CN116464905A - 等压放热与等容复热过程耦合热力升压储供氢系统及方法 - Google Patents

等压放热与等容复热过程耦合热力升压储供氢系统及方法 Download PDF

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CN116464905A
CN116464905A CN202210033594.0A CN202210033594A CN116464905A CN 116464905 A CN116464905 A CN 116464905A CN 202210033594 A CN202210033594 A CN 202210033594A CN 116464905 A CN116464905 A CN 116464905A
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hydrogen
tank
pressure
temperature
tanks
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朱家骅
夏素兰
李季
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Sichuan University
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C5/00Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures
    • F17C5/02Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures for filling with liquefied gases
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/081Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F17C13/00Details of vessels or of the filling or discharging of vessels
    • F17C13/005Details of vessels or of the filling or discharging of vessels for medium-size and small storage vessels not under pressure
    • F17C13/006Details of vessels or of the filling or discharging of vessels for medium-size and small storage vessels not under pressure for Dewar vessels or cryostats
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    • F17C13/00Details of vessels or of the filling or discharging of vessels
    • F17C13/02Special adaptations of indicating, measuring, or monitoring equipment
    • F17C13/025Special adaptations of indicating, measuring, or monitoring equipment having the pressure as the parameter
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    • F17C13/00Details of vessels or of the filling or discharging of vessels
    • F17C13/04Arrangement or mounting of valves
    • F17C13/045Automatic change-over switching assembly for bottled gas systems with two (or more) gas containers
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    • F17C5/00Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures
    • F17C5/002Automated filling apparatus
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    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
