CN116555798A - A high-temperature electrolyzed water hydrogen production system and hydrogen production method with full utilization of heat - Google Patents
A high-temperature electrolyzed water hydrogen production system and hydrogen production method with full utilization of heat Download PDFInfo
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Abstract
Description
技术领域technical field
本发明涉及电解水制氢技术领域，具体涉及一种热量充分利用的高温电解水制氢系统及其制氢方法。The invention relates to the technical field of electrolytic water hydrogen production, in particular to a high-temperature electrolytic water hydrogen production system and a hydrogen production method that fully utilizes heat.
背景技术Background technique
氢气作为重要的二次能源，是构建以清洁能源为主的综合能源供给系统的重要载体，开发利用氢能已成为能源技术发展的重要战略方向。目前氢气广泛应用于石油加工、合成氨、金属冶炼，以及氢燃料电池和氢能汽车等众多领域。氢气主要来源于天然气工业，石油化工业和煤气化工业，这些工业技术的制氢过程会产生大量的CO2，与低碳产业的理念不相符合。As an important secondary energy source, hydrogen is an important carrier for building a comprehensive energy supply system based on clean energy. The development and utilization of hydrogen energy has become an important strategic direction for the development of energy technology. At present, hydrogen is widely used in many fields such as petroleum processing, synthetic ammonia, metal smelting, hydrogen fuel cells and hydrogen vehicles. Hydrogen mainly comes from the natural gas industry, petrochemical industry and coal gasification industry. The hydrogen production process of these industrial technologies will produce a large amount of CO 2 , which is not in line with the concept of low-carbon industry.
电解水制氢技术的产物是氢气和氧气，符合低碳产业的理念，属于可再生过程，是实现氢能与电能之间高效转化的重要手段，同时也有望成为风力、光伏发电的重要调节手段。在质子交换膜水电解制氢(PEM)，阴离子交换膜水电解制氢(AEM)和固体氧化物水电解制氢(SOEC)等各种电解制氢的技术中，碱性电解水制氢(ALK)技术因其研究较早，成本低廉，是最为成熟，也是最具规模化的一种，其中高温碱性电解水制氢系统开始得到初步研究和应用。The products of electrolytic water hydrogen production technology are hydrogen and oxygen, which conforms to the concept of low-carbon industry and belongs to the renewable process. It is an important means to realize the efficient conversion between hydrogen energy and electric energy, and it is also expected to become an important adjustment means for wind power and photovoltaic power generation. . In various electrolytic hydrogen production technologies such as proton exchange membrane water electrolysis (PEM), anion exchange membrane water electrolysis (AEM) and solid oxide water electrolysis (SOEC), alkaline electrolysis of water ( ALK) technology is the most mature and large-scale one because of its early research and low cost. Among them, the high-temperature alkaline electrolysis water hydrogen production system has begun to be initially studied and applied.
高温碱性电解水制氢系统的工作温度即电解液温度是制氢的核心过程，电解过程中随着工作温度的升高，电解电压即理论分解电压、催化剂过电压和其他电阻电压之和会得到明显降低，从而降低电解过程产生的能耗，提高电解效率。The working temperature of the high-temperature alkaline electrolysis water hydrogen production system, that is, the temperature of the electrolyte, is the core process of hydrogen production. With the increase of the working temperature during the electrolysis process, the electrolysis voltage is the sum of the theoretical decomposition voltage, catalyst overvoltage and other resistance voltages. Obvious reduction, thereby reducing the energy consumption produced by the electrolysis process, and improving the electrolysis efficiency.
如公开号CN 114481158 A公开的一种高温碱性电解水制氢系统及其方法，其包括电解液供应装置、电解槽和气体分离系统，电解槽为压滤式结构电解槽；电解槽与电解液供应装置之间连接有热源装置，以加热电解液。该制氢系统的工作压力和工作温度分别是1-4MPa和95-220℃，工作温度由电解装置与电解液供应装置之间连接的热源装置来提供，加热装置对电解液进行加热。Such as the publication number CN 114481158 A discloses a high-temperature alkaline electrolyzed water hydrogen production system and its method, which includes an electrolyte supply device, an electrolyzer and a gas separation system, the electrolyzer is an electrolyzer with a filter press structure; the electrolyzer and the electrolyzer A heat source device is connected between the liquid supply devices to heat the electrolyte. The working pressure and temperature of the hydrogen production system are 1-4MPa and 95-220°C respectively, and the working temperature is provided by the heat source device connected between the electrolysis device and the electrolyte supply device, and the heating device heats the electrolyte.
