WO2023035712A1 - 一种燃料电池氢气纯化管路、方法及系统 - Google Patents

一种燃料电池氢气纯化管路、方法及系统 Download PDF

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WO2023035712A1
WO2023035712A1 PCT/CN2022/098819 CN2022098819W WO2023035712A1 WO 2023035712 A1 WO2023035712 A1 WO 2023035712A1 CN 2022098819 W CN2022098819 W CN 2022098819W WO 2023035712 A1 WO2023035712 A1 WO 2023035712A1
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fuel cell
pipeline
purification
hydrogen
purification pipeline
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PCT/CN2022/098819
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English (en)
French (fr)
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刘蓉
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中国华能集团清洁能源技术研究院有限公司
华能国际电力股份有限公司
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Publication of WO2023035712A1 publication Critical patent/WO2023035712A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0668—Removal of carbon monoxide or carbon dioxide
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the application belongs to the technical field of clean energy, and specifically relates to a fuel cell hydrogen purification pipeline, method and system.
  • Hydrogen energy is one of the most ideal clean energy sources in the future.
  • Hydrogen fuel cell vehicles use hydrogen as fuel, have high energy conversion efficiency, clean and zero emissions, and are one of the main development directions of new energy and clean power vehicles in the future.
  • the promotion of hydrogen fuel cell vehicles is still full of difficulties.
  • One of the key problems is the CO poisoning of hydrogen fuel cell electrodes.
  • As the "heart" of hydrogen fuel cell vehicles fuel cell electrodes are easily poisoned by CO and CO2 impurity gases.
  • hydrogen is mainly derived from steam reforming of hydrocarbons such as methanol and natural gas, water gas shift reaction, etc., and usually contains 0.5% to 2% of trace CO and CO 2 .
  • hydrogen purification technology is mainly divided into physical purification technology and chemical purification technology.
  • Physical purification technology uses the difference in physical properties between H2 and impurities to remove impurities, including: pressure swing adsorption (PSA), high temperature diffusion (HTD) method, low temperature diffusion (LTD) method, and solvent absorption method, etc. Although these physical purification techniques are well established, they require complex and cumbersome designs.
  • Chemical purification technology removes impurities in low-grade hydrogen through chemical oxidation reaction, including: low temperature shift (LTS) technology, selective oxidation (PROX) technology, etc.
  • Microchannel reactor impurity removal technology is an emerging technology for removing trace impurities in hydrogen.
  • the methanation catalyst is filled with a fixed bed, and a large amount of heat is released during the reaction process. If a heat exchange system is installed, the equipment will be complicated and bulky , If the over-temperature control is not good, the heat is easy to accumulate, causing the catalyst to be deactivated, and the catalyst needs to be replaced frequently, which will affect the hydrogen purification effect.
  • the technical problem to be solved in this application is to overcome defects such as heat accumulation and easy deactivation of the catalyst in the reaction process of purifying hydrogen through methanation reaction in the prior art, thereby providing a fuel cell hydrogen purification pipeline and method and system.
  • the present application provides a fuel cell hydrogen purification pipeline, the inner wall of the purification pipeline is printed with a methanation catalyst layer using 3D printing technology.
  • the methanation catalyst layer has a honeycomb structure
  • the pattern printed on the methanation catalyst layer is a hollow square, a hollow four-pointed star, a gear, a hollow circle, a six-pointed star, a cross, a four-pointed star or a three-pointed star.
  • the thickness of the methanation catalyst layer is 0.5-5 mm, and the inner diameter of the pipeline is 1-2 cm.
  • the present application also provides a fuel cell hydrogen purification method, which includes the following steps of passing the hydrogen through the above-mentioned purification pipeline to perform a methanation reaction to obtain purified hydrogen.
  • the temperature of the methanation reaction is 150-300° C.
  • the pressure is 1-4 MPa
  • the hydrogen flow rate is 100-300 mL/min.
  • the methanation catalyst is a methanation catalyst commonly used in the art, for example, the active component may contain at least one transition metal of Ni, Rh, Ru, Fe, Cr or Pd.
