阅读说明：本技术 一种燃料电池氢气纯化管路、方法及系统 (Fuel cell hydrogen purification pipeline, method and system ) 是由 刘蓉 于 2021-09-09 设计创作，主要内容包括：本发明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。本发明采用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。本发明采用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。(The invention belongs to the technical field of clean energy, and particularly relates to a hydrogen purification pipeline, method and system for a fuel cell. The methanation catalyst is printed on the inner wall of the pipeline by adopting a 3D printing technology, the purification pipeline replaces the existing methanation reactor, the heat transfer and mass transfer rates of the reaction can be greatly enhanced, and the methanation catalyst is superior to the traditional reactor in the aspects of mass transfer, heat transfer, constant temperature and the like; by utilizing the purification pipeline structure, the high-efficiency transfer of reaction heat can be realized, the methanation reaction is carried out under the condition close to constant temperature, the formation of hot spots is avoided, the catalyst is inactivated, and the potential safety hazard is reduced. In addition, the purification pipeline has simple amplification process and strong operability, and the number of the reactor modules can be flexibly designed according to the requirement of working condition load. The invention also has the advantages of saving materials, reducing cost and saving production period by adopting the 3D printing technology, and can really realize digital and intelligent processing.)

1. The fuel cell hydrogen purification pipeline is characterized in that a methanation catalyst layer is printed on the inner wall of the purification pipeline by adopting a 3D printing technology.

2. The fuel cell hydrogen purification pipeline of claim 1, wherein the methanation catalyst layer has a honeycomb structure;

optionally, the patterns printed on the methanation catalyst layer are hollow squares, hollow quadrangle stars, gears, hollow circles, hexagonal stars, crosses, quadrangle stars or triangular stars.

3. The fuel cell hydrogen purification pipeline according to claim 1 or 2, wherein the thickness of the methanation catalyst layer is 0.5-5mm, and the pipeline inner diameter is 1-2 cm.

4. A method for purifying and purifying hydrogen gas of a fuel cell, which is characterized by comprising the following steps of passing the hydrogen gas through the purification pipeline of any one of claims 1-3, and performing methanation reaction to obtain purified hydrogen gas.

5. The method for purifying fuel cell hydrogen according to claim 4, wherein the temperature of the methanation reaction is 150-300 ℃, the pressure is 1-4MPa, and the hydrogen flow rate is 100-300 mL/min.

6. The fuel cell hydrogen purification method according to claim 4, wherein the methanation catalyst comprises at least one of Ni, Rh, Ru, Fe, Cr or Pd transition metals.

7. The fuel cell hydrogen purification method according to any one of claims 4 to 6, wherein 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 5-12 mm/s.

8. A fuel cell system characterized in that the purification circuit according to any one of claims 1 to 4 is a hydrogen gas intake circuit.

9. The fuel cell system of claim 8, wherein the purification conduit has a length of 5-50 cm.

Technical Field

The invention belongs to the technical field of clean energy, and particularly relates to a hydrogen purification pipeline, method and system for a fuel cell.

Background

Hydrogen energy is one of the most ideal clean energy sources in the future. The hydrogen fuel cell automobile takes hydrogen as fuel, has high energy conversion efficiency and zero emission, and is one of the main development directions of new energy clean power automobiles in the future. However, the popularization of the hydrogen fuel cell automobile is still difficult at presentOne of the key challenges is the problem of CO poisoning of the hydrogen fuel cell electrode, which is highly susceptible to CO and CO as the "heart" of the hydrogen fuel cell vehicle₂Poisoning of impurity gases. At present, hydrogen mainly comes from steam reforming, water gas shift reaction and the like of hydrocarbons such as methanol and natural gas, and usually contains 0.5% to 2% of trace amounts of CO and CO₂. However, H for fuel cell₂The CO content should be below 10ppm, and SAE J-2719 and ISO/PDTS 14687-2 define the minimum purity of "fuel cell grade hydrogen" as 99.99% (99.97% if helium is considered), allowing less than 100ppm total impurities.