但是该热源装置突兀于整个制氢系统，增加了系统的制备成本和占地面积，同时也受限于电解装置的位置，制氢系统用户端无法做到便携转移和安装。However, the heat source device is protruding from the entire hydrogen production system, which increases the preparation cost and floor space of the system. At the same time, it is also limited by the location of the electrolysis device, and the hydrogen production system client cannot be portable and installed.
除此之外，高温电解装置在电解过程中可以产生大量的热，如果忽略这部分热量的有效利用，而使用外热源装置，一方面外热源装置在加热过程中存在大量热的损失，另一方面也增加了整个制氢系统的能耗。In addition, the high-temperature electrolysis device can generate a large amount of heat during the electrolysis process. If the effective use of this part of heat is ignored and an external heat source device is used, on the one hand, there will be a large amount of heat loss during the heating process of the external heat source device, and on the other hand It also increases the energy consumption of the entire hydrogen production system.
发明内容Contents of the invention
本发明的目的是提供一种热量充分利用的高温电解水制氢系统，通过氢气、氧气热量回收器对补充水进行热交换，回收氢气、氧气热量，可减少电解过程的热量损失。此外，制氢系统的保温层，可进一步减少电解过程的热量损失，以及整个制氢系统的能耗和电解效率。本发明系统结构和制备工艺简单，适于大规模工业化应用。本发明还提供一种制氢方法，通过提高电解槽电解液的工作温度，达到221-350℃，实现更高制氢效率，降低能耗。The purpose of the present invention is to provide a high-temperature electrolytic water hydrogen production system that makes full use of heat. The hydrogen and oxygen heat recovery device performs heat exchange on the supplementary water to recover the heat of hydrogen and oxygen, which can reduce the heat loss in the electrolysis process. In addition, the insulation layer of the hydrogen production system can further reduce the heat loss in the electrolysis process, as well as the energy consumption and electrolysis efficiency of the entire hydrogen production system. The system structure and preparation process of the invention are simple and suitable for large-scale industrial application. The present invention also provides a method for hydrogen production. By increasing the working temperature of the electrolyte in the electrolytic cell to 221-350° C., higher hydrogen production efficiency can be achieved and energy consumption can be reduced.
为了达到上述技术目的，本发明的技术方案是：In order to achieve the above-mentioned technical purpose, technical scheme of the present invention is:
一种热量充分利用的高温电解水制氢系统，包括电解槽，所述电解槽连接有氢气气液分离器和氧气气液分离器，所述氢气气液分离器内设置有氢气热量回收器，所述氢气热量回收器设置有第一补充水进口和第一补充水出口，所述第一补充水出口与电解槽连接，补充水由第一补充水进口进入氢气热量回收器后，经第一补充水出口进入电解槽内，所述氢气热量回收器用于补充水与氢气进行热交换；A high-temperature electrolyzed water hydrogen production system that fully utilizes heat, comprising an electrolyzer, the electrolyzer is connected with a hydrogen gas-liquid separator and an oxygen gas-liquid separator, and the hydrogen gas-liquid separator is provided with a hydrogen heat recovery device, The hydrogen heat recovery device is provided with a first supplementary water inlet and a first supplementary water outlet, and the first supplementary water outlet is connected to the electrolytic cell. After the supplementary water enters the hydrogen heat recovery device from the first supplementary water inlet, it passes through the first The replenishment water outlet enters the electrolyzer, and the hydrogen heat recovery device is used for heat exchange between the replenishment water and hydrogen;
所述氧气气液分离器内设置有氧气热量回收器，所述氧气热量回收器设置有第二补充水进口和第二补充水出口，所述第二补充水出口与电解槽连接，补充水由第二补充水进口进入氧气热量回收器后，经第二补充水出口进入电解槽内，所述氧气热量回收器用于补充水与氧气进行热交换。The oxygen gas-liquid separator is provided with an oxygen heat recovery device, and the oxygen heat recovery device is provided with a second supplementary water inlet and a second supplementary water outlet, and the second supplementary water outlet is connected to the electrolytic cell, and the supplementary water is provided by After the second supplementary water inlet enters the oxygen heat recovery device, it enters the electrolytic cell through the second supplementary water outlet, and the oxygen heat recovery device is used for heat exchange between the supplementary water and oxygen.