  • the operating conditions of the 3D printing are: the laser power is 400-1000W, the powder feeding speed is 1-30g/min, and the scanning speed is 5-12mm/s.
  • the present application also provides a fuel cell system, using the above-mentioned purification pipeline as a hydrogen gas intake pipeline.
  • the length of the purification pipeline is 5-50 cm.
  • the fuel cell hydrogen purification pipeline provided by this application, the inner wall of the purification pipeline is printed with a methanation catalyst layer using 3D printing technology.
  • This application uses 3D printing technology to print the methanation catalyst on the inner wall of the pipeline, and replace the current methanation reactor with this purification pipeline, which can greatly enhance the heat transfer and mass transfer rate of the reaction. All aspects are superior to traditional reactors; the purification pipeline structure can realize efficient transfer of reaction heat, realize methanation reaction at close to constant temperature conditions, avoid the formation of hot spots, cause catalyst deactivation, and reduce safety hazards.
  • the synthesis gas methanation reaction is a strongly exothermic reaction process, and the adiabatic temperature rises per conversion of 1% CO and 1% CO2 are 72°C and 57°C, respectively, while traditional fixed-bed reactors
  • the heat and mass transfer efficiency is low, and it is easy to form temperature hot spots locally in the reactor bed, causing the catalyst to be deactivated due to high-temperature sintering, and the excessively high reaction temperature promotes the reverse water gas shift reaction, which is not conducive to the purification of hydrogen.
  • the methanation reaction is a reaction in which the number of gas molecules is reduced. High pressure is conducive to the generation of CH 4 , but high pressure puts forward higher requirements on the material and processing technology of the reactor; Large thermal stress.
  • the amplification process of the purification pipeline is simple and highly operable.
  • the number of reactor modules can be flexibly designed according to the needs of the working conditions, and it can realize intelligent processing and batch production, ensuring the structure and process of each set of purification pipelines. Consistency of parameters.
  • the use of 3D printing technology in this application also has the advantages of saving materials, reducing costs, and saving production cycles, and can truly realize digital and intelligent processing.
  • the above-mentioned purification pipeline is used as the hydrogen gas intake pipeline.
  • the system has a simple structure and can achieve high hydrogen purification without additional hydrogen purification units, avoiding poisoning caused by CO/CO 2 .
  • the hydrogen to be purified takes the pure hydrogen in GB/T 3634.2-2011 as an example, in which the concentration of CO is 5ppm, and the concentration of CO 2 is 10ppm.
  • This embodiment provides a fuel cell hydrogen purification method, comprising the following steps:
  • the powder feeding parameters and processing parameters are set. Among them, the laser power is 500W, the powder feeding speed is 10g/min, and the scanning speed is 8mm/s.
  • Print the catalyst under these conditions the printed shape is a hollow four-pointed star, and the specific composition of the catalyst is that the NiFeCr alloy material is composed of Ni (20%) Fe (70%) Cr (10%) and the printing thickness is 0.8mm.
  • the hydrogen to be purified is passed through the purification pipeline at 3Mpa and the flow rate is 100mL/min.
  • the temperature in the pipeline system is controlled at 280°C and the pressure is 3MPa.
  • the concentration of CO was 0.1ppm and the concentration of CO2 was 1ppm after the purification process.
  • the temperature of the catalyst bed basically did not rise, and the purification effect remained unchanged for 100 hours.
  • This embodiment provides a fuel cell hydrogen purification method, comprising the following steps:
  • the laser power is 400W
  • the powder feeding speed is 30g/min
  • the scanning speed is 5mm/s.
  • the catalyst is printed, and the printed shape is Hollow circle, the specific composition of the catalyst is Ni (99.5%) Pd (0.5%) alloy material, and the printing thickness is 0.5mm.
  • This embodiment provides a fuel cell hydrogen purification method, comprising the following steps:
  • the laser power is 1000W
  • the powder feeding speed is 1g/min
  • the scanning speed is 12mm/s.
  • the catalyst is printed, and the printed shape is Hollow circle, the specific composition of the catalyst is Ni(99.5%)Ru(0.5%) alloy material, and the printing thickness is 1.5mm.
