WO2023040110A1 - Photothermal coupled thermochemical hydrogen production system and method - Google Patents

Photothermal coupled thermochemical hydrogen production system and method Download PDF

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WO2023040110A1
WO2023040110A1 PCT/CN2021/140597 CN2021140597W WO2023040110A1 WO 2023040110 A1 WO2023040110 A1 WO 2023040110A1 CN 2021140597 W CN2021140597 W CN 2021140597W WO 2023040110 A1 WO2023040110 A1 WO 2023040110A1
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thermochemical
hydrogen production
photothermal
heat storage
heat
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PCT/CN2021/140597
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French (fr)
Chinese (zh)
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王凡
刘丽萍
王韬
郭海礁
王金意
余智勇
王鹏杰
任志博
张畅
徐显明
潘龙
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中国华能集团清洁能源技术研究院有限公司
四川华能氢能科技有限公司
华能集团技术创新中心有限公司
四川华能太平驿水电有限责任公司
四川华能宝兴河水电有限责任公司
四川华能嘉陵江水电有限责任公司
四川华能东西关水电股份有限公司
四川华能康定水电有限责任公司
四川华能涪江水电有限责任公司
华能明台电力有限责任公司
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Publication of WO2023040110A1 publication Critical patent/WO2023040110A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • thermochemical hydrogen production in particular to a photothermal coupled thermochemical hydrogen production system and method.
  • H2 is a kind of clean energy, which is of great significance to the realization of carbon emission reduction and carbon neutrality goals.
  • 90% of H2 comes from the reforming reaction of fossil fuels, but fossil fuels are not renewable, so it is particularly important to find alternatives to fossil energy.
  • Biomass energy can replace fossil energy for hydrogen production reaction, which is renewable and abundant in total.
  • the potential of biomass energy will be as high as 500EJ per year after 2050.
  • One of the effective ways to convert biomass energy into hydrogen energy is thermochemical hydrogen production, and heat energy can be obtained from photothermal systems. At present, there is no way to realize the synergy of light energy and biomass energy through photothermal coupling thermochemical hydrogen production. Conversion of hydrogen energy.
  • This application aims to solve one of the technical problems in the related art at least to a certain extent.
  • thermochemical hydrogen production which converts solar radiation energy into heat energy through a photothermal system and a heat storage system, and then supplies heat energy to a thermochemical reaction system through a heat supply system for hydrogen production.
  • Thermochemical hydrogen production combines renewable energy heating with biomass thermochemical hydrogen production. While realizing the utilization of renewable energy, it also provides a method for the resource utilization of biomass waste. Compared with the method of photoelectric hydrogen production, this method provides a resourceful means of consuming biomass waste for areas with large biomass waste production.
  • thermochemical hydrogen production system in the first aspect, including a photothermal system, a heat storage system, a heat supply system and a thermochemical reaction system.
  • the photothermal system is arranged around the The surrounding of the heat storage system, the concentrated solar energy of the photothermal system irradiates the heat storage medium in the heat storage system, the heat storage medium absorbs solar radiation energy, and the heat supply system is sleeved on the heat storage system.
  • the heat supply system is used to supply heat to the thermochemical reaction system, and the heat storage system is bidirectionally connected with the heat supply system to form a circulation flow path through a heat supply pipeline and a return pipeline.
  • the upper end of the supply system has a first interface and a second interface respectively connected to the heat supply pipeline and the return pipeline, and the heat storage system is used to provide high-temperature heat storage medium to the heat supply system and collect The low-temperature heat storage medium returned in the heat supply system mentioned above.
  • the photothermal system is a combination of one or more of a trough system, a Fresnel system, a disk system or a tower system.
  • the heat storage system is a calciner.
  • thermochemical reaction system is a combination of one or more of a gasification furnace, a pyrolysis furnace, a vertical furnace, a horizontal furnace, a two-stage furnace, and a three-stage furnace.
  • thermochemical reaction system has a feed inlet, and the feed inlet is used for inputting biomass and/or biomass waste.
  • the feed inlet is further used for inputting catalyst.
  • the photothermal coupled thermochemical hydrogen production system also includes a gas purification system.
  • the upper end of the thermochemical reaction system has a gas outlet, the gas purification system communicates with the gas outlet of the thermochemical reaction system, and the gas purification system is used to purify the gas produced by the thermochemical reaction system.