所述氢气热量回收器位于氢气气液分离器的氢气出口处，所述氧气热量回收器位于氧气气液分离器的氧气出口处。The hydrogen heat recovery device is located at the hydrogen outlet of the hydrogen gas-liquid separator, and the oxygen heat recovery device is located at the oxygen outlet of the oxygen gas-liquid separator.
所述氢气热量回收器和氧气热量回收器为管壳式回收器或水、气直接热量回收器。The hydrogen heat recovery device and the oxygen heat recovery device are shell and tube type recovery devices or water and gas direct heat recovery devices.
所述电解槽和/或氢气气液分离器和/或氧气气液分离器设有保温层。The electrolytic cell and/or the hydrogen gas-liquid separator and/or the oxygen gas-liquid separator are provided with an insulating layer.
所述保温层为电伴热带。The insulation layer is an electric heating cable.
所述电解槽的阴极由双极板和金属丝网或泡沫镍板阴极组成，电解槽的阳极由双极板和金属丝网或泡沫镍板阳极组成；且阴极一侧与阳极一侧以渗透隔膜进行隔离，同时使用垫片对电解槽进行密封。The negative electrode of described electrolytic cell is made up of bipolar plate and wire mesh or foamed nickel plate cathode, and the anode of electrolytic cell is made up of bipolar plate and wire mesh or foamed nickel plate anode; The diaphragm is used for isolation, while the electrolytic cell is sealed with a gasket.
所述渗透隔膜由有机高分子材料、无机材料或复合材料制成。The permeable membrane is made of organic polymer material, inorganic material or composite material.
所述密封垫片由有机高分子材料或复合材料制成。The sealing gasket is made of organic polymer material or composite material.
所述有机高分子材料为聚苯硫醚和聚四氟乙烯中的一种或两种。The organic polymer material is one or both of polyphenylene sulfide and polytetrafluoroethylene.
所述无机材料为硅酸镁、氧化铝、氧化铁、氧化锆和氧化钙中的一种或多种。The inorganic material is one or more of magnesium silicate, aluminum oxide, iron oxide, zirconium oxide and calcium oxide.
所述复合材料为有机或无机材料经表面改性复合而成。The composite material is compounded by surface modification of organic or inorganic materials.
所述有机高分子材料为聚四氟乙烯、聚碳酸酯和聚醚砜中的一种或两种。The organic polymer material is one or two of polytetrafluoroethylene, polycarbonate and polyethersulfone.
所述复合材料为有机高分子材料经表面改性复合而成。The composite material is composed of organic polymer materials through surface modification.
本发明还提供一种基于上述一种热量充分利用的高温电解水制氢系统的制氢方法，所述电解槽工作温度为221℃-350℃。The present invention also provides a hydrogen production method based on the above-mentioned high-temperature electrolyzed water hydrogen production system that fully utilizes heat, and the working temperature of the electrolytic cell is 221°C-350°C.
本发明制氢方法通过提高电解槽电解液的工作温度，达到221-350℃，实现更高制氢效率，降低能耗。本发明制氢系统通过氢气、氧气热量回收器对补充水进行热交换，回收氢气、氧气热量，可减少电解过程的热量损失。本发明还对电解槽、氢气气液分离器和氧气气液分离器进行保温，减少电解过程的热量损失，以及整个制氢系统的能耗，进一步提升电解效率。The hydrogen production method of the present invention achieves higher hydrogen production efficiency and reduces energy consumption by increasing the working temperature of the electrolyte in the electrolytic cell to 221-350°C. The hydrogen production system of the present invention performs heat exchange on supplementary water through a hydrogen and oxygen heat recovery device, recovers hydrogen and oxygen heat, and can reduce heat loss in the electrolysis process. The invention also heats the electrolytic cell, the hydrogen gas-liquid separator and the oxygen gas-liquid separator to reduce the heat loss in the electrolysis process and the energy consumption of the entire hydrogen production system, thereby further improving the electrolysis efficiency.
