次级氢中所含的氢。去除这些其它成分增加了复杂性,并且进一步使次级氢中所含的氢的再利用变得复杂。
因此本发明的目标是通过回收和再利用来自加氢站的一个或多个操作单元中的泄漏、汽化或排放的次级氢中的至少一部分来改进和进一步集成加氢站及其操作方法。
发明内容
本发明基于以下发现,如果来自加氢站的一个或多个操作单元中的泄漏、汽化或排放的次级氢被收集并在电化学压缩机中压缩,则可以实现该目标。
因此本发明在第一实施例中提供了一种用于向车辆罐中加氢的集成式加氢站,其特征在于包括电化学压缩单元,来自一个或多个燃料站操作单元中含氢气体的泄漏、汽化或排放的次级氢在所述电化学压缩单元中被压缩,其中所述次级氢含有氢和其它气态成分。
在实施例中,所述加氢站包括产生次级氢的一个或多个机械式氢压缩单元,所述次级氢被收集并转移到所述电化学压缩单元。
在实施例中,所述加氢站包括产生次级氢的一个或多个氢分配单元,所述次级氢被收集并转移到所述电化学压缩单元。
在实施例中,所述加氢站包括产生次级氢的一条或多条氢输送管线,所述次级氢被收集并转移到所述电化学压缩单元。
在实施例中,所述次级氢含有1质量%至99质量%的量、优选地5质量%至95质量%的量、甚至更优选地25质量%至90质量%的量的氢。
在实施例中,氮占次级氢中所含的其它气态成分的50质量%或更多。
在实施例中,在电化学压缩单元中压缩后获得的加压氢中氢的杂质水平为1,000ppm或更低、更优选地为500ppm或更低、并且最优选地为300ppm或更低。
在实施例中,所述加氢站包括次级氢收集系统,所述次级氢收集系统收集由所述一个或多个加氢站操作单元产生的所述次级氢,并且所述次级氢收集系统连接至所述电化学压缩单元。
在实施例中,所述次级氢收集系统包括次级氢缓冲罐。
在实施例中,从所述电化学压缩单元获得的压缩氢被转移到中间氢存储体积或与高压初级氢相结合。
在第二实施例中,本发明提供了一种用于向车辆罐加氢的加氢站的操作方法,其特征在于来自一个或多个燃料站操作单元中含氢气体的泄漏、汽化或排放的次级氢在电化学压缩单元中被压缩,其中所述次级氢含有氢和其它气态成分。
本发明能够在加氢站中实现否则将损失的次级氢的非常有效的回收和再利用,次级氢包括与其它气态成分混合的泄漏、排放或汽化的氢,并且因此实现此类站的更好集成,从而提供经济效益。
电化学压缩机(也称为电化学膜泵)利用跨膜电极组件的电场来将氢分解为质子,然后携带这些质子穿过所述膜电极组件,并最终在阴极处将它们转换为氢气。例如,已经在美国专利号6,168,705中描述了此类工艺以在整个装置上选择性地积聚氢气。电化学压缩机没有移动部件并且尺寸紧凑。可通过电化学压缩机获得压力为100MPa的氢。
在本发明中使用电化学压缩单元来压缩次级氢提供以下优点:在同一步骤/同一装置中,其中待再利用的氢被压缩,并且次级氢中所含的其它成分(诸如氮气)与氢分离,即氢在压缩的同时被纯化。因此,通过使用所述电化学压缩单元,仅在一步内就可以从所述次级氢中获得可直接再利用来为车辆加燃料的纯化和加压状态的氢。
此外,电化学压缩机可以在可变的入口和出口压力下以可变的流速运行,并且在原料气中以可变的氢浓度运行,这使得它们特别适用于以各种量、压力、流速产生的次级氢的压缩,并且在燃料站的各个单元的操作期间具有变化的氢浓度。由于其紧凑的尺寸以及缺乏移动部件,电化学压缩机是具有低维护成本的简单系统。
当然,电化学压缩单元的集成增加了加氢站的投资成本,但是否则将损失的次级氢成分的回收利用的优点补偿并超出了这些较高成本。
附图说明
本发明将在下文结合图1进行描述,其中相同的标号指代相同的元件。
图1示出本发明的集成式燃料站和方法的实施例的一部分。
具体实施方式
优选地,加氢站包括产生次级氢的一个或多个机械式氢压缩单元,次级氢被收集并转移到电化学压缩单元。