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    • F17C7/00Methods or apparatus for discharging liquefied, solidified, or compressed gases from pressure vessels, not covered by another subclass
    • F17C7/02Discharging liquefied gases
    • F17C7/04Discharging liquefied gases with change of state, e.g. vaporisation
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F17C2201/00Vessel construction, in particular geometry, arrangement or size
    • F17C2201/03Orientation
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    • F17C2201/00Vessel construction, in particular geometry, arrangement or size
    • F17C2201/05Size
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    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2205/00Vessel construction, in particular mounting arrangements, attachments or identifications means
    • F17C2205/01Mounting arrangements
    • F17C2205/0123Mounting arrangements characterised by number of vessels
    • F17C2205/013Two or more vessels
    • F17C2205/0134Two or more vessels characterised by the presence of fluid connection between vessels
    • F17C2205/0142Two or more vessels characterised by the presence of fluid connection between vessels bundled in parallel
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    • F17C2205/00Vessel construction, in particular mounting arrangements, attachments or identifications means
    • F17C2205/03Fluid connections, filters, valves, closure means or other attachments
    • F17C2205/0302Fittings, valves, filters, or components in connection with the gas storage device
    • F17C2205/0352Pipes
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    • F17C2205/00Vessel construction, in particular mounting arrangements, attachments or identifications means
    • F17C2205/03Fluid connections, filters, valves, closure means or other attachments
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    • F17C2221/00Handled fluid, in particular type of fluid
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    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2223/00Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/01Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
    • F17C2223/0146Two-phase
    • F17C2223/0153Liquefied gas, e.g. LPG, GPL