本发明摒弃了以往高温电解制氢系统中电解装置与电解液供应装置之间的热源装置，有效解决了热源装置增加了占地面积和制备成本、无法便携转移和安装的问题。本发明系统结构和制备工艺简单，适于大规模工业化应用。The invention abandons the heat source device between the electrolysis device and the electrolyte supply device in the high-temperature electrolysis hydrogen production system in the past, and effectively solves the problems that the heat source device increases the floor area and preparation cost, and cannot be portable, transferred and installed. The system structure and preparation process of the invention are simple and suitable for large-scale industrial application.
附图说明Description of drawings
下面结合附图和具体实施方式对本发明作进一步详细的说明。The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.
图1为本发明制氢系统结构示意图。Fig. 1 is a schematic structural diagram of the hydrogen production system of the present invention.
图2为本发明电伴热带布置结构示意图。Fig. 2 is a schematic diagram of the arrangement structure of the electric heating cable of the present invention.
具体实施方式Detailed ways
如图1-2所示，一种热量充分利用的高温电解水制氢系统，包括电解槽1，所述电解槽1连接有氢气气液分离器5和氧气气液分离器4，所述氢气气液分离器5内设置有氢气热量回收器7，所述氢气热量回收器7位于氢气气液分离器5的氢气出口处，所述氢气热量回收器7设置有第一补充水进口71和第一补充水出口72，所述第一补充水出口72与电解槽1连接，补充水由第一补充水进口71进入氢气热量回收器7后，经第一补充水出口72进入电解槽1内，所述氢气热量回收器7用于补充水与氢气进行热交换；As shown in Figure 1-2, a high-temperature electrolyzed water hydrogen production system that fully utilizes heat includes an electrolytic cell 1 connected to a hydrogen gas-liquid separator 5 and an oxygen gas-liquid separator 4, the hydrogen The gas-liquid separator 5 is provided with a hydrogen heat recovery device 7, and the hydrogen heat recovery device 7 is located at the hydrogen outlet of the hydrogen gas-liquid separator 5, and the hydrogen heat recovery device 7 is provided with a first supplementary water inlet 71 and a second A supplementary water outlet 72, the first supplementary water outlet 72 is connected to the electrolytic cell 1, after the supplementary water enters the hydrogen heat recovery device 7 from the first supplementary water inlet 71, it enters the electrolytic cell 1 through the first supplementary water outlet 72, The hydrogen heat recovery device 7 is used to make up water and carry out heat exchange with hydrogen;
所述氧气气液分离器4内设置有氧气热量回收器6，所述氧气热量回收器6位于氧气气液分离器4的氧气出口处，所述氧气热量回收器6设置有第二补充水进口61和第二补充水出口62，所述第二补充水出口62与电解槽1连接，补充水由第二补充水进口61进入氧气热量回收器6后，经第二补充水出口62进入电解槽1内，所述氧气热量回收器6用于补充水与氧气进行热交换。The oxygen gas-liquid separator 4 is provided with an oxygen heat recovery device 6, the oxygen heat recovery device 6 is located at the oxygen outlet of the oxygen gas-liquid separator 4, and the oxygen heat recovery device 6 is provided with a second supplementary water inlet 61 and the second supplementary water outlet 62, the second supplementary water outlet 62 is connected with the electrolytic cell 1, after the supplementary water enters the oxygen heat recovery device 6 from the second supplementary water inlet 61, it enters the electrolytic cell through the second supplementary water outlet 62 1, the oxygen heat recovery device 6 is used to make up water and oxygen for heat exchange.
所述电解槽1和氧气气液分离器4和氢气气液分离器5以及之间连接的管道、泵、阀门均设有保温层。如图1所示，所述电解槽1外表面设置第一保温层81，所述氧气气液分离器4外表面设置第二保温层82，所述氢气气液分离器5外表面设置第三保温层83。The electrolytic cell 1, the oxygen gas-liquid separator 4, the hydrogen gas-liquid separator 5 and the pipelines, pumps and valves connected therebetween are all provided with insulation layers. As shown in Figure 1, the outer surface of the electrolytic cell 1 is provided with a first insulation layer 81, the outer surface of the oxygen gas-liquid separator 4 is provided with a second insulation layer 82, and the outer surface of the hydrogen gas-liquid separator 5 is provided with a third insulation layer. Insulation layer 83.