  • This embodiment provides a fuel cell hydrogen purification method, comprising the following steps:
  • This embodiment provides a fuel cell hydrogen purification method, comprising the following steps:
  • the laser power is 1000W
  • the powder feeding speed is 1g/min
  • the scanning speed is 12mm/s.
  • the catalyst is printed, and the printed shape is Hollow circle, the specific composition of the catalyst is Ni(99.7%)Ru(0.3%) alloy material, and the printing thickness is 1.5mm.
  • the hydrogen to be purified is passed through the conventional purification pipeline filled with Ni-based methanation catalyst at 1Mpa and flow rate of 100mL/min.
  • the temperature of the pipeline system is controlled at 150°C and the pressure is 1MPa.
  • the concentration of CO after purification is 3ppm, and the concentration of CO2 is 8ppm.
  • the temperature of the catalyst bed rises to 850°C. After 3 hours, the catalyst is deactivated and the purification effect is lost.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Fuel Cell (AREA)

Abstract

本申请属于清洁能源技术领域，具体涉及一种燃料电池氢气纯化管路、方法及系统。本申请采用3D打印技术将甲烷化催化剂打印到管路内壁，以该纯化管路取代现行的甲烷化反应器，可以大大强化反应的传热和传质速率，在传质、传热、恒温等方面都优于传统的反应器；利用该纯化管路结构可实现反应热量的高效传递，实现甲烷化反应在接近于恒温条件下进行，避免形成热点，造成催化剂失活，减少安全隐患。另外，该纯化管路放大工艺简单、可操作性强，可以根据工况负荷的需要灵活设计反应器模块的数量。本申请采用3D打印技术还具有节省材料，降低成本，节省生产周期的优势，可真正实现数字化、智能化加工。

Description

一种燃料电池氢气纯化管路、方法及系统
相关申请的交叉引用
本申请要求在2021年9月9日提交中国专利局、申请号为202111057265.1、发明名称为“一种燃料电池氢气纯化管路、方法及系统”的中国专利申请的优先权，其全部内容通过引用的方式并入本文中。
技术领域
本申请属于清洁能源技术领域，具体涉及一种燃料电池氢气纯化管路、方法及系统。
背景技术
氢能是未来最理想的一种清洁能源之一。氢燃料电池汽车以氢气为燃料，能量转化效率高，清洁零排放，是未来新能源清洁动力汽车的主要发展方向之一。然而氢燃料电池汽车的推广目前仍然困难重重，其中一个关键难题是氢燃料电池电极的CO中毒问题，作为氢燃料电池汽车的“心脏”，燃料电池电极极易被CO和CO 2杂质气体毒化。现阶段，氢气主要来源于甲醇和天然气等碳氢化合物的水蒸汽重整、水煤气变换反应等，通常含有0.5％～2％的微量CO和CO 2。但是，用于燃料电池的H 2中CO含量应低于10ppm，SAE J-2719和ISO/PDTS 14687-2将“燃料电池级氢”的最低纯度定义为99.99％(如果考虑氦，则为99.97％)，允许总杂质少于100ppm。