    • F17C2223/0161Liquefied gas, e.g. LPG, GPL cryogenic, e.g. LNG, GNL, PLNG
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    • F17C2223/00Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/03Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
    • F17C2223/035High pressure (>10 bar)
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    • F17C2223/00Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/03Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
    • F17C2223/036Very high pressure (>80 bar)
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    • F17C2227/00Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
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    • F17C2227/00Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
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    • F17C2227/0302Heat exchange with the fluid by heating
    • F17C2227/0306Heat exchange with the fluid by heating using the same fluid
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    • F17C2227/00Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
    • F17C2227/03Heat exchange with the fluid
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    • F17C2227/00Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
    • F17C2227/03Heat exchange with the fluid
    • F17C2227/0367Localisation of heat exchange
    • F17C2227/0369Localisation of heat exchange in or on a vessel
    • F17C2227/0376Localisation of heat exchange in or on a vessel in wall contact
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    • F17C2227/00Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
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    • F17C2265/00Effects achieved by gas storage or gas handling
    • F17C2265/01Purifying the fluid
    • F17C2265/015Purifying the fluid by separating
    • F17C2265/017Purifying the fluid by separating different phases of a same fluid
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/30Hydrogen technology
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Abstract

等压放热与等容复热过程耦合热力升压储供氢系统及方。针对绿电及谷电周期性特点,利用氢气在常温‑深冷(290‑30K)温区热力学性质构建等压放热等容复热的热力升压储供氢系统,实现8小时电解水制氢和90MPa高压储氢、24小时连续稳定供氢。预压缩至<6MPa的氢气在该温区等压放热后膨胀液化、液氢又吸取此热量等容复热升压至常温90MPa,从而以6MPa预压缩实现90MPa高压储/供氢,单耗<3kWh/kg。系统主要包括水平阵列常温储供氢罐内置翅片式换热器,全过程由自控阀执行;例如日供氢1000kg制/储/供一体化加氢站32罐阵列、单罐容积0.625m3,每小时2250kg的合成氨供氢站96罐阵列、单罐容积11.0m3