  • the gas purification system is a combination of one or more of a pressure swing adsorption hydrogen production device, a low temperature adsorption hydrogen production industrial device, a membrane separation method hydrogen production device and a metal hydride extraction ultrapure hydrogen device.
  • the heat storage medium is one or a combination of molten carbonate, potassium chloride, sodium fluoride or sodium chloride.
  • the temperature of the heat supply system is between 500°C and 800°C.
  • the present application proposes a photothermal coupling thermochemical hydrogen production method, which is applied to the above-mentioned photothermal coupling thermochemical hydrogen production system, including the following steps:
  • thermochemical reaction system is heated by using the heat supply system as a heat source, and the biomass material in the thermochemical reaction system undergoes a thermochemical reaction and produces gas, wherein the thermochemical reaction system simultaneously inputs reaction materials with catalyst.
  • thermochemical reaction is an alkali-thermal reaction.
  • the catalyst is an alkali metal hydroxide.
  • alkali metal hydroxide is any one of the first main group alkali metal hydroxide or the second main group alkali metal hydroxide or a mixture thereof.
  • the purification method is a combination of one or more of pressure swing adsorption, temperature swing adsorption, membrane separation method and metal hydride method.
  • Fig. 1 is a schematic structural diagram of a light-thermal coupled thermochemical hydrogen production system proposed by an embodiment of the present application.
  • Fig. 1 is a schematic structural diagram of a light-thermal coupled thermochemical hydrogen production system proposed by an embodiment of the present application.
  • a photothermal coupled thermochemical hydrogen production system includes a photothermal system 1, a heat storage system 2, a heat supply system 3 and a thermochemical reaction system 4, and the heat storage system 2 can be a calciner or other suitable container device, the heat storage medium is injected into the calciner, and the conversion of light energy and heat energy is realized through the phase change of the heat storage medium.
  • the photothermal system 1 concentrates solar energy to irradiate the heat storage medium in the heat storage system, and the heat storage medium absorbs solar radiation energy.
  • the photothermal system 1 can be arranged around the heat storage system 2, and the Sunlight is evenly focused and irradiated on the heat storage medium in the heat storage system 2, allowing the sun photons to directly interact with the heat storage medium to heat the reactant particles, and the heat storage medium can capture and absorb solar radiation energy in a full spectrum to achieve solar energy absorption , convert solar energy into thermal energy, drive thermochemical reactions, and convert solar energy into chemical energy.
  • the heat supply system 3 is sleeved on the outside of the thermochemical reaction system 4, and the heat supply system 3 is used to supply heat to the thermochemical reaction system 4.
  • the high-temperature heat storage medium When the high-temperature heat storage medium flows into the heat supply system 3, The high-temperature heat storage medium directly heats the thermochemical reaction system 4 through the outer wall of the thermochemical reaction system 4, so that the temperature in the thermochemical reaction system 4 rises rapidly, and a thermochemical reaction occurs.
  • the heat storage system 2 and the heat supply system 3 are bidirectionally connected through a heat supply pipeline and a return pipeline to form a circulating flow path, and the upper end of the heat supply system 3 has a The first interface and the second interface, specifically, the heat supply pipeline is connected to the first interface, and the return pipeline is connected to the second interface.
  • the high-temperature heat storage medium is injected into the heat supply system and flows out from the upper end of the heat supply system, extending the high temperature
  • the residence time of the heat storage medium in the heat supply system can fully heat the thermochemical reaction system and help the thermochemical reaction in the thermochemical reaction system to occur.
  • the heat storage system 2 is used to provide high-temperature heat storage medium to the heat supply system 3, and at the same time collect the low-temperature heat storage medium returning from the heat supply system 3.
  • the heat storage medium flows continuously in the circulation flow path, continuously Continuously heat the thermochemical reaction system to realize the conversion of light energy and heat energy.
  • the photothermal system 1 is a combination of one or more of the trough system, Fresnel system, disk system or tower system.
  • the specific form of the photothermal system 1 can be determined according to the site and user requirements. The present application does not limit this, as long as the effective collection of solar energy can be realized.
  • the thermochemical reaction system 4 is a combination of one or more of a gasification furnace, a pyrolysis furnace, a vertical furnace, a horizontal furnace, a two-stage furnace, and a three-stage furnace.
  • the specific form of the thermochemical reaction system 4 is It can be determined according to the site and user requirements. This application does not limit this, as long as the biomass can be fully converted. In this embodiment, it is preferably a pyrolysis furnace.