机械式压缩机通常用于将气态氢压缩至填充车辆罐所需的压力,优选地30MPa或更高的压力。例如,对于H35加燃料,氢被加压至40MPa或更高,或者对于H70加燃料,氢被加压至90MPa或更高。此类机械式压缩机在操作期间具有固有的氢泄漏率,因为氢例如经由活塞环或轴密封从多个点泄漏,包含窜漏、蒸汽回流和/或压缩机的出口。传统的机械式氢压缩机因泄漏而损失1%至5%的氢。
由机械压缩获得的压缩氢然后通常被转移到中间氢存储体积,诸如氢存储体。然后可以通过将氢从存储体的不同存储罐级联到氢分配单元并最终级联到车辆罐来完成车辆罐的加燃料。级联对于本领域技术人员来说是众所周知的并且描述于例如美国专利号8,899,278中,从第1卷第17行开始。
来自加氢站的一个或多个或全部机械式压缩机的泄漏的次级氢被收集并转移到电化学压缩单元以进行压缩。
由于出于安全原因,机械式压缩机的氢从其泄漏或泄漏到其中的部件(诸如封装箱和/或曲柄箱)必须使用惰性气体(通常为氮)进行吹扫,从机械式压缩机手机的次级氢通常包括大量的此类惰性气体,诸如氮。
优选地,加氢站包括产生次级氢的一个或多个氢分配单元,次级氢被收集并转移到电化学压缩单元。
每个分配单元包括喷嘴,压缩氢通过该喷嘴而传递到车辆罐。在操作期间,在分配后,一定体积的气态氢被遗留在分配系统和分配管线中。该剩余氢通常被排放。从加氢站的一个或多个或全部氢分配单元中排放的次级氢被收集并转移到电化学压缩单元以进行压缩。
优选地,加氢站包括产生次级氢的一条或多条氢输送管线,次级氢被收集并转移到电化学压缩单元。
在氢输送管线中输送氢期间,氢可能会泄漏,并且在输送液态氢的情况下,通常在形成被排放的氢汽化气体时,这些管线必须被冷却。来自加氢站的一条或多条或全部氢输送管线的泄漏和/或排放的次级氢被收集并转移到电化学压缩单元以进行压缩。
被收集并转移到电化学压缩单元以进行压缩的次级氢可含有1质量%或更多、2质量%或更多、5质量%或更多、10质量%或更多、25质量%或更多或甚至40质量%或更多的量的氢。
被收集并转移到电化学压缩单元以进行压缩的次级氢可含有高达99质量%、高达95质量%、高达90质量%、高达80质量%或高达65质量%的量的氢。
剩余的次级氢,即除氢外的成分为其它气态成分,该其它气态成分可以包括氮、二氧化碳和/或氧,或由它们组成。通常,其它气态成分的主要部分或全部由氮组成。例如,如果其它气态成分的总量为100质量%,氮可能占所述其它气态成分的50质量%或更多、75质量%或更多、90质量%或更多或甚至95质量%或更多。
转移到电化学压缩单元的次级氢的流速可为20至2000SCFH(0.57至56.6Sm3/h),诸如30至1500SCFH(0.85至42.5Sm3/h)、或40至1000SCFH(1.1至28.3Sm3/h)、或50至750SCFH(1.4至21.2Sm3/h)。次级氢到电化学压缩单元的流速在所述单元的操作期间可变化,优选地在上述范围中的一个的限制范围内变化。
优选地,加氢站包括次级氢收集系统,该次级氢收集系统收集由一个或多个或全部加氢站操作单元产生的次级氢,并且该次级氢收集系统连接至电化学压缩单元。
由次级氢收集系统收集的次级氢然后被转移到电化学压缩单元。
次级氢收集系统可包括次级氢缓冲罐。在所述次级氢缓冲罐中,次级氢被从一个或多个、优选地全部次级氢源收集,其中收集系统从次级氢源收集次级氢,并且次级氢在被转移到电化学压缩单元之前被储存。次级氢缓冲罐的出口通常直接连接至电化学压缩单元的入口。次级氢缓冲罐的出口和入口通常配备有阀门,使得可以控制,例如切断次级氢的进出流。次级氢缓冲罐的使用允许实现对次级氢向电化学压缩单元的流动的更好控制。
然而,由于电化学压缩单元可改变原料气混合物的压缩率,本发明的燃料站也可以在没有次级氢缓冲罐的情况下操作,即本发明的燃料站中可不存在此类缓冲罐,使得从燃料站的任一个或上述单元中收集的次级氢被直接转移到电化学压缩单元的入口并以一定流速压缩,该流速可变化以匹配进入气流。
可替代地,出于同样的原因,本发明的燃料站还可以在具有相对较小体积的次级氢缓冲罐的情况下操作。