Description

等压放热与等容复热过程耦合热力升压储供氢系统及方法
技术领域
本发明涉及储氢与供氢技术领域,特别是深冷低温区伴随氢气状态变化产生的热力过程耦合与能量高效转换技术,应用于氢能源制、储、输、用一体化。
背景技术
电解水制氢是绿电替代化石能源的重要途径之一,低碳时代备受关注。氢的优良性质之一是单位质量热值高(120 MJ/kg);但其质量密度却很低或换言之比容很大(298K/0.1MPa温度/压力下密度仅0.0824 kg/m3而比容达12.14 m3/kg),对大规模氢能源储、输、用各环节均不利。提高氢的密度(增密)或降低比容(降容)的现有技术有两类:深冷液化(LH2)与机械加压(MGH2),例如29K/0.685MPa的液氢密度达56.55 kg/m3、273K/90MPa的高压氢气密度也可达60 kg/m3。不过,深冷液化过程要消耗动力5~8 kWh/kg-LH2(殷靓等. 氢液化流程设计和优化方法研究进展. 制冷学报,2020, 3/41: 1-10);根据常规氢温-熵图计算,机械加压至90MPa也要消耗动力4~6 kWh/kg-GH2(Michael Hirscher et al. Handbook ofHydrogen Storage, 2010, WILEY-Verlag GmbH & Co. KGaA, Weinheim)。此外,深冷液氢温区绝热保冷和高压机械压缩过程都还需要提供辅助冷媒。而且,从适用角度,目前90MPa氢气压缩机仅见于氢燃料汽车加氢站用小型离子液体压缩机(刘泽坤等. 加氢站用离子压缩机及离子液体简述. 化工设备与管道,2020, 6/57: 47-53),用于大规模储/供氢的技术经济可行性不大。
另一方面,从氢能源制、储、输、用一体化角度分析,虽然液氢适于储存和运输,但绝大部分使用场合(地面及水面交通用氢发动机、氢燃料电池和化工原料等)用氢状态是加压氢气。例如储氢状态是液氢、加氢站再汽化加压至所需的90MPa,则储/供过程耗用于氢气状态变化的能量将达10 kWh/kg-GH2(超过氢能源热值的30%)。因此,通过优化氢能源储/供过程状态变化热力学路径从而降低储/供氢能耗,对氢能源大规模工业化应用具有重要意义。
本发明的技术思想是,利用氢气从常温区(273~303K)到低温区(<50K)等压放热同时降温/降容/增密和从低温区到常温区等容复热同时升温/升压两过程(以下所述“等压放热”与“等压放热同时降温/降容/增密”有相同含义、所述“等容复热”与“等容复热同时升温/升压”有相同含义)的热力学性质,构建等压放热与等容复热过程耦合推动高压储/供氢的热力转换系统(结合常规氢温-熵图):预加压3~6MPa的氢气先从常温区至低温区沿等压线放热降温降容提升密度后,再保持密度不变从低温区折返至常温区沿等容线吸热升温升压,从而实现≥55MPa的热力高压储/供氢。本发明的技术路线是,经预压缩的常温氢等压放热降温(至<50K)增密(至大于临界值31.36kg/m3)后沿等容线折返吸热升温升压的耦合过程在同一组封闭的储罐内耦合进行:储罐内置双程翅片管换热器,氢气等压放热降温增密的过程在换热管内进行、降温增密后进入封闭的罐内(等容)空间通过自然对流传热从翅片换热管外表面吸取管内释放的热量,利用常温氢气自身等压放热增密释放的热量对增密后的氢气进行热力加压,从而实现回收低温(273K~50K)热能并直接转换为≥55MPa氢气压力能的高效热力耦合。
实现本发明热力耦合过程的循环系统包括数量不限且可完全互换的储/供氢罐(及其内置的双程翅片管换热器)阵列组合和氢压缩机及氢膨胀机。储/供氢罐(以下也简称氢罐)内置的双程翅片管换热器(以下也简称换热器),流入管口和流出管口布置在氢罐同一端的进/出口管箱内,氢气从流入管口到其端部又折流从流出管端部流出到管口、来回双程都与翅片管外封闭空间自然对流的氢气进行换热过程,其有效传热面积与氢罐储氢容积之比≥200 m2/m3、与氢罐内表面积之比≥20 m2/m2,且任一氢罐经历降温(常温→低温)后又升温(低温→常温)串联耦合的热力转换过程历时不超过2小时,置于静止室温环境的氢罐内表面与罐内自然对流的氢气之间次生自然对流传热量小于双程翅片管换热器传热负荷的5%、氢罐外表面不必绝热保冷。
本发明以换热器替代高压压缩机,通过等压放热与等容复热过程耦合实现深冷温区热力转换,以小于3 kWh/kg的储/供氢电耗实现≥55 kg/m3常温高密度储氢和≥90MPa高压供氢,且采取自动控制切换式储氢罐阵列组合,适配于电网电力冗余时段(用电“谷期”及发电冗余“峰期”)电解水制氢/储氢,储氢量灵活可调满足全时段供氢量所需,是绿电制氢、高效储能的一种实用技术手段,具有可持续的技术经济性优势和市场竞争力。
发明内容