所述保温层为电伴热带，电伴热采用缠绕或平行排列布置。如图2所示，电伴热带2平行排列布置在电解槽1外。The insulation layer is an electric heating cable, and the electric heating is arranged in a winding or parallel arrangement. As shown in FIG. 2 , the electric heating cables 2 are arranged in parallel outside the electrolytic cell 1 .
所述氢气热量回收器7和氧气热量回收器6为管壳式回收器，也可以设置为水、气直接热量回收器。The hydrogen heat recovery device 7 and the oxygen heat recovery device 6 are shell-and-tube type recovery devices, and can also be set as direct heat recovery devices for water and gas.
所述电解槽的阴极由双极板和金属丝网或泡沫镍板阴极组成，电解槽的阳极由双极板和金属丝网或泡沫镍板阳极组成；且阴极一侧与阳极一侧以渗透隔膜进行隔离，同时使用垫片对电解槽进行密封。The negative electrode of described electrolytic cell is made up of bipolar plate and wire mesh or foamed nickel plate cathode, and the anode of electrolytic cell is made up of bipolar plate and wire mesh or foamed nickel plate anode; The diaphragm is used for isolation, while the electrolytic cell is sealed with a gasket.
所述渗透隔膜由有机高分子材料、无机材料或复合材料制成。The permeable membrane is made of organic polymer material, inorganic material or composite material.
所述密封垫片由有机高分子材料或复合材料制成。The sealing gasket is made of organic polymer material or composite material.
所述有机高分子材料为聚苯硫醚和聚四氟乙烯中的一种或两种。The organic polymer material is one or both of polyphenylene sulfide and polytetrafluoroethylene.
所述无机材料为硅酸镁、氧化铝、氧化铁、氧化锆和氧化钙中的一种或多种。The inorganic material is one or more of magnesium silicate, aluminum oxide, iron oxide, zirconium oxide and calcium oxide.
所述复合材料为有机或无机材料经表面改性复合而成。The composite material is compounded by surface modification of organic or inorganic materials.
所述有机高分子材料为聚四氟乙烯、聚碳酸酯和聚醚砜中的一种或两种。The organic polymer material is one or two of polytetrafluoroethylene, polycarbonate and polyethersulfone.
所述复合材料为有机高分子材料经表面改性复合而成。The composite material is composed of organic polymer materials through surface modification.
一种基于上述热量充分利用的高温电解水制氢系统的制氢方法，所述电解槽工作温度为221℃-350℃。A method for producing hydrogen based on a high-temperature electrolyzed water hydrogen production system based on the full utilization of the above-mentioned heat, the operating temperature of the electrolyzer is 221°C-350°C.
试验1：Test 1:
渗透隔膜采用聚苯硫醚，组装电解水制氢系统后，施加2V直流电进行电解工作。随着电解过程的进行，控制工作温度为300℃。经测得，电解槽小室电压1.812V，电流密度为7015A/m2，能耗为4.331kWh/Nm3。The osmotic diaphragm is made of polyphenylene sulfide. After assembling the electrolysis water hydrogen production system, apply 2V DC for electrolysis. As the electrolysis process proceeds, the working temperature is controlled to be 300°C. It is measured that the cell voltage of the electrolytic cell is 1.812V, the current density is 7015A/m 2 , and the energy consumption is 4.331kWh/Nm 3 .
试验2：Test 2:
渗透隔膜采用聚苯硫醚、聚四氟乙烯，组装电解水制氢系统后，施加2V直流电进行电解工作。随着电解过程的进行，控制工作温度为300℃。经测得，电解槽小室电压1.789V，电流密度为7219A/m2，能耗为4.275kWh/Nm3。The osmotic diaphragm is made of polyphenylene sulfide and polytetrafluoroethylene. After assembling the electrolysis water hydrogen production system, apply 2V direct current for electrolysis. As the electrolysis process proceeds, the working temperature is controlled to be 300°C. It is measured that the cell voltage of the electrolytic cell is 1.789V, the current density is 7219A/m 2 , and the energy consumption is 4.275kWh/Nm 3 .