At present, the hydrogen purification technology is mainly classified into physical purification technology and chemical purification technology. The physical purification technique is to utilize H₂And impurities, including: pressure Swing Adsorption (PSA), High Temperature Diffusion (HTD), Low Temperature Diffusion (LTD), and solvent absorption. These physical purification techniques, while relatively sophisticated, require complex and cumbersome designs. Chemical purification techniques remove impurities from low grade hydrogen by chemical oxidation reactions, including: low Temperature Shift (LTS) techniques, selective oxidation (PROX) techniques, and the like. The impurity removal technology of the microchannel reactor is a novel technology for removing trace impurities in hydrogen, but in the prior art, a fixed bed is adopted for filling a methanation catalyst, a large amount of heat is released in the reaction process, and if a heat exchange system is installed, equipment is complex and huge, if the over-temperature control is not good, heat is easy to accumulate, the catalyst is inactivated, the catalyst needs to be frequently replaced, and the hydrogen purification effect is influenced.

Trace amount of CO and CO₂The separation is a short plate for extracting hydrogen by traditional pressure swing adsorption, and the CO is less than or equal to 0.2ppm₂The requirement of less than or equal to 2ppm (GB/T37244 and 2018 fuel hydrogen for proton exchange membrane fuel cell automobiles) requires that N with low content in the fuel hydrogen is required to be simultaneously used₂And Ar and other impurities are removed to a very low level, so that the hydrogen yield is lost, the fuel hydrogen cost is increased, and the potential instability of the fuel hydrogen quality caused by the fluctuation of the raw material gas components and the reduction of the long-term operation performance of the adsorbent is difficult to solveAnd (4) risks.

Disclosure of Invention

Therefore, the technical problem to be solved by the invention is to overcome the defects that in the prior art, heat accumulation is easily caused in the reaction process of hydrogen purification through methanation reaction, the catalyst is easily inactivated and the like, so that a hydrogen purification pipeline, a hydrogen purification method and a hydrogen purification system for a fuel cell are provided.

Therefore, the invention provides the following technical scheme:

the invention provides a hydrogen purification pipeline of a fuel cell, wherein a methanation catalyst layer is printed on the inner wall of the purification pipeline by adopting a 3D printing technology.

Optionally, the methanation catalyst layer has a honeycomb structure;

optionally, the patterns printed on the methanation catalyst layer are hollow squares, hollow quadrangle stars, gears, hollow circles, hexagonal stars, crosses, quadrangle stars or triangular stars.

Optionally, the thickness of the methanation catalyst layer is 0.5-5mm, and the inner diameter of the pipeline is 1-2 cm.

The invention also provides a fuel cell hydrogen purification method, which comprises the following steps of passing the hydrogen through the purification pipeline to perform methanation reaction to obtain purified hydrogen.

Optionally, the temperature of the methanation reaction is 150-.

Alternatively, the methanation catalyst is a methanation catalyst commonly used in the art, for example, the active component may comprise at least one of Ni, Rh, Ru, Fe, Cr or Pd transition metals.

Optionally, 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 5-12 mm/s.

The invention also provides a fuel cell system, which takes the purification pipeline as a hydrogen gas inlet pipeline.

Optionally, the length of the purification pipeline is 5-50 cm.

The technical scheme of the invention has the following advantages:

1. according to the fuel cell hydrogen purification pipeline provided by the invention, the methanation catalyst layer is printed on the inner wall of the purification pipeline by adopting a 3D printing technology. The methanation catalyst is printed on the inner wall of the pipeline by adopting a 3D printing technology, the purification pipeline replaces the existing methanation reactor, the heat transfer and mass transfer rates of the reaction can be greatly enhanced, and the methanation catalyst is superior to the traditional reactor in the aspects of mass transfer, heat transfer, constant temperature and the like; by utilizing the purification pipeline structure, the high-efficiency transfer of reaction heat can be realized, the methanation reaction is carried out under the condition close to constant temperature, the formation of hot spots is avoided, the catalyst is inactivated, and the potential safety hazard is reduced. This is because the synthesis gas methanation reaction is a strongly exothermic reaction process, with 1% CO and 1% CO converted₂The adiabatic temperature rise of the catalyst is 72 ℃ and 57 ℃, respectively, while the traditional fixed bed reactor has low heat transfer and mass transfer efficiency, and is easy to form a temperature hot spot on the local part of a bed layer of the reactor, thereby causing the inactivation of the catalyst due to high-temperature sintering, and the excessive reaction temperature promotes the reverse water-gas shift reaction, which is not beneficial to the purification of hydrogen. Meanwhile, methanation reaction is a reaction that the number of gas molecules is reduced, and high pressure is favorable for CH₄The high pressure puts higher requirements on the material and the processing technology of the reactor; a large amount of heat released by methanation reaction can produce great thermal stress in the twinkling of an eye, and to traditional samming shell and tube reactor, the internal pipeline interface is more, and local thermal stress can cause the potential safety hazard. In addition, the amplification process of the purification pipeline is simple, the operability is strong, the number of the reactor modules can be flexibly designed according to the requirement of working condition load, intelligent processing and batch production can be realized, and the consistency of the structural process parameters of each set of purification pipeline is ensured. The invention also has the advantages of saving materials, reducing cost and saving production period by adopting the 3D printing technology, and can really realize digital and intelligent processing.