本发明公开一种等压放热与等容复热过程耦合的高压储/供氢系统与热力升压方法。如图1所示,该循环系统包括水平阵列排布的氢罐10、其数量根据需要而定,罐体用耐氢蚀、耐低温交变应力的金属材质制作,氢罐内置铝制双程翅片管换热器11。所有氢罐(包括其内置换热器)构造相同、可以互换,氢罐上的接口与相应总管连接(包括氢罐与低温液氢总管5和高压供氢总管6的连接、换热器进口与循环补充氢总管7或换热器连通管9的连接、换热器出口与氢膨胀机进口总管8或连通管9的连接)方式也对应相同;5、6、7、8各总管各自为一个闭环回路,通过自动控制阀12~16执行每一个氢罐与各总管接通/断开状态切换、由此进行氢罐操作周期切换以及氢罐动态分区,所有氢罐循环遍历如下所述的各种动态分区操作:
如图1虚线框1系统构成及空罐冷却区范围所示,动态空罐冷却区包括12~24个氢罐(动态编号1-1、1-2、…、1-n,从气液分离器18顶部来的低温循环氢气接入1-1罐开始、顺其气体串联通过双程翅片管换热器的个数而递增、直至其离开最后的1-n罐去氢压缩机19为止),与每个氢罐连接的翅片换热器出口截止阀12开启、出口换向阀13与连通管9连通、入口换向阀14也与连通管9连通、进/出口截止阀15关闭,由此形成低温循环氢气通过翅片换热器管内强制对流吸热(罐内保留的氢气自然对流放热,详述于后)冷却氢罐的动态空罐冷却区;离1-1罐越近空罐温度越低(空间分布)、经历冷却时间越长空罐温度也越低(时间分布),至一个动态空罐冷却周期(5~30分钟)终点时刻1-1罐内温度已降至≤38K(比接入的低温循环氢气温度高5~10K)、启动切换程序:即1-1罐退出该区而进入液氢充注区(详述于后),原1-2罐自动替代原1-1罐的阀门连接状态而成为新1-1罐、同时原排在1-n罐之后的一个空罐自动替代原1-n罐的阀门连接状态而成为新1-n罐,由此从新1-1罐到新1-n罐、开始一个新的动态空罐冷却周期。
如图1虚线框2范围所示,动态充注液氢区2包括氢罐的个数不限,空罐温度≤38K、罐内保留氢气压力≤0.5MPa;在任一充注液氢周期内至少有一个氢罐的进/出口截止阀15开启、与之相连的换向阀16使该氢罐充注空间与低温液氢总管5连通、接受从气液分离器18底部输送来的液氢其压力比空罐内保留氢气的压力高0.05~0.1MPa;在一个动态充注周期(5~30分钟)终点时刻充满该罐、关闭该罐截止阀15的同时开启另一个待充液氢罐的截止阀15,开始一个新的动态充注液氢周期;充注液氢区内所有氢罐的双程翅片管换热器出口截止阀12始终关闭、换向阀13和14始终与连通管9连通。
如图1虚线框3范围所示,氢罐等压放热/等容复热过程耦合动态传热区包括12~24个氢罐(动态编号3-1、3-2、…、3-n,从循环及补充氢总管7接入3-1罐开始、顺其串联通过换热器的个数而递增、直至其最后离开3-n罐去氢膨胀机17为止),该区内所有换热器出口截止阀12均开启、3-1罐换向阀14使该罐换热器的进口与循环及补充氢总管7连通、3-n罐换向阀13使该罐换热器的出口与膨胀机进口总管8连通、其余氢罐的换向阀13和14均与连通管9连通,罐内已充满低温液氢、所有氢罐进/出口截止阀15关闭;循环及补充氢总管7输送的3~6MPa预加压常温(<303K)氢气进入3-1罐换热器进口、顺序串联流经该区所有氢罐的翅片管双程换热器、直至离开最后的3-n罐换热器出口进入膨胀机进口总管8,翅片管内流动的氢气等压(3~6MPa)放热、管外低温氢自然对流等容复热,管内等压放热的氢气沿串联流动方向温度递降、使罐内等容复热的低温氢沿与之逆流的方向温度递升,至一个等压放热/等容复热动态传热周期(5~30分钟)终点时刻,3-1罐内吸热的氢温度比翅片管内来流放热的预压缩常温氢气温度低10~50K达到传热平衡、罐内相应达到储氢所需高压(≥55MPa),启动切换程序:即3-1罐退出该区而进入高压供氢罐区4(详述于后)、原3-2罐自动替代原3-1罐的阀门连接与开启状态而成为新3-1罐、同时使紧邻原最后3-n罐之后的一个充满低温液氢罐自动替代原3-n罐的阀门连接与开启状态而成为新3-n罐,由此从新3-1罐到新3-n罐开始一个新的动态传热区周期。
如图2虚线框4范围所示,高压供氢罐区包括氢罐的个数不限,经过等容升温升压至常温高压(55~90MPa)的储氢罐进入该罐区,根据用户需求供氢量(1.0~40.0kg/min)和供氢压力(1.0~90MPa),调控该区内阀门开闭状态,实现单罐对外供氢和多罐同时对外供氢:单罐供氢时只有该罐的进/出口截止阀15开启并通过换向阀16与高压供氢总管6连通、区内其它罐的截止阀15关闭;多罐供氢时所有供氢罐阀门15的开启及与总管6的连通状态与单罐供氢相同;该区内所有氢罐的翅片换热器出口截止阀12关闭、换向阀13及14与连通管9连通。采取单罐与多罐组合,实现压力递增式梯级供氢方式:供氢罐区内多罐组合的12~24个储氢罐、各罐内保有氢气压力按从低到高的顺序从2MPa递增至90MPa,通过自动控制阀门开闭状态切换供氢罐使其正在对外供氢压力与正在受氢容器内氢气压力之比在1.1~1.5范围之内,从而确保任何时刻受氢容器内因氢气压缩产生的温升<20K;任何时刻当正在供氢罐内的压力下降至罐内保留氢气规定值(≥1.0MPa)时该罐停止供氢并关闭截止阀15,随之该罐作为空罐退出高压供氢罐区并进入动态空罐冷却区排队候补(成为新1-1罐)。
氢罐等压放热/等容复热过程耦合动态传热区一个周期内(5~30分钟),循环与补充氢气串联通过3-1~3-n所有双程翅片管换热器放热降温、至3-n换热器出口其温度比该罐内等容复热的低温氢平均温度高5~8K;该过程中,罐内等容复热的氢通过自然对流接受翅片管表面传出的热量而升温升压、其温度和压力按3-n~3-1的顺序逐罐上升并进入超临界状态、至3-1罐内超临界氢压力达到储/供氢需求(55~90MPa)、平均温度比该罐换热器入口循环及补充氢气温度低10~50K、此时该罐退出等压放热/等容复热过程耦合动态传热区进入高压供氢罐区4,同时启动如前所述的切换程序、开始一个新的动态传热区周期。