在次级氢收集系统和/或次级氢缓冲罐中,次级氢可处于环境压力下,或者可处于高于环境压力的压力下。优选地,次级氢收集系统和/或次级氢缓冲罐中收集的次级氢处于0.1至4MPa的压力下。
例如,次级氢缓冲罐可以是含有次级氢的气袋,或者也可以是含有次级氢的刚性容器。
次级氢缓冲罐(如果存在的话)可以配备有压力传感器,在达到限定压力阈值时,该压力传感器触发次级氢缓冲罐的出口阀的打开,并且因此触发次级氢向电化学压缩单元的转移。在触发出口阀的打开的相同压力阈值或时间下,可以触发入口阀的关闭。
在次级氢压缩单元的操作期间,将从连接至电化学压缩单元的入口的次级氢储存器,诸如次级氢收集系统和/或次级氢缓冲罐中提取氢。因此,次级氢中的非氢成分,诸如氮将积聚在电化学压缩单元的入口侧处。
因此,优选地,电化学压缩单元的入口侧包括排放装置,诸如排放阀,以允许对气体进行吹扫。例如,在电化学压缩单元的入口侧处次级氢的氢含量变得太低而无法实现在电化学压缩单元中的有效压缩时,可以进行吹扫。
电化学压缩单元的入口侧可以配备有传感器,在达到限定浓度阈值时,该传感器检测电化学压缩单元的入口侧处的氢的浓度,这触发排放装置的打开,并且因此触发对含有在其中的气体的吹扫。
例如,当罐中的氢浓度达到阈值的1质量%或5质量%时,可以对来自次级氢缓冲罐的气体进行吹扫。
可替代地或附加地,次级氢收集系统,优选地次级氢缓冲罐可以例如在罐的入口或出口处或入口和出口两者处配备有流量计。在电化学压缩单元的入口侧处的氢浓度的降低已知根据进入流和/或输出流变化的情况下,流量计可以触发排出装置的打开,并且因此在达到限定通流时触发对含有在其中的气体的吹扫。
此外,可替代的或附加地,在经过预定时间后,排放装置的打开也可能会被触发,这取决于电化学压缩机的操作。
仍进一步地,可替代的或附加地,在达到电化学压缩单元的能耗的预定阈值时,排放装置的打开也可能会被触发,因为单元的功耗取决于入口流的氢浓度。
吹扫也可以以固定的时间间隔进行。
在电化学压缩单元中压缩后可获得纯化和加压的氢。
优选地,在电化学压缩单元中压缩后获得的加压氢中氢的杂质水平,即压缩气体中不同于氢的成分的量为1,000ppm或更低,更优选地为500ppm或更低,并且最优选地为300ppm或更低。
进一步优选地,在电化学压缩单元中压缩后获得的氢的压力为30MPa或更高。
从电化学压缩单元中获得的压缩氢可以在任何情况下通过常规操作与高压初级氢(即从加氢站获得的加压氢或存在于加氢站中的加压氢)相结合。例如,其可以被转移到在一个或多个机械式压缩机的出口侧处获得的加压初级氢并与之相结合。
优选地,在本发明的加氢站中,从电化学压缩单元获得的压缩氢被转移到中间氢存储体积,诸如本文前面描述的氢存储体,初级加压氢也被存储在该中间氢存储体积中。
来自中间氢存储体积的氢出口流可被进料到氢分配系统。
此外,本发明还涉及一种用于向车辆罐加氢的加氢站的操作方法,其特征在于来自一个或多个燃料站操作单元中含氢气体的泄漏、汽化或排放的次级氢在电化学压缩单元中被压缩,其中次级氢含有氢和其它气态成分。
本文中关于本发明的加氢站所描述的实施例中的任一个也适用于本发明的方法。
具体地,本发明的加氢站的操作方法优选地包括收集由一个或多个机械式氢压缩单元产生的、由一个或多个氢分配单元产生的和/或由一条或多条氢输送管线产生的次级氢,并将其转移到电化学压缩单元。
在例示的实施例中,本发明的燃料站包括机械式压缩机1,其包括定距隔块2。
在使用中,待压缩的气态氢以低压进入机械式压缩机1的入口,在其中被压缩,并以期望的高压离开压缩机。在压缩机1的操作期间,氢从其泄漏,例如,从压缩机封装泄漏,并且泄漏的氢由通过吹扫开口进入定距隔块2的氮流吹扫,从而形成次级氢。次级氢(氮气和氢气的混合物)以大气压力通过吹扫气体出口开口离开定距隔块2。
该次级氢由次级氢收集系统收集并被转移到电化学压缩单元3,次级氢收集系统包含,例如,围绕机械式压缩机1的外壳。