  • thermochemical reaction system 4 has a feed inlet, and the feed inlet is used to input biomass and/or biomass waste. It is worth noting that the reaction material biomass and catalyst are input at the same time, which can absorb the thermal chemical reaction in time.
  • the CO 2 produced by the reaction can be converted into carbonate complexes, which can achieve the goal of carbon emission reduction in the process of thermochemical hydrogen production.
  • a photothermal coupled thermochemical hydrogen production system also includes a gas purification system 5, the upper end of the thermochemical reaction system 4 has a gas outlet, and the gas purification system 5 communicates with the gas outlet of the thermochemical reaction system 4, so The gas purification system 5 is used to purify the gas produced by the thermochemical reaction system 4 .
  • the purification method can be a combination of one or more of pressure swing adsorption, temperature swing adsorption, membrane separation and metal hydride method.
  • the gas purification system can be a pressure swing adsorption hydrogen production device, a low temperature adsorption hydrogen production industrial device A combination of one or more of the membrane separation method hydrogen production device and the metal hydride extraction ultra-pure hydrogen device.
  • the purified hydrogen can be used in one or a combination of proton exchange membrane fuel cell power generation systems, solid oxide fuel cell power generation systems, molten carbonate fuel cell power generation systems, and phosphoric acid fuel cell power generation systems.
  • the heat storage medium is a combination of one or more of molten carbonate, potassium chloride, sodium fluoride or sodium chloride.
  • molten carbonate is preferred, which has better heat storage Ability to store solar energy with high efficiency and high energy density.
  • the temperature of the heat supply system 3 is between 500°C and 800°C. Improve the better temperature conditions for the thermochemical reaction of the thermochemical reaction system 4, and have higher gas production efficiency.
  • a photothermal coupling thermochemical hydrogen production method applied to the above photothermal coupling thermochemical hydrogen production system, comprising the following steps:
  • thermochemical reaction system 4 is heated with the heat supply system 3 as a heat source, and the biomass in the thermochemical reaction system 4 undergoes a thermochemical reaction to produce gas, wherein the thermochemical reaction system is input with reaction materials and catalysts at the same time.
  • thermochemical reaction is an alkali-thermal reaction.
  • the gas product after the alkali-thermal reaction does not contain carbon oxides, which can achieve the goal of carbon emission reduction in the process of thermochemical hydrogen production.
  • the catalyst is an alkali metal hydroxide.
  • the alkali catalyst can be the first main group alkali metal hydroxide represented by sodium hydroxide, or the second main group alkali metal hydroxide represented by calcium hydroxide, the activity of the catalyst is high, It has high catalytic efficiency.

Abstract

The present application sets forth a photothermal coupled thermochemical hydrogen production system and method. The photothermal coupled thermochemical hydrogen production system comprises a photothermal system, a heat storage system, a heat supply system and a thermochemical reaction system. The photothermal system concentrates solar energy to irradiate a heat storage medium in the heat storage system, the heat storage medium absorbs the solar radiation energy, the heat supply system is sleeved on an outer side of the thermochemical reaction system, and the heat supply system is used to supply heat to the thermochemical reaction system; solar radiation energy is converted into thermal energy by means of the photothermal system and the heat storage system, and then heat energy is supplied to the thermochemical reaction system by the heat supply system for thermochemical hydrogen production.

Description

一种光热耦合热化学制氢***及方法A photothermal coupled thermochemical hydrogen production system and method
相关申请的交叉引用Cross References to Related Applications
本申请基于申请号为202111082821.0、申请日为2021年9月15日的中国专利申请提出，并要求该中国专利申请的优先权，该中国专利申请的全部内容在此引入本申请作为参考。This application is based on a Chinese patent application with application number 202111082821.0 and a filing date of September 15, 2021, and claims the priority of this Chinese patent application. The entire content of this Chinese patent application is hereby incorporated by reference into this application.
技术领域technical field
本申请涉及热化学制氢技术领域，尤其涉及一种光热耦合热化学制氢***及方法。The present application relates to the technical field of thermochemical hydrogen production, in particular to a photothermal coupled thermochemical hydrogen production system and method.