目前，氢气纯化技术主要分为物理纯化技术和化学纯化技术。物理纯化技术是利用H 2与杂质之间的物理性质差异来除去杂质，包括：变压吸附法(PSA)，高温扩散(HTD)法，低温扩散(LTD)法，以及溶剂吸收法等。这些物理纯化技术虽然已经比较完善，但需要复杂而笨重的设计。化学纯化技术通过化学氧化反应除去低等级氢中的杂质，包括：低温变换(LTS)技术，选择性氧化(PROX)技术等。微通道反应器除杂技术是一种新兴的氢气中微量杂质脱出技术，但是，现有技术中甲烷化催化剂采用固定床进行装填，反应过程大量放热，如果安装 换热系统，造成设备繁杂庞大，如过温度控制不好，热量容易积累，造成催化剂失活，需要频繁更换催化剂，影响氢气纯化效果。
微量CO及CO 2分离是传统变压吸附提氢的“短板”，要想达到CO≤0.2ppm，CO 2≤2ppm的要求(GB/T 37244-2018《质子交换膜燃料电池汽车用燃料氢气》)，就需要同时将燃料氢气中含量要求不高的N 2和Ar等杂质一并脱除至很低的水平，结果就是损失了氢气收率，导致燃料氢气成本升高，同时还难以解决原料气组分波动和吸附剂长期运行性能下降所导致的燃料氢气品质不稳定的潜在风险。
发明内容
因此，本申请要解决的技术问题在于克服现有技术中通过甲烷化反应进行氢气提纯的反应过程中容易造成热量积累，催化剂易失活等缺陷，从而提供一种燃料电池氢气纯化管路、方法及系统。
为此，本申请提供如下技术方案：
本申请提供一种燃料电池氢气纯化管路，所述纯化管路内壁采用3D打印技术打印有甲烷化催化剂层。
可选的，所述甲烷化催化剂层具有蜂窝结构；
可选的，所述甲烷化催化剂层打印的图案为空心正方形，空心四角星形，齿轮形，空心圆形，六角星形，十字形，四角星形或三角星形。
可选的，所述甲烷化催化剂层的厚度为0.5-5mm，管路内径为1-2cm。
本申请还提供一种燃料电池氢气纯化纯化方法，包括如下步骤，将氢气通过上述的纯化管路，进行甲烷化反应，得到纯化后的氢气。
可选的，所述甲烷化反应的温度为150-300℃，压力为1-4MPa，氢气流速为100-300mL/min。
可选的，所述甲烷化催化剂为本领域常用的甲烷化催化剂，例如，活性组分可以包含Ni，Rh，Ru，Fe，Cr或Pd过渡金属中的至少一种。
可选的，所述3D打印的操作条件为：激光功率为400-1000W，送粉速度为1-30g/min，扫描速度为5-12mm/s。
本申请还提供一种燃料电池系统，以上述的纯化管路为氢气进气管路。
可选的，所述纯化管路的长度为5-50cm。
本申请技术方案，具有如下优点：
1.本申请提供的燃料电池氢气纯化管路，所述纯化管路内壁采用3D打印技术打印有甲烷化催化剂层。本申请采用3D打印技术将甲烷化催化剂打印到管路内壁，以该纯化管路取代现行的甲烷化反应器，可以大大强化反应的传热和传质速率，在传质、传热、恒温等方面都优于传统的反应器；利用该纯化管路结构可实现反应热量的高效传递，实现甲烷化反应在接近于恒温条件下进行，避免形成热点，造成催化剂失活，减少安全隐患。这是因为，合成气甲烷化反应是一个强放热的反应过程，每转化1％的CO和1％的CO 2的绝热温升分别是72℃和57℃，而传统的固定床反应器传热、传质效率低，容易在反应器床层局部形成温度热点，造成催化剂因高温烧结而失活，而且过高的反应温度有促进了逆水煤气变换反应的进行，不利于氢气的纯化。同时，甲烷化反应是一个气体分子数减少的反应，高压有利于CH 4的生成，但高压对反应器材质和加工工艺提出了较高的要求；甲烷化反应放出的大量热量会在瞬间产生较大的热应力，对于传统的均温列管反应器，内部管道接口较多，局部的热应力会造成安全隐患。另外，该纯化管路放大工艺简单、可操作性强，可以根据工况负荷的需要灵活设计反应器模块的数量，并且能够实现智能加工、批量化生产，保证每一套纯化管路的结构工艺参数的一致性。本申请采用3D打印技术还具有节省材料，降低成本，节省生产周期的优势，可真正实现数字化、智能化加工。