动态空罐冷却区一个周期(不超过10分钟)内,低温循环氢气串联通过1-1~1-n所有双程翅片管换热器吸热升温至1-n罐换热器出口其温度比该空罐(罐内保留氢气以及换热器自身)平均温度低8~15K;该过程中,氢罐内保留氢气通过自然对流向翅片管表面放热而使空罐按1-n~1-1的顺序逐罐降温,至1-1罐平均温度仅比该罐换热器入口的低温循环氢气温度高8~15K、该罐退出动态空罐冷却区1而进入动态充注液氢区2,同时启动如前所述的切换程序、开始一个新的动态空罐冷却区周期。
上述所有动态分区切换程序调控相关自动阀门开或闭的幅度及速度配合,使系统内连接氢膨胀机17、气液分离器18和氢压缩机19的管道(包括低温液氢总管5、高压供氢总管6、循环及补充氢总管7、氢膨胀机进口总管8和翅片换热器连通管9)内保持稳态流动。
通过氢膨胀机进口总管8进入氢膨胀机17的循环与补充氢气压力3~6MPa、温度≤40K,通过膨胀机做功后压力下降至0.3~0.8MPa、温度26~30K、液/气质量比≥3/2,通过气液分离器18分离后,液氢由低温液氢总管5输送到氢罐充注液氢区2,氢气作为低温循环氢气输送到动态空罐冷却区1、按前述通过翅片换热器连通管9串联流过动态空罐冷却区1-1~1-n所有双程翅片管换热器管内强制对流传热吸取空罐的热量至换热器1-n出口其温度升至比该空罐平均温度低8~15K、离开该罐后与质量流量与充注液氢相同的补充(待增密加压储存)氢气等压汇合进入氢气压缩机19,预加压到3~6MPa,通过冷却器20等压降温至≤303K、通过循环与补充氢气总管7输送到等压放热/等容复热传热区3,在一个动态传热周期内(5~30分钟),串联通过动态编号为3-1~3-n的12~24个换热器管内等压放热降温至最后3-n换热器出口其温度降至≤40K,通过氢膨胀机进口总管8进入氢膨胀机17膨胀做功,由此构成预加压氢气(包括空罐内的保留氢气)从常温(273~303K)至低温(<50K)再折返常温的等压放热与等容复热过程耦合热力加压循环。
本发明适用于水、风、光电及电网“谷电”制氢储能,特别是制、储、供、用一体化氢能源加工,通过3~6MPa压缩-膨胀循环,推动等压放热与等容复热过程耦合热力升压,实现55 kg/m3高密度和90MPa高压储/供氢、电耗小于3 kWh/kg(约为电解水制氢能耗的6%)。
附图说明
附图1和附图2是本发明提供的等压放热与等容复热过程耦合热力升压储/供氢系统及方法的示意图。
附图1和附图2中:1–系统构成及空罐冷却区;2–氢罐充注液氢区;3–氢罐等容复热/等压放热传热区;4–氢罐高压供氢区;5–低温液氢总管;6–高压供氢总管;7–循环与补充氢总管;8–膨胀机进口总管;9–翅片换热器连通管;10–储氢罐;11–储氢罐内双程管式翅片换热器;12–翅片换热器出口截止阀;13–总管8与连通管9的换向阀;14–总管7与连通管9的换向阀;15–进/出口截止阀;16–切换总管5与总管6的换向阀;17–氢气膨胀机;18–气液分离器;19–氢气循环压缩机;20–冷却器;1-1、1-2、1-n–空罐冷却区动态编号;3-1、3-2、3-n–氢罐等压放热与等容复热传热区动态编号。
具体实施方式
以下结合但不限于实施例阐述本发明具体实施方式
实施例1:制/储/供一体化的氢燃料汽车加氢站,采用本发明热力升压90MPa储/供氢系统与方法,供氢能力1000kg/日(24h),车载氢气罐受氢压力35~75MPa。
本例储/供氢罐内径0.4m、直筒段长度5m、单罐容积0.625m3,内置双程翅片管式换热器有效传热面积150m2。8小时谷电期内,电解水制氢1000kg同时预压缩至5MPa等压放热降温增密液化装罐并等容升压至90MPa储氢的系统与方法已详述于前,1000kg氢分装于32个储氢罐。
每日24小时稳定加氢能力不低于40kg/h(平均),峰值加氢能力不超过100kg/h。32个90MPa储氢罐逐罐加入供氢的步骤是:单罐与多罐组合供氢工作罐区包括12个储/供氢罐组合、各罐内保有氢气压力按从低到高的顺序从2MPa开始逐罐递增1.414倍至90MPa;该区内所有氢罐的翅片换热器出口截止阀12关闭、换向阀13及14与连通管9连通,通过自动控制阀门开闭状态切换供氢罐使其对外加氢压力与正在受氢的车载氢气罐内氢气压力之比在1.1~1.414范围之内、符合该条件的供氢罐的进/出口截止阀15开启并通过换向阀16与高压供氢总管6连通对外供氢、区内其它供氢罐的截止阀15关闭;任何时刻当正在供氢罐内的压力下降至罐内保留氢气规定值2.0MPa时该罐停止供氢并关闭截止阀15、退出供氢工作罐区,随之补入一个90MPa储氢罐。
实施例2:采用本发明热力升压90MPa储/供氢系统与方法的制/储/供一体化装置,供氢能力53000kg/日(24h),满足10万吨/年合成氨生产装置长周期(8000小时/年)连续运行要求。
本例储/供氢罐内径1.0m、直筒段长度14.0m,单罐容积11.0m3,内置双程翅片管式换热器有效传热面积3600m2。8小时谷电期内,电解水制氢53000kg同时预压缩至5MPa等压放热降温增密液化装罐并等容升压至90MPa储氢的系统与方法已详述于前,53000kg氢分装于96个储氢罐。