背景技术Background technique
H 2是一种清洁能源，对于碳减排和碳中和目标的实现具有重要意义。目前90％的H 2来自于化石燃料的重整反应，但是化石燃料不可再生，所以寻找化石能源的替代品尤为重要。生物质能可替代化石能源进行产氢反应，其具有可再生性，并且总量丰富。生物质能的潜力在2050年后，每年将高达500EJ。将生物质能转化为氢能的有效方式之一是热化学制氢，而热能又可以从光热***得到，目前尚没有通过光热耦合热化学制氢的方式实现光能协同生物质能到氢能的转化。 H2 is a kind of clean energy, which is of great significance to the realization of carbon emission reduction and carbon neutrality goals. At present, 90% of H2 comes from the reforming reaction of fossil fuels, but fossil fuels are not renewable, so it is particularly important to find alternatives to fossil energy. Biomass energy can replace fossil energy for hydrogen production reaction, which is renewable and abundant in total. The potential of biomass energy will be as high as 500EJ per year after 2050. One of the effective ways to convert biomass energy into hydrogen energy is thermochemical hydrogen production, and heat energy can be obtained from photothermal systems. At present, there is no way to realize the synergy of light energy and biomass energy through photothermal coupling thermochemical hydrogen production. Conversion of hydrogen energy.
发明内容Contents of the invention
本申请旨在至少在一定程度上解决相关技术中的技术问题之一。This application aims to solve one of the technical problems in the related art at least to a certain extent.
为此，本申请的目的在于提出一种光热耦合热化学制氢***，通过光热***和储热***将太阳辐射能转化为热能，然后通过热力供应***将热能供应到热化学反应***进行热化学制氢，采用可再生能源发热与生物质热化学制氢相结合，在实现可再生能源利用的同时，也为生物质废物的资源化提供了方法。相比于光电制氢的方式，该方法为生物质废物产量大的地区提供了一种消纳生物质废物的资源化手段。For this reason, the purpose of this application is to propose a photothermal coupling thermochemical hydrogen production system, which converts solar radiation energy into heat energy through a photothermal system and a heat storage system, and then supplies heat energy to a thermochemical reaction system through a heat supply system for hydrogen production. Thermochemical hydrogen production combines renewable energy heating with biomass thermochemical hydrogen production. While realizing the utilization of renewable energy, it also provides a method for the resource utilization of biomass waste. Compared with the method of photoelectric hydrogen production, this method provides a resourceful means of consuming biomass waste for areas with large biomass waste production.
为达到上述目的，本申请在第一方面提出一种光热耦合热化学制氢***，包括光热***、储热***、热力供应***和热化学反应***，所述光热***围绕设置在所述储热***的周围，所述光热***聚光太阳能照射到所述储热***中的储热介质上，所述储热介质吸收太阳辐射能，所述热力供应***套设于所述热化学反应***外侧，所述热力供应***用于向所述热化学反应***供热，所述储热***与所述热力供应***通过供热管道和回流管道双向连接形成循环流路，所述热力供应***的上端具有分别与所述供热管道和所述回流管道连接的第一接 口和第二接口，所述储热***用于提供高温储热介质到所述热力供应***中，同时收集所述热力供应***中回流的低温储热介质。In order to achieve the above purpose, the present application proposes a photothermal coupling thermochemical hydrogen production system in the first aspect, including a photothermal system, a heat storage system, a heat supply system and a thermochemical reaction system. The photothermal system is arranged around the The surrounding of the heat storage system, the concentrated solar energy of the photothermal system irradiates the heat storage medium in the heat storage system, the heat storage medium absorbs solar radiation energy, and the heat supply system is sleeved on the heat storage system. On the outside of the chemical reaction system, the heat supply system is used to supply heat to the thermochemical reaction system, and the heat storage system is bidirectionally connected with the heat supply system to form a circulation flow path through a heat supply pipeline and a return pipeline. The upper end of the supply system has a first interface and a second interface respectively connected to the heat supply pipeline and the return pipeline, and the heat storage system is used to provide high-temperature heat storage medium to the heat supply system and collect The low-temperature heat storage medium returned in the heat supply system mentioned above.
进一步地，所述光热***为槽式***、菲涅尔式***、盘式***或者塔式***中的一种或多种的组合。Further, the photothermal system is a combination of one or more of a trough system, a Fresnel system, a disk system or a tower system.
进一步地，所述储热***为煅烧炉。Further, the heat storage system is a calciner.
进一步地，所述热化学反应***为气化炉、热解炉、立式炉、卧式炉、两段炉、三段炉中的一种或多种的组合。Further, the thermochemical reaction system is a combination of one or more of a gasification furnace, a pyrolysis furnace, a vertical furnace, a horizontal furnace, a two-stage furnace, and a three-stage furnace.