2.本申请提供的燃料电池系统，以上述纯化管路为氢气进气管路。该系统结构简单，无需另外设置氢气纯化单元即可实现氢气的高度纯化，避免CO/CO 2引起的的中毒。
具体实施方式
提供下述实施例是为了更好地进一步理解本申请，并不局限于所述最佳实施方式，不对本申请的内容和保护范围构成限制，任何人在本申请的启示下或 是将本申请与其他现有技术的特征进行组合而得出的任何与本申请相同或相近似的产品，均落在本申请的保护范围之内。
实施例中未注明具体实验步骤或条件者，按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品。
为了方便数据之间的对比，待纯化氢气以GB/T 3634.2-2011中的纯氢为例，其中，CO的浓度为5ppm，CO 2的浓度为10ppm。
实施例1
本实施例提供一种燃料电池氢气纯化方法，包括以下步骤：
纯化管路的准备：
1)将用于打印的基板放置在工艺室内，并确保平整干净。
2)确保打印腔的干净整洁和工具完备性。
3)确保给粉机料斗中有足够的金属粉末供应。
4)确保系统有足够的氩气供应。
5)确保激光器打开并工作。
3D打印：
准备45cm长，内径为1cm的管路，内壁经过清洁处理，设置送粉参数和加工参数，其中，激光功率为500W，送粉速度10g/min，扫描速度8mm/s，在该条件下打印催化剂，打印形状为空心四角星形，催化剂的具体组成是NiFeCr合金材料组成为Ni(20％)Fe(70％)Cr(10％)打印厚度为0.8mm。
将待纯化氢气以3Mpa，流速100mL/min，通过纯化管路，管路系统内温度控制280℃，压力为3MPa。经过气相色谱和烟气分析仪检测，纯化处理之后CO浓度为0.1ppm，CO 2浓度为1ppm，纯化过程中，催化剂床层温度基本无上升，且100小时纯化效果未发生变化。
实施例2
本实施例提供一种燃料电池氢气纯化方法，包括以下步骤：
纯化管路的准备：
1)将用于打印的基板放置在工艺室内，并确保平整干净。
2)确保打印腔的干净整洁和工具完备性。
3)确保给粉机料斗中有足够的金属粉末供应。
4)确保系统有足够的氩气供应。
5)确保激光器打开并工作。
3D打印：
准备5cm长，内径为1cm的管路，内壁经过清洁处理，在设置送粉参数和加工参数，激光功率为400W，送粉速度30g/min，扫描速度5mm/s条件下打印催化剂，打印形状为空心圆形，催化剂的具体组成是Ni(99.5％)Pd(0.5％)合金材料，打印厚度为0.5mm。
将待纯化氢气以1Mpa，流速100mL/min，常温的条件下通过纯化管路，管路系统内温度控制150℃，压力为1MPa。经过气相色谱和烟气分析仪检测，纯化处理之后CO浓度为0.19ppm，CO 2浓度为4.8ppm，纯化过程中，催化剂床层温度基本无上升，且100小时纯化效果未发生变化。
实施例3
本实施例提供一种燃料电池氢气纯化方法，包括以下步骤：
纯化管路的准备：
1)将用于打印的基板放置在工艺室内，并确保平整干净。
2)确保打印腔的干净整洁和工具完备性。
3)确保给粉机料斗中有足够的金属粉末供应。
4)确保系统有足够的氩气供应。
5)确保激光器打开并工作。
3D打印：
准备50cm长，内径为1cm的管路，内壁经过清洁处理，在设置送粉参数和加工参数，激光功率为1000W，送粉速度1g/min，扫描速度12mm/s条件下打印催化剂，打印形状为空心圆形，催化剂的具体组成是Ni(99.5％)Ru(0.5％)合金材料，打印厚度为1.5mm。
将待纯化氢气以1Mpa，流速300mL/min，常温的条件下通过纯化管路，管路系统内温度控制150℃，压力为1MPa。经过气相色谱和烟气分析仪检测，纯化处理之后CO浓度为0.12ppm，CO 2浓度为3.9ppm，纯化过程中，催化剂床层温度基本无上升，且100小时纯化效果未发生变化。
实施例4
本实施例提供一种燃料电池氢气纯化方法，包括以下步骤：
纯化管路的准备：
1)将用于打印的基板放置在工艺室内，并确保平整干净。
2)确保打印腔的干净整洁和工具完备性。