每日24小时连续稳定供氢量2250kg/h,合成氨生产装置受氢压力恒定为15MPa。96个90MPa储氢罐加入供氢工作罐区的步骤是:96罐同步加入多罐组合供氢工作罐区,该区内所有氢罐的翅片换热器出口截止阀12关闭、换向阀13及14与连通管9连通,进/出口截止阀15开启并通过换向阀16与高压供氢总管6连通对外供氢;高压供氢总管6与合成氨生产装置受氢容器之间,串联配置一组由膨胀分支管路与压缩分支管路并联构成的恒压供氢单元,确保任何时刻受氢容器接受的氢气压力恒定在设定值(15MPa);在24小时供氢周期内氢罐压力随时间持续下降,从90MPa下降至受氢压力设定值(15MPa)期间开启膨胀分支管路、关闭压缩分支管路、总管6供氢通过膨胀机降压至设定值(15MPa)后输送给合成氨装置受氢容器、同时回收膨胀机输出的动力和冷量,从15MPa至1MPa期间开启压缩分支管路、关闭膨胀分支管路、总管6供氢通过压缩机升压至设定值(15MPa)后输送给合成氨装置受氢容器;当氢罐压力降至1MPa时,该多罐组合退出供氢工作罐区同时将高压供氢总管6切换到新加入的96罐供氢组合。上述压力在线监测、管路切换、膨胀机和压缩机运行、回收动力与冷量的操作均通过自动控制执行。
本发明不限于上述实施例,其技术方案已在发明内容部分予以说明。

Claims (4)

1.一种等压放热与等容复热过程耦合热力升压储/供氢系统,其特征是该循环系统包括水平阵列排布的储/供氢罐,氢罐内置铝制双程翅片管换热器,氢罐数量根据需要而定,所有氢罐及其内置换热器构造相同、可以互换,氢罐上的接口与低温液氢总管、高压供氢总管、循环补充氢总管、氢膨胀机进口总管及换热器连通管的连接方式也对应相同;
低温液氢总管、高压供氢总管、循环补充氢总管、氢膨胀机进口总管各自为一个闭环回路,通过自动控制阀组执行每一个氢罐与各总管接通/断开的状态切换、由此进行氢罐操作周期切换以及氢罐动态分区,调控相关自动阀门开或闭的幅度及速度配合,以使系统内连接氢膨胀机、气液分离器和氢压缩机的管道内保持稳态流动;
氢罐内置铝制双程翅片管换热器有效传热面积与氢罐储氢容积之比≥200 m2/m3、与氢罐内表面积之比≥20 m2/m2,任一氢罐经历从常温降至液氢低温区后又复热升温至常温的串联耦合热力转换过程历时不超过2小时,通过氢罐表面的传热量小于罐内换热器传热负荷的5%,氢罐无绝热保冷层。
2.一种等压放热与等容复热过程耦合热力升压储/供氢的方法,其特征是通过自动控制阀组使热力升压储/供氢系统内水平阵列排布的所有氢罐循环遍历以下各种动态分区操作过程:
动态空罐冷却区,包括12~24个氢罐,与每个氢罐连接的翅片换热器出口截止阀开启、出口换向阀与连通管连通、入口换向阀也与连通管连通、进/出口截止阀关闭,由此形成低温循环氢气通过翅片换热器管内强制对流吸热冷却氢罐的动态空罐冷却区;至一个动态空罐冷却周期5~30分钟的终点时刻,该区离低温循环氢气接入点最近的氢罐内温已降至≤38K、启动切换程序即该罐退出该区而进入液氢充注区、顺低温循环氢气流下游最靠近该罐的一罐自动替代该罐的阀门连接状态而成为新的离低温循环氢气最近的氢罐、同时原排在该罐区下游离低温循环氢气接入点最远一罐之后的一个常温空罐自动替代原最远一罐的阀门连接状态而成为新最远一罐,由此从新的离低温循环氢气最近的氢罐到新的最远一罐、开始一个新的动态空罐冷却周期;
动态充注液氢区,包括氢罐的个数根据需要而定,该区内所有氢罐的双程翅片管换热器出口截止阀始终关闭、进口换向阀和出口换向阀始终与翅片换热器连通管连通,空罐温度≤38K、罐内保留氢气压力≤0.5MPa,在任一充注液氢周期内至少有一个氢罐的进/出口截止阀开启、与之相连的换向阀使该氢罐充注空间与低温液氢总管连通、接受从气液分离器底部输送来的、压力比空罐内保留氢气压力高0.05~0.1MPa的液氢,在一个动态充注周期5~30分钟的终点时刻充满该罐、关闭该罐截止阀的同时开启另一个待充液氢罐的截止阀,开始一个新的动态充注液氢周期;
氢罐等压放热/等容复热过程耦合动态传热区,包括12~24个已充注低温液氢的氢罐,所有氢罐进/出口截止阀均关闭、换热器出口截止阀均开启,离循环及补充氢接入点最近的氢罐换热器进口换向阀使该进口与循环及补充氢总管连通、使输送来的预加压3~6MPa常温<303K的循环及补充氢气进入该罐换热器、顺序串联流经该区所有氢罐的翅片管双程换热器直至离循环及补充氢接入点最远的氢罐换热器出口、通过与膨胀机进口总管连通的换向阀进入膨胀机,该区内其余氢罐换热器进口及出口换向阀均与连通管连通构成循环及补充氢串联流程、流经该区所有翅片管内等压放热、使管外低温氢在氢罐内自然对流等容复热,管内等压放热的循环及补充氢沿串联流动方向温度递降、罐内等容复热的低温氢则沿与之逆流的方向温度递升,至一个等压放热/等容复热动态传热周期5~30分钟终点时刻,最先接入预压缩常温氢气的罐内自然对流等容复热的氢气温升至比接入的预压缩常温氢气温度低10~50K、罐内相应达到≥55MPa的储氢压力,启动切换程序即该罐退出该区而进入高压供氢罐区、顺循环及补充氢气流下游最靠近该罐的一个罐自动替代该罐的阀门连接与开启状态而成为新的预压缩常温氢气接入罐、同时使紧邻原离补充氢接入点最远的氢罐之后一个充满低温液氢的罐自动替代原罐的阀门连接与开启状态而成为新的与膨胀机进口总管连通的罐,由此从新的预压缩常温氢气接入罐到新的膨胀机进口总管连通罐、开始一个新的动态传热区周期;