次级氢在电化学压缩单元3中被压缩并纯化,然后,例如被转移到与机械式压缩机1的出口的加压初级氢相结合,其经由加压氢分配系统被转移到氢存储体以用于填充车辆罐。
电化学压缩单元配备有排放阀4以允许在入口罐处次级氢的氢含量变得太低而无法实现在电化学压缩单元中的有效压缩时,对来自压缩单元的入口部分的气体进行吹扫。
次级氢收集系统可以包括次级氢缓冲罐,其配备有传感器(未示出),在达到限定浓度阈值时,该传感器检测罐中的氢的浓度,这触发次级氢缓冲罐的排放阀的打开,并且因此触发对含有在其中的气体的吹扫。

Claims (20)

1.一种用于用氢向车辆罐加燃料的集成式加氢站,所述加氢站包括电化学压缩单元,在所述电化学压缩单元中,源自燃料站操作单元中的一个或多个中的含氢气体的泄漏、汽化或排放的次级氢受压缩,其中,所述次级氢含有氢和另外的气态成分。
2.根据权利要求1所述的加氢站,所述加氢站包括产生次级氢的一个或多个机械式氢压缩单元,所述次级氢收集和转移到所述电化学压缩单元。
3.根据权利要求1所述的加氢站,所述加氢站包括产生次级氢的一个或多个氢分配单元,所述次级氢收集和转移到所述电化学压缩单元。
4.根据权利要求1所述的加氢站,所述加氢站包括产生次级氢的一个或多个氢输送管线,所述次级氢收集和转移到所述电化学压缩单元。
5.根据权利要求1所述的加氢站,其中,所述次级氢含有呈25质量%至90质量%的量的氢。
6.根据权利要求1所述的加氢站,其中,氮占所述次级氢中含有的所述另外的气态成分的50质量%或更多。
7. 根据权利要求1所述的加氢站,其中,在所述电化学压缩单元中压缩后获得的加压氢中,氢的杂质水平为300 ppm或更低。
8.根据权利要求1所述的加氢站,所述加氢站包括次级氢收集系统,所述次级氢收集系统收集由加氢站操作单元中的一个或多个所产生的所述次级氢,并且所述次级氢收集系统连接至所述电化学压缩单元。
9.根据权利要求8所述的加氢站,其中,所述次级氢收集系统包括次级氢缓冲罐。
10.根据权利要求1所述的加氢站,其中,从所述电化学压缩单元获得的压缩氢转移到中间氢存储体积或与高压初级氢相结合。
11.一种用于操作加氢站的方法,所述加氢站用于用氢向车辆罐加燃料,其中,源自燃料站操作单元中的一个或多个中的含氢气体的泄漏、汽化或排放的次级氢在电化学压缩单元中受压缩,并且其中,所述次级氢含有氢和另外的气态成分。
12.根据权利要求11所述的方法,所述方法包括收集由一个或多个机械式氢压缩单元或者一个或多个氢分配单元所产生的次级氢,并将它转移到所述电化学压缩单元。
13.根据权利要求11所述的方法,所述方法包括收集由一个或多个氢输送管线所产生的次级氢,并将它转移到所述电化学压缩单元。
14.根据权利要求11所述的方法,其中,所述次级氢含有呈25质量%至90质量%的量的氢。
15.根据权利要求11所述的方法,其中,氮占所述次级氢中含有的所述另外的气态成分的50质量%或更多。
16. 根据权利要求11所述的方法,其中,在所述电化学压缩单元中压缩后获得的加压氢中,氢的杂质水平为300 ppm或更低。
17.根据权利要求11所述的方法,其中,由加氢站操作单元中的一个或多个所产生的次级氢由次级氢收集系统收集,并转移到所述电化学压缩单元。
18.根据权利要求17所述的方法,其中,所述次级氢收集系统包括次级氢缓冲罐。
19.根据权利要求11所述的方法,所述方法包括从所述电化学压缩单元的入口吹扫次级氢。
20.根据权利要求11所述的方法,其中,从所述电化学压缩单元获得的压缩氢转移到中间氢存储体积或与高压初级氢相结合。
CN202211198915.9A 2021-10-04 2022-09-29 加氢站气态氢回收系统和方法 Pending CN115930096A (zh)

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