2. The fuel cell system provided by the invention takes the purification pipeline as a hydrogen inlet pipeline. The system has simple structure, can realize high purification of hydrogen without additionally arranging a hydrogen purification unit, and avoids CO/CO₂The resulting poisoning.

Detailed Description

The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.

The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.

To facilitate comparison between the data, the hydrogen to be purified is exemplified by pure hydrogen in GB/T3634.2-2011, wherein the concentration of CO is 5ppm and CO is₂The concentration of (2) is 10 ppm.

Example 1

The embodiment provides a method for purifying hydrogen of a fuel cell, which comprises the following steps:

preparation of a purification pipeline:

1) the substrate for printing is placed in a process chamber and is guaranteed to be flat and clean.

2) Ensuring the cleanliness and tool integrity of the printing chamber.

3) Ensuring an adequate supply of metal powder in the hopper of the powder feeder.

4) Ensuring that the system has an adequate supply of argon.

5) Ensuring that the laser is on and working.

3D printing:

preparing a 45cm long pipeline with an inner diameter of 1cm, cleaning the inner wall, setting powder feeding parameters and processing parameters, wherein the laser power is 500W, the powder feeding speed is 10g/min, the scanning speed is 8mm/s, printing a catalyst under the condition, and the printing shape is a hollow quadrangle star, wherein the specific composition of the catalyst is NiFe

The composition of the Cr alloy material is Ni (20%) Fe (70%) Cr (10%) with a printing thickness of 0.8 mm.

Will be purifiedThe hydrogen oxide gas passes through a purification pipeline at the flow rate of 100mL/min under the pressure of 3MPa, the temperature in the pipeline system is controlled at 280 ℃, and the pressure is 3 MPa. Detected by a gas chromatography and a flue gas analyzer, the concentration of CO is 0.1ppm and the concentration of CO is 0.1ppm after purification treatment₂The concentration is 1ppm, the temperature of the catalyst bed layer is basically not increased in the purification process, and the purification effect is not changed in 100 hours.

Example 2

The embodiment provides a method for purifying hydrogen of a fuel cell, which comprises the following steps:

preparation of a purification pipeline:

1) the substrate for printing is placed in a process chamber and is guaranteed to be flat and clean.

2) Ensuring the cleanliness and tool integrity of the printing chamber.

3) Ensuring an adequate supply of metal powder in the hopper of the powder feeder.

4) Ensuring that the system has an adequate supply of argon.

5) Ensuring that the laser is on and working.

3D printing:

preparing a pipeline with the length of 5cm and the inner diameter of 1cm, cleaning the inner wall, printing a catalyst under the conditions of setting powder feeding parameters and processing parameters, laser power of 400W, powder feeding speed of 30g/min and scanning speed of 5mm/s, wherein the printing shape is a hollow circle, the catalyst is specifically composed of an Ni (99.5%) Pd (0.5%) alloy material, and the printing thickness is 0.5 mm.

The hydrogen to be purified passes through a purification pipeline under the conditions of 1Mpa, the flow rate of 100mL/min and normal temperature, the temperature in a pipeline system is controlled at 150 ℃, and the pressure is 1 MPa. Detected by a gas chromatography and a flue gas analyzer, the concentration of CO after purification treatment is 0.19ppm, and the concentration of CO is₂The concentration is 4.8ppm, the temperature of the catalyst bed layer is basically not increased in the purification process, and the purification effect is not changed within 100 hours.

Example 3

The embodiment provides a method for purifying hydrogen of a fuel cell, which comprises the following steps:

preparation of a purification pipeline:

1) the substrate for printing is placed in a process chamber and is guaranteed to be flat and clean.

2) Ensuring the cleanliness and tool integrity of the printing chamber.

3) Ensuring an adequate supply of metal powder in the hopper of the powder feeder.

4) Ensuring that the system has an adequate supply of argon.

5) Ensuring that the laser is on and working.