进一步地，所述热化学反应***的上端具有进料口，所述进料口用于投入生物质和/或生物质废物。Further, the upper end of the thermochemical reaction system has a feed inlet, and the feed inlet is used for inputting biomass and/or biomass waste.
进一步地，所述进料口进一步用于投入催化剂。Further, the feed inlet is further used for inputting catalyst.
进一步地，所述光热耦合热化学制氢***还包括气体纯化***。所述热化学反应***的上端具有出气口，所述气体纯化***与所述热化学反应***的出气口连通，所述气体纯化***用于对所述热化学反应***产出的气体进行纯化。Further, the photothermal coupled thermochemical hydrogen production system also includes a gas purification system. The upper end of the thermochemical reaction system has a gas outlet, the gas purification system communicates with the gas outlet of the thermochemical reaction system, and the gas purification system is used to purify the gas produced by the thermochemical reaction system.
进一步地，所述气体纯化***为变压吸附制氢装置、低温吸附法制氢工业装置、膜分离法制氢装置和用金属氢化物提取超纯氢装置中的一种或多种的组合。Further, the gas purification system is a combination of one or more of a pressure swing adsorption hydrogen production device, a low temperature adsorption hydrogen production industrial device, a membrane separation method hydrogen production device and a metal hydride extraction ultrapure hydrogen device.
进一步地，所述储热介质为熔融碳酸盐、氯化钾、氟化钠或氯化钠中的一种或多种的组合。Further, the heat storage medium is one or a combination of molten carbonate, potassium chloride, sodium fluoride or sodium chloride.
进一步地，所述热力供应***的温度在500℃至800℃之间。本申请在第二方面提出一种光热耦合热化学制氢方法，应用于上述所述的光热耦合热化学制氢***，包括如下步骤：Further, the temperature of the heat supply system is between 500°C and 800°C. In the second aspect, the present application proposes a photothermal coupling thermochemical hydrogen production method, which is applied to the above-mentioned photothermal coupling thermochemical hydrogen production system, including the following steps:
通过所述光热***将太阳能转化为热能并储存在所述储热***的所述储热介质中；converting solar energy into heat energy through the photothermal system and storing it in the heat storage medium of the heat storage system;
将所述储热***中的所述储热介质泵入所述热力供应***；pumping the heat storage medium in the heat storage system into the heat supply system;
以所述热力供应***为热源对所述热化学反应***进行加热，所述热化学反应***中的生物质材料发生热化学反应并产出气体，其中，所述热化学反应***同时投入反应物料与催化剂。The thermochemical reaction system is heated by using the heat supply system as a heat source, and the biomass material in the thermochemical reaction system undergoes a thermochemical reaction and produces gas, wherein the thermochemical reaction system simultaneously inputs reaction materials with catalyst.
进一步地，所述热化学反应为碱热反应。Further, the thermochemical reaction is an alkali-thermal reaction.
进一步地，在所述碱热反应中，所述催化剂为碱金属氢氧化物。Further, in the alkali thermal reaction, the catalyst is an alkali metal hydroxide.
进一步地，所述碱金属氢氧化物为第一主族碱金属氢氧化物或第二主族碱金属氢氧化物中的任一种或它们的混合物。Further, the alkali metal hydroxide is any one of the first main group alkali metal hydroxide or the second main group alkali metal hydroxide or a mixture thereof.
进一步地，当所述光热耦合热化学制氢***包括所述纯化***时，纯化方式为变压吸附、变温吸附、膜分离法和金属氢化物法中的一种或多种的组合。Further, when the photothermal coupling thermochemical hydrogen production system includes the purification system, the purification method is a combination of one or more of pressure swing adsorption, temperature swing adsorption, membrane separation method and metal hydride method.
本申请附加的方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本申请的实践了解到。Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.
附图说明Description of drawings
本申请上述的和/或附加的方面和优点从下面结合附图对实施例的描述中将变得明显和容易理解，其中：The above and/or additional aspects and advantages of the present application will become apparent and easy to understand from the following description of the embodiments in conjunction with the accompanying drawings, wherein:
图1是本申请一实施例提出的一种光热耦合热化学制氢***的结构示意图。Fig. 1 is a schematic structural diagram of a light-thermal coupled thermochemical hydrogen production system proposed by an embodiment of the present application.