3)确保给粉机料斗中有足够的金属粉末供应。
4)确保系统有足够的氩气供应。
5)确保激光器打开并工作。
3D打印：
准备15cm长，内径为1.5cm的管路，内壁经过清洁处理，在设置送粉参数和加工参数，激光功率为800W，送粉速度20g/min，扫描速度12mm/s条件下打印催化剂，打印形状为齿轮形，催化剂的具体组成是Ni(99.9％)Ru(0.1％)合金材料，打印厚度为1mm。
将待纯化氢气以1Mpa，流速100mL/min，常温的条件下通过纯化管路，管路系统内温度控制150℃，压力为1MPa。经过气相色谱和烟气分析仪检测，纯化处理之后CO浓度为0.25ppm，CO 2浓度为1.8ppm，纯化过程中，催化剂床层温度基本无上升，且100小时纯化效果未发生变化。
实施例5
本实施例提供一种燃料电池氢气纯化方法，包括以下步骤：
纯化管路的准备：
1)将用于打印的基板放置在工艺室内，并确保平整干净。
2)确保打印腔的干净整洁和工具完备性。
3)确保给粉机料斗中有足够的金属粉末供应。
4)确保系统有足够的氩气供应。
5)确保激光器打开并工作。
3D打印：
准备25cm长，内径为1cm的管路，内壁经过清洁处理，在设置送粉参数和加工参数，激光功率为1000W，送粉速度1g/min，扫描速度12mm/s条件下打印催化剂，打印形状为空心圆形，催化剂的具体组成是Ni(99.7％)Ru(0.3％)合金材料，打印厚度为1.5mm。
将待纯化氢气以1Mpa，流速100mL/min，常温的条件下通过纯化管路，管路系统内温度控制150℃，压力为1MPa。经过气相色谱和烟气分析仪检测，纯化处理之后CO浓度为0.09ppm，CO 2浓度为1.8ppm，纯化过程中，催化剂床层温度基本无上升，且100小时纯化效果未发生变化。
对比例1
准备25cm长，内径为1cm的管路，内壁经过清洁处理，装填Ni基甲烷化催化剂，催化剂的组成为11.2％NiO负载在γ-Al 2O 3，装填量为20g。
将待纯化氢气以1Mpa，流速100mL/min，通过装填Ni基甲烷化催化剂的常规纯化管路，管路系统温度控制150℃，压力为1MPa。经过气相色谱和烟气分析仪检测，纯化处理之后CO浓度为3ppm，CO 2浓度为8ppm，纯化过程中，催化剂床层温度上升至850℃，3小时后催化剂失活，失去纯化效果效果。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (9)

  1. 一种燃料电池氢气纯化管路，其特征在于，所述纯化管路内壁采用3D打印技术打印有甲烷化催化剂层。
  2. 根据权利要求1所述的燃料电池氢气纯化管路，其特征在于，所述甲烷化催化剂层具有蜂窝结构；
    可选的，所述甲烷化催化剂层打印的图案为空心正方形，空心四角星形，齿轮形，空心圆形，六角星形，十字形，四角星形或三角星形。
  3. 根据权利要求1或2所述的燃料电池氢气纯化管路，其特征在于，所述甲烷化催化剂层的厚度为0.5-5mm，管路内径为1-2cm。
  4. 一种燃料电池氢气纯化纯化方法，其特征在于，包括如下步骤，将氢气通过权利要求1-3任一项所述的纯化管路，进行甲烷化反应，得到纯化后的氢气。
  5. 根据权利要求4所述的燃料电池氢气纯化方法，其特征在于，所述甲烷化反应的温度为150-300℃，压力为1-4MPa，氢气流速为100-300mL/min。
  6. 根据权利要求4所述的燃料电池氢气纯化方法，其特征在于，所述甲烷化催化剂包含Ni，Rh，Ru，Fe，Cr或Pd过渡金属中的至少一种。
  7. 根据权利要求4-6任一项所述的燃料电池氢气纯化方法，其特征在于，所述3D打印的操作条件为：激光功率为400-1000W，送粉速度为1-30g/min，扫描速度为5-12mm/s。
  8. 一种燃料电池系统，其特征在于，以权利要求1-4任一项所述的纯化管路为氢气进气管路。
  9. 根据权利要求8所述的燃料电池系统，其特征在于，所述纯化管路的长度为5-50cm。
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