Fundamental mechanical problems in hydrogen energy utilization technology: State-of-art review
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摘要: 氢能作为一种零碳排放的能源载体, 在应对全球气候变化和推动能源体系脱碳化发展中扮演着重要角色. 本文系统性地综述了氢能利用技术中的关键力学问题及其研究进展, 涵盖氢制取、纯化、储运、加注、应用以及安全等多个核心环节. 分别介绍了氢制取领域中化石能源制氢、电解水制氢及生物质制氢技术中的复杂流动、反应过程以及不同制氢方法下的力学挑战; 探讨了氢纯化环节中变压吸附法和膜分离法中的耦合集成技术及其优化; 分析了氢储运过程中高压气态储氢、低温液态储运及固态储氢技术中的力学问题, 包括容器结构力学性能的优化、氢液化过程效率的提升以及绝热管理技术的改进等; 研究了氢应用领域中氢加注过程的多因素耦合影响、氢燃料电池的传质与水热管理优化以及氢内燃机的燃烧特性; 强调了氢安全中的泄漏与爆炸问题, 涉及氢气的泄漏扩散、燃爆机理及防范措施; 最后, 针对管道输氢中的界面损伤与管内流动问题, 提出了若干研究建议, 为未来氢能产业的大规模发展提供理论支撑.Abstract: Hydrogen energy, as a zero-carbon energy source, is crucial for addressing climate change and promoting energy decarbonization. This paper systematically reviews key mechanical issues in hydrogen energy technologies, covering production, purification, storage and transportation, fueling, application, and safety. It introduces complex processes and mechanical challenges in fossil-fuel-based, water electrolysis, and biomass-based hydrogen production. The coupling and optimization of pressure swing adsorption and membrane separation for hydrogen purification are discussed. Mechanical issues in high-pressure gaseous, low-temperature liquid, and solid-state hydrogen storage are analyzed, including container structural optimization, liquefaction efficiency improvement, and thermal insulation management. In terms of application, the paper explores multi-factor coupling in the fueling process, optimization of mass transfer and water-thermal management in fuel cells, and combustion characteristics of hydrogen internal combustion engines. It emphasizes the risks of hydrogen leakage and explosion, discussing related mechanisms and preventive measures. Finally, suggestions are proposed for addressing interface damage and flow issues in hydrogen pipeline transportation, providing theoretical support for the large-scale development of the hydrogen energy industry in the future.
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图 2 以氢能为枢纽的“能源互联” (本图源自网络公开资料, 原图出自(Ruth et al. 2020))
图 4 煤炭超临界水气化制氢反应机理(Hui et al. 2015, 吕友军 等 2022). (a)煤炭超临界水气化制氢主要物理、化学过程、集总参数模型示意, (b)超临界水流态化分解示意
图 5 典型橇装天然气制氢加氢一体站工艺流程(宋鹏飞 等 2023)
图 6 电解水制氢技术基本原理(Kumar & Himabindu. 2019, 陈彬 等 2022)
图 7 不同类型电解池设计理念. (a)离子选择性AquaPIM膜及其液流电池示意图(Baran et al. 2019), (b)无电解质隔膜流动电解池工作原理(Yan et al. 2021), (c)传统膜电极与整体有序化膜电极结构设计(Wan et al. 2022)
图 8 生物质的主要存在形式(李亮荣 等 2022)
图 9 (a)氢气分离膜的分类 , (b)膜内气体传输机制示意图(Li P Y et al. 2015), (c)催化膜反应器中催化剂的几种负载方式(王金亮和黑悦鹏 2021)
注: A Poiseuille流动; B努森扩散; C分子筛分; D毛细管冷凝; E表面扩散; F溶解扩散; G促进传递.