3D printing:

preparing a pipeline with the length of 50cm and the inner diameter of 1cm, cleaning the inner wall, printing a catalyst under the conditions of setting powder feeding parameters and processing parameters, laser power of 1000W, powder feeding speed of 1g/min and scanning speed of 12mm/s, wherein the printing shape is a hollow circle, the catalyst is specifically composed of Ni (99.5%) Ru (0.5%) alloy material, and the printing thickness is 1.5 mm.

Passing hydrogen to be purified through a purification pipeline at the normal temperature of 1Mpa and the flow rate of 300mL/min, controlling the temperature in a pipeline system to be 150 ℃ and the pressure to be 1 MPa. Detected by a gas chromatography and a flue gas analyzer, the concentration of CO after purification treatment is 0.12ppm, and the concentration of CO is₂The concentration is 3.9ppm, the temperature of the catalyst bed layer is basically not increased in the purification process, and the purification effect is not changed within 100 hours.

Example 4

The embodiment provides a method for purifying hydrogen of a fuel cell, which comprises the following steps:

preparation of a purification pipeline:

1) the substrate for printing is placed in a process chamber and is guaranteed to be flat and clean.

2) Ensuring the cleanliness and tool integrity of the printing chamber.

3) Ensuring an adequate supply of metal powder in the hopper of the powder feeder.

4) Ensuring that the system has an adequate supply of argon.

5) Ensuring that the laser is on and working.

3D printing:

preparing a 15cm long pipeline with the inner diameter of 1.5cm, cleaning the inner wall, printing a catalyst under the conditions of setting powder feeding parameters and processing parameters, laser power of 800W, powder feeding speed of 20g/min and scanning speed of 12mm/s, wherein the printing shape is a gear shape, the specific composition of the catalyst is Ni (99.9%) Ru (0.1%) alloy material, and the printing thickness is 1 mm.

The hydrogen to be purified passes through a purification pipeline under the conditions of 1Mpa, the flow rate of 100mL/min and normal temperature, the temperature in a pipeline system is controlled at 150 ℃, and the pressure is 1 MPa. Detected by a gas chromatography and a flue gas analyzer, the concentration of CO after purification treatment is 0.25ppm, and the concentration of CO is₂The concentration is 1.8ppm, the temperature of the catalyst bed layer is basically not increased in the purification process, and the purification effect is not changed within 100 hours.

Example 5

The embodiment provides a method for purifying hydrogen of a fuel cell, which comprises the following steps:

preparation of a purification pipeline:

1) the substrate for printing is placed in a process chamber and is guaranteed to be flat and clean.

2) Ensuring the cleanliness and tool integrity of the printing chamber.

3) Ensuring an adequate supply of metal powder in the hopper of the powder feeder.

4) Ensuring that the system has an adequate supply of argon.

5) Ensuring that the laser is on and working.

3D printing:

preparing a pipeline with the length of 25cm and the inner diameter of 1cm, cleaning the inner wall, printing a catalyst under the conditions of setting powder feeding parameters and processing parameters, laser power of 1000W, powder feeding speed of 1g/min and scanning speed of 12mm/s, wherein the printing shape is a hollow circle, the catalyst is specifically composed of Ni (99.7%) Ru (0.3%) alloy material, and the printing thickness is 1.5 mm.

The hydrogen to be purified passes through a purification pipeline under the conditions of 1Mpa, the flow rate of 100mL/min and normal temperature, the temperature in a pipeline system is controlled at 150 ℃, and the pressure is 1 MPa. Detected by a gas chromatography and a flue gas analyzer, the concentration of CO after purification treatment is 0.09ppm, and the concentration of CO is₂The concentration is 1.8ppm, the temperature of the catalyst bed layer is basically not increased in the purification process, and the purification effect is not changed within 100 hours.

Comparative example 1

Preparing a pipeline with the length of 25cm and the inner diameter of 1cm, cleaning the inner wall of the pipeline, filling a Ni-based methanation catalyst, wherein the catalyst comprises 11.2 percent of NiO loaded on gamma-Al₂O₃The loading was 20 g.

The hydrogen to be purified passes through a conventional purification pipeline filled with the Ni-based methanation catalyst at the flow rate of 100mL/min under the pressure of 1Mpa, the temperature of a pipeline system is controlled at 150 ℃, and the pressure is 1 MPa. Detected by a gas chromatography and a flue gas analyzer, the concentration of CO is 3ppm and the concentration of CO is 3ppm after purification treatment₂The concentration is 8ppm, the temperature of the catalyst bed layer rises to 850 ℃ in the purification process, and the catalyst is deactivated after 3 hours, so that the purification effect is lost.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.