具体实施方式Detailed ways
下面详细描述本申请的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。相反，本申请的实施例包括落入所附加权利要求书的精神和内涵范围内的所有变化、修改和等同物。Embodiments of the present application are described in detail below, examples of which are shown in the drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the figures are exemplary, and are only for explaining the present application, and should not be construed as limiting the present application. On the contrary, the embodiments of the present application include all changes, modifications and equivalents falling within the spirit and scope of the appended claims.
图1是本申请一实施例提出的一种光热耦合热化学制氢***的结构示意图。Fig. 1 is a schematic structural diagram of a light-thermal coupled thermochemical hydrogen production system proposed by an embodiment of the present application.
参见图1，一种光热耦合热化学制氢***，包括光热***1、储热***2、热力供应***3和热化学反应***4，储热***2可以为煅烧炉或其他合适的容器装置，煅烧炉里面注入储热介质，通过储热介质的相变实现光能和热能的转化。所述光热***1聚光太阳能照射到储热***中的储热介质上，所述储热介质吸收太阳辐射能，具体地，光热***1可以围绕设置在储热***2的周围，将太阳光均匀地聚焦照射到储热***2内的储热介质上，让太阳光子与储热介质直接作用，加热反应物颗粒，储热介质能够全光谱捕获与吸收太阳辐射能，实现太阳能体吸收，把太阳能转换为热能，驱动热化学反应，从而把太阳能转换为化学能。所述热力供应***3套设于所述热化学反应***4外侧，所述热力供应***3用于向所述热化学反应***4供热，当高温储热介质流进热力供应***3后，高温储热介质通过热化学反应***4的外侧壁直接对热化学反应***4进行加热，使热化学反应***4内的温度迅速升高，发生热化学反应。所述储热***2与所述热力供应***3通过供热管道和回流管道双向连接形成循环流路，所述热力供应***3的上端具有分别与所述供热管道和所述回流管道连接的第一接口和第二接口，具体地，供热管道和第一接口连接，回流管道和第二接口连接，高温储热介质注入热力供应***内，并从热力供应***的上端流出，延长了高温储热介质在热力供应***内的停留时间，能够充分对热化学反应***进行加热，有助于热化学反应***内的热化学反应发生。所述储热***2用于提供高温储热介质到所述热力供应***3中，同时收 集所述热力供应***3中回流的低温储热介质，储热介质在循环流路中不断流动，持续不断地为热化学反应***进行供热，实现光能和热能的转化。Referring to Figure 1, a photothermal coupled thermochemical hydrogen production system includes a photothermal system 1, a heat storage system 2, a heat supply system 3 and a thermochemical reaction system 4, and the heat storage system 2 can be a calciner or other suitable container device, the heat storage medium is injected into the calciner, and the conversion of light energy and heat energy is realized through the phase change of the heat storage medium. The photothermal system 1 concentrates solar energy to irradiate the heat storage medium in the heat storage system, and the heat storage medium absorbs solar radiation energy. Specifically, the photothermal system 1 can be arranged around the heat storage system 2, and the Sunlight is evenly focused and irradiated on the heat storage medium in the heat storage system 2, allowing the sun photons to directly interact with the heat storage medium to heat the reactant particles, and the heat storage medium can capture and absorb solar radiation energy in a full spectrum to achieve solar energy absorption , convert solar energy into thermal energy, drive thermochemical reactions, and convert solar energy into chemical energy. The heat supply system 3 is sleeved on the outside of the thermochemical reaction system 4, and the heat supply system 3 is used to supply heat to the thermochemical reaction system 4. When the high-temperature heat storage medium flows into the heat supply system 3, The high-temperature heat storage medium directly heats the thermochemical reaction system 4 through the outer wall of the thermochemical reaction system 4, so that the temperature in the thermochemical reaction system 4 rises rapidly, and a thermochemical reaction occurs. The heat storage system 2 and the heat supply system 3 are bidirectionally connected through a heat supply pipeline and a return pipeline to form a circulating flow path, and the upper end of the heat supply system 3 has a The first interface and the second interface, specifically, the heat supply pipeline is connected to the first interface, and the return pipeline is connected to the second interface. The high-temperature heat storage medium is injected into the heat supply system and flows out from the upper end of the heat supply system, extending the high temperature The residence time of the heat storage medium in the heat supply system can fully heat the thermochemical reaction system and help the thermochemical reaction in the thermochemical reaction system to occur. The heat storage system 2 is used to provide high-temperature heat storage medium to the heat supply system 3, and at the same time collect the low-temperature heat storage medium returning from the heat supply system 3. The heat storage medium flows continuously in the circulation flow path, continuously Continuously heat the thermochemical reaction system to realize the conversion of light energy and heat energy.