图 11 (a)瓶口组合阀组合形式(Hausmann 2021), (b)单个空心玻璃微球(Kohli et al.2008), (c)圆柱体和六角形微管阵列(Zhevago & Glebov 2007), (d)高压−固态复合气态储氢罐结构 (蒲亮 等 2022)
图 12 (a)结合了MR制冷系统, 以及MR-H2焦耳−布雷顿级联制冷系统, (b)设备低温段JB循环流的MR组成(Asadnia & Mehrpooya 2018)
图 14 (a)充气过程结束时喷注器向上、垂直和向下(直径6 mm)时的温度场(Melideo et al. 2019), (b)不同充氢质量流量下氢气温度的变化(何青和胡华为 2022)
图 16 (a)不同肋板位置排布的阴极侧流道结构(Heidary et al. 2017), (b)肋下通过气体扩散层的对流(Wilberforce et al. 2019), (c)波浪形仿生结构流道(Cai et al. 2020), (d)叶脉形仿生结构流道(Ouellette et al. 2018)
图 17 (a)氢气循环系统 (引射器) 组成及器件(赵海贺 等 2022), (b)三叶转子型线(Zhou et al. 2021)
图 18 (a)缸内直喷氢内燃机的3种燃烧模型(李星国 2023), (b)混合气均匀性系数随喷氢流量的变化(杨振中 等 2022), (c)不同压缩比匀速压缩下, NOx排放量随燃空当量比的变化(Jilakara et al. 2015)
图 19 (a)高压欠膨胀射流激波结构示意(Wilkes et al. 2008), (b)高压欠膨胀射流发展过程(Li X et al. 2021), (c)不同工况、不同孔径下监测点氢气浓度变化(赵泽滢 2022)
图 20 (a)环形涡旋结构的发展过程(Wang et al. 2020), (b)截面尺寸对火焰传播速度的影响: 早/中期二维火焰面切片流场(周宁 等 2020)
图 21 氢吸附及渗透过程. (a)液相电化学阴极极化充氢及氢原子渗透过程示意(Vecchi et al. 2018), (b)氢气管道表面可能存在的两种氢原子产生机理示意(Sun & Cheng 2021a)
图 22 (a)钢的各种氢捕获位置(刘神光 等 2020), (b)同应力下X80钢焊件(Ⅰ)热影响区、(Ⅱ)基钢、(Ⅲ)焊缝金属不同区域的电化学氢渗透电流曲线(Sun & Cheng 2021b), (c)腐蚀速率和氢气浓度的关系(Wasim & Djukic 2020)
表 1 氢气与石油 (气)、天然气性质比较
参数 氢气 石油 (气) 天然气 热值 (KJ/kg) 142351 50179 38931 气态密度 (kg/m3) 0.089 2.35 0.7174 能量密度 (MJ/kg) 143 44 42 燃点 (℃) 574 426 538 燃烧点能量 (MJ) 0.02 0.2 0.29 燃烧产物 H2O CO\CO2 CO\C\CO2\H2O 爆炸极限 (%) 4.1-75 1.4-7.6 5.3-15 毒性 无毒 一般 较低 
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表 2 主要生物制氢技术
生物制氢技术 原理 热化学转化 热解法 生物质热解产生气−液−固三相产物后继续催化重整制氢 气化法 生物质在高温或超临界物质中气化为含氢产物 微生物转化 光解法 微生物利用光合作用分解水制氢 发酵法 发酵细菌在光照或厌氧环境下分解生物质制取氢气
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表 3 等温吸附模型
模型种类 表达式 模型种类 表达式 Freundlich模型 $ V = {K_b}{p^n} $ 二参数BET模型 $ V = \dfrac{{{V_m}Cp}}{{\left( {{P^0} - P} \right)\left[ {1 + \left( {C - 1} \right)\dfrac{p}{{{p^0}}}} \right]}} $ Langmuir模型 $ V = V_L^{}p/\left( {{P_L} + p} \right) $ 三参数BET模型 $ V = \dfrac{{{V_m}Cp\left[ {1 - \left( {n + 1} \right){{\left( {\dfrac{p}{{{p^0}}}} \right)}^n} + n{{\left( {\dfrac{p}{{{p^0}}}} \right)}^{n + 1}}} \right]}}{{\left( {{P^0} - P} \right)\left[ {1 + \left( {C - 1} \right)\dfrac{p}{{{p^0}}} - C{{\left( {\dfrac{p}{{{p^0}}}} \right)}^{n + 1}}} \right]}} $ 扩展的Langmuir模型 $ V = \dfrac{{{V_L}{K_b}p}}{{1 + {K_b}p + n\sqrt {{K_b}p} }} $ Toth模型 $ V = \dfrac{{V_L^{}{K_b}p}}{{{{\left[ {1 + {{\left( {{K_b}p} \right)}^n}} \right]}^{\frac{1}{n}}}}} $ Dubinin-
Radushkevich模型$ V = {V_0}\exp \left[ { - DL{n^2}\left( {\dfrac{{{p^0}}}{p}} \right)} \right] $ L-F模型 $ V = {V_L}\dfrac{{{K_b}{p^n}}}{{1 + {K_b}{p^n}}} $ Dubinin-
Astakhov模型$ V = {V_0}\exp \left[ { - DL{n^n}\left( {\dfrac{{{p^0}}}{p}} \right)} \right] $
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表 5 气态燃料的相对泄漏率及流动参数
物质 相对泄漏率 流动参数 (0℃, 101.3 kPa (标况)) 扩散 层流 湍流 空气中的扩散系数/(cm2·s−1) 密度/(kg·m−1) 动力粘度/(Pa·s) 甲烷 1.0 1.0 1.0 0.223 0.717 10.3 氢气 3.8 1.26 2.83 0.611 0.08985 8.42 丙烷 0.63 1.38 0.6 0.121 (丙烷为主的液化石油气) 2.02 7.95 (18℃)
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表 6 关键力学问题一览表
研究领域 关键技术 关键力学问题 氢制取 化石能源制氢 煤制氢——煤浆的固流转化与气化过程中的流动与流变特性复杂多变, 涉及非牛顿流体流动、多相耦合流动及传热传质问题.
天然气制氢——反应过程中的物料平衡、热量平衡及各种反应速率的精确控制, 以及反应器内复杂的多相流动和传热现象.电解水制氢 碱性电解水——隔膜的结构设计对流体传输和电能损耗的影响, 以及电解过程中的气−液−固三相传质机制.
PEM电解水——膜电极的有序化设计、流体在多孔介质中的复杂流动及传热传质现象.
SOEC电解水——高温高压环境下的材料性能要求, 以及电堆内部的热梯度和热应力管理.生物质制氢 热化学转化——焦油颗粒的堵塞问题, 催化重整反应中的积炭结焦现象, 以及反应器内的复杂气−液−固三相流动.
微生物转化——反应器内生物质与微生物的相互作用, 以及流态化反应器的设计与优化.氢纯化 变压吸附法 吸附穿透与平衡过程——吸附过程中的热效应对吸附量及吸附热值的影响, 以及多组分气体在吸附床内的流动与传热传质问题. 膜分离法 膜内传输与成膜材质——膜的结构设计与气体传输机制, 以及膜的机械强度、耐高温性能等关键性能的提升. 氢储运 高压气态储氢 容器结构及力学性能优化——高压储氢容器的材料选择、结构设计及瓶口组合阀的优化, 以及氢脆和渗透问题. 低温液态储运 氢液化与振荡漏热——氢液化过程中的能耗与效率问题, 以及液氢输运过程中的漏热和蒸发损失问题. 固态储氢 充放氢过程中的热力学与动力学问题——固态储氢材料的吸放氢温度、速度及循环性能的优化. 氢应用 氢加注 多因素耦合加注及设备研制设计——加注过程中的质量、动量、能量传递机理, 以及加注设备的优化设计与制造. 氢燃料电池 传质与水热管理优化——流道内的气/液体流动行为及流场结构设计, 以及水管理策略的优化. 氢内燃机 燃烧特性优化——氢气喷射技术、混合气形成过程及燃烧特性的优化, 以及排气及过滤系统的性能提升. 氢安全 泄漏与爆炸 泄漏扩散与燃爆机理——氢气泄漏后的扩散规律、燃爆机理及防范措施, 以及高压氢气泄漏燃爆的规律及机理研究. 管道输氢 界面损伤与管内流动——管道壁面在氢环境下的损伤机制, 以及管道内氢气流动与传热的跨尺度、多维度、多因素耦合机理研究.
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