高压供氢罐区,经过等容升温复热升压至常温高压55~90MPa的储氢罐进入该罐区、氢罐数量根据需要而定,供氢量1.0~40.0kg/min、供氢压力1.0~90MPa;调控该区内阀门开闭状态,实现单罐对外供氢和多罐同时对外供氢,单罐供氢时该罐的进/出口截止阀开启并通过换向阀与高压供氢总管连通、供氢区内其它罐的进/出口截止阀关闭,多罐供氢时所有供氢罐的进/出口阀门均开启并与高压供氢总管连通;供氢罐区内所有氢罐的翅片换热器出口截止阀关闭、换热器进口换向阀及出口换向阀与连通管连通;采取单罐与多罐组合,实现压力递增式梯级供氢方式,即供氢罐区内多罐组合的12~24个储氢罐、各罐内保有氢气压力按从低到高的顺序从2MPa递增至90MPa、通过自动控制阀门开闭状态切换供氢罐使其正在对外供氢压力与正在受氢容器内氢气压力之比在1.1~1.5范围之内,从而确保任何时刻受氢容器内因氢气压缩产生的温升<20K;任何时刻当正在供氢罐内的压力下降至罐内保留氢气规定值≥1.0MPa时、该罐停止供氢并关闭截止阀,随之该罐作为空罐退出高压供氢罐区、进入动态空罐冷却区排队;
通过氢膨胀机进口总管进入氢膨胀机的循环与补充氢气压力3~6MPa、温度≤40K,通过膨胀机做功后压力下降至0.3~0.8MPa、温度26~30K、液/气质量比≥3/2,通过气液分离器分离后,液氢由低温液氢总管输送到氢罐充注液氢区、氢气作为低温循环氢气输送到动态空罐冷却区、通过翅片换热器连通管串联流过动态空罐冷却区内所有氢罐的双程翅片管换热器管内强制对流传热吸取空罐的热量至该区的最后一个换热器出口其温度升至比该空罐平均温度低8~15K、离开该罐后等压汇合补充氢气的质量流量与充注液氢相同,汇合后的循环与补充氢气进入氢气压缩机预加压到3~6MPa、通过冷却器等压降温至≤303K、通过循环与补充氢气总管输送到等压放热/等容复热传热区串联通过12~24个换热器管内等压放热降温至≤40K、通过氢膨胀机进口总管进入氢膨胀机膨胀做功,由此构成循环与补充氢气预加压并冷却至273~303K常温后等压放热降温至<50K低温及膨胀液化、再折返等容复热至常温的过程耦合热力升压循环。
3.根据权利要求1和权利要求2等压放热与等容复热过程耦合热力升压储/供氢系统与方法,其特征是制/储/供一体化的氢燃料汽车加氢站,8小时谷电期内电解水制氢1000kg同时预压缩至5MPa通过等压放热/等容复热升压至90MPa分装于32个内径0.4m、直筒段长度5m、单罐容积0.625m3的储氢罐、罐内置双程翅片管式换热器有效传热面积150m2
采取单罐与多罐组合供氢方式,12个氢罐为一组、为受氢压力35~75MPa的车载氢气罐加氢,24小时稳定加氢能力不低于40kg/h、峰值加氢能力不超过100kg/h;12个一组的氢罐内保有氢气压力按从低到高的顺序从2MPa开始逐罐递增1.414倍至90MPa,通过自动控制阀门开闭状态切换供氢罐、使其对外加氢压力与正在受氢的车载氢气罐内氢气压力之比在1.1~1.414范围之内,符合该条件的供氢罐进/出口截止阀开启、通过高压供氢总管对外供氢,其它供氢罐的截止阀关闭;任何时刻当正在供氢罐内的压力下降至罐内保留氢气规定值2.0MPa时该罐停止供氢并关闭截止阀、退出供氢工作罐,随之补入一个90MPa储氢罐;
所述压力在线监测、阀门切换均通过自动控制执行。
4.根据权利要求1和权利要求2等压放热与等容复热过程耦合热力升压储/供氢系统与方法,其特征是制/储/供一体化为10万吨/年合成氨供氢的装置,8小时谷电期内电解水制氢53000kg同时预压缩至5MPa通过等压放热/等容复热升压至90MPa分装于96个内径1.0m、直筒段长度14.0m、单罐容积11.0m3的储氢罐、罐内置双程翅片管式换热器有效传热面积3600m2
采取96罐同步加入多罐组合、每日24小时连续稳定为合成氨生产装置供氢2250kg/h;合成氨生产装置受氢容器压力恒定为15MPa;
同步加入多罐组合供氢工作罐区所有氢罐的翅片换热器出口截止阀关闭、换热器出口换向阀及入口换向阀均与连通管连通,所有氢罐的进/出口截止阀开启、通过换向阀与高压供氢总管连通对外供氢;高压供氢总管与合成氨生产装置受氢容器之间串联配置一组由膨胀分支管路与压缩分支管路并联构成的恒压供氢单元,确保任何时刻受氢容器接受的氢气压力恒定在设定值15MPa;在24小时供氢周期内氢罐压力随时间持续下降,从90MPa下降至受氢压力设定值15MPa期间开启膨胀分支管路、关闭压缩分支管路、总管供氢通过膨胀机降压至15MPa后输送给合成氨装置受氢容器、同时回收膨胀机输出的动力和冷量,氢罐压力从15MPa下降至1MPa期间开启压缩分支管路、关闭膨胀分支管路、总管供氢通过压缩机升压至15MPa后输送给合成氨装置受氢容器;任何时刻当氢罐压力降至1MPa时,该多罐组合退出供氢工作罐区同时将高压供氢总管切换到新加入的96罐供氢组合;
上述压力在线监测、管路切换、膨胀机和压缩机运行、回收动力与冷量的操作,均通过自动控制执行。
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