试验3：Trial 3:
渗透隔膜采用硅酸镁，组装电解水制氢系统后，施加2V直流电进行电解工作。随着电解过程的进行，控制工作温度为300℃。经测得，电解槽小室电压1.753V，电流密度为7356A/m2，能耗为4.189kWh/Nm3。The osmotic diaphragm is made of magnesium silicate. After assembling the electrolysis water hydrogen production system, apply 2V direct current for electrolysis. As the electrolysis process proceeds, the working temperature is controlled to be 300°C. It is measured that the cell voltage of the electrolytic cell is 1.753V, the current density is 7356A/m 2 , and the energy consumption is 4.189kWh/Nm 3 .
试验4：Test 4:
渗透隔膜采用硅酸镁、氧化铝，组装电解水制氢系统后，施加2V直流电进行电解工作。随着电解过程的进行，控制工作温度为300℃。经测得，电解槽小室电压1.742V，电流密度为8689A/m2，能耗为4.163kWh/Nm3。The osmotic diaphragm is made of magnesium silicate and alumina. After assembling the electrolysis water hydrogen production system, apply 2V DC for electrolysis. As the electrolysis process proceeds, the working temperature is controlled to be 300°C. It is measured that the cell voltage of the electrolytic cell is 1.742V, the current density is 8689A/m 2 , and the energy consumption is 4.163kWh/Nm 3 .
试验5：Test 5:
渗透隔膜采用硅酸镁、氧化铝、氧化错、氧化钙，组装电解水制氢系统后，施加2V直流电进行电解工作。随着电解过程的进行，控制工作温度为300℃。经测得，电解槽小室电压1.738V，电流密度为9013A/m2，能耗为4.154kWh/Nm3。The permeable diaphragm is made of magnesium silicate, alumina, zirconia, and calcium oxide. After assembling the electrolysis water hydrogen production system, apply 2V direct current for electrolysis. As the electrolysis process proceeds, the working temperature is controlled to be 300°C. It is measured that the cell voltage of the electrolytic cell is 1.738V, the current density is 9013A/m 2 , and the energy consumption is 4.154kWh/Nm 3 .
试验6：Test 6:
渗透隔膜采用有机材料表面改性复合而成，组装电解水制氢系统后，施加2V直流电进行电解工作。随着电解过程的进行，控制工作温度为300℃。经测得，电解槽小室电压1.729V，电流密度为9512A/m2，能耗为4.132kWh/Nm3。The osmotic diaphragm is made of surface modified organic materials. After assembling the electrolysis water hydrogen production system, apply 2V DC for electrolysis. As the electrolysis process proceeds, the working temperature is controlled to be 300°C. It is measured that the cell voltage of the electrolytic cell is 1.729V, the current density is 9512A/m 2 , and the energy consumption is 4.132kWh/Nm 3 .
试验7：Test 7:
渗透隔膜采用硅酸镁隔膜，组装电解水制氢系统后，施加2V直流电进行电解工作。随着电解过程的进行，控制工作温度为350℃。经测得，电解槽小室电压1.712V，电流密度为8000A/m2，能耗为4.092kWh/Nm3。The osmotic diaphragm adopts magnesium silicate diaphragm, and after assembling the electrolysis water hydrogen production system, apply 2V direct current to carry out electrolysis work. As the electrolysis process proceeds, the operating temperature is controlled to be 350°C. It is measured that the cell voltage of the electrolytic cell is 1.712V, the current density is 8000A/m 2 , and the energy consumption is 4.092kWh/Nm3.
从上述试验1-7试验结果可以看出，与传统碱性水电解制氢的电流密度为3000A/m2和能耗为4.5kWh/Nm3相比，本方案整体能耗低，系统和工艺简单。From the test results of the above tests 1-7, it can be seen that compared with the current density of 3000A/m 2 and the energy consumption of 4.5kWh/Nm 3 in the traditional alkaline water electrolysis hydrogen production, the overall energy consumption of this scheme is low, and the system and process Simple.
上述实施例不以任何方式限制本发明，凡是采用等同替换或等效变换的方式获得的技术方案均落在本发明的保护范围内。The above embodiments do not limit the present invention in any way, and all technical solutions obtained by means of equivalent replacement or equivalent transformation fall within the protection scope of the present invention.
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