所述光热***1为槽式***、菲涅尔式***、盘式***或者塔式***中的一种或多种的组合，光热***1的具体形式可以根据场地及用户要求进行确定，本申请对此不作限制，能够实现对太阳光能的有效收集即可。The photothermal system 1 is a combination of one or more of the trough system, Fresnel system, disk system or tower system. The specific form of the photothermal system 1 can be determined according to the site and user requirements. The present application does not limit this, as long as the effective collection of solar energy can be realized.
所述热化学反应***4为为气化炉、热解炉、立式炉、卧式炉、两段炉、三段炉中的一种或多种的组合，热化学反应***4的具体形式可以根据场地及用户要求进行确定，本申请对此不作限制，能够实现对生物质充分转化即可，本实施例中，优选为热解炉。The thermochemical reaction system 4 is a combination of one or more of a gasification furnace, a pyrolysis furnace, a vertical furnace, a horizontal furnace, a two-stage furnace, and a three-stage furnace. The specific form of the thermochemical reaction system 4 is It can be determined according to the site and user requirements. This application does not limit this, as long as the biomass can be fully converted. In this embodiment, it is preferably a pyrolysis furnace.
所述热化学反应***4的上端具有进料口，所述进料口用于投入生物质和/或生物质废物，值得注意的是，反应物料生物质与催化剂同时投入，可以及时吸收热化学反应产生的CO 2，把CO 2转换为碳酸盐复合物，可以在热化学制氢的过程中实现碳减排的目标。 The upper end of the thermochemical reaction system 4 has a feed inlet, and the feed inlet is used to input biomass and/or biomass waste. It is worth noting that the reaction material biomass and catalyst are input at the same time, which can absorb the thermal chemical reaction in time. The CO 2 produced by the reaction can be converted into carbonate complexes, which can achieve the goal of carbon emission reduction in the process of thermochemical hydrogen production.
一种光热耦合热化学制氢***还包括气体纯化***5，所述热化学反应***4的上端具有出气口，所述气体纯化***5与所述热化学反应***4的出气口连通，所述气体纯化***5用于对所述热化学反应***4产出的气体进行纯化。纯化方式可以为变压吸附、变温吸附、膜分离法和金属氢化物法中的一种或多种的组合，相应地，气体纯化***可以为变压吸附制氢装置、低温吸附法制氢工业装置、膜分离法制氢装置和用金属氢化物提取超纯氢装置其中一种或多种的组合。纯化后的氢气可用于质子交换膜燃料电池发电***、固体氧化物燃料电池发电***、熔融碳酸盐燃料电池发电***、磷酸燃料电池发电***中的一种或多种的组合。A photothermal coupled thermochemical hydrogen production system also includes a gas purification system 5, the upper end of the thermochemical reaction system 4 has a gas outlet, and the gas purification system 5 communicates with the gas outlet of the thermochemical reaction system 4, so The gas purification system 5 is used to purify the gas produced by the thermochemical reaction system 4 . The purification method can be a combination of one or more of pressure swing adsorption, temperature swing adsorption, membrane separation and metal hydride method. Correspondingly, the gas purification system can be a pressure swing adsorption hydrogen production device, a low temperature adsorption hydrogen production industrial device A combination of one or more of the membrane separation method hydrogen production device and the metal hydride extraction ultra-pure hydrogen device. The purified hydrogen can be used in one or a combination of proton exchange membrane fuel cell power generation systems, solid oxide fuel cell power generation systems, molten carbonate fuel cell power generation systems, and phosphoric acid fuel cell power generation systems.
所述储热介质为熔融碳酸盐、氯化钾、氟化钠或氯化钠中的一种或多种的组合，本实施例中，优选为熔融碳酸盐，具有较好的储热能力，可以高效率、高能量密度存储太阳能。The heat storage medium is a combination of one or more of molten carbonate, potassium chloride, sodium fluoride or sodium chloride. In this embodiment, molten carbonate is preferred, which has better heat storage Ability to store solar energy with high efficiency and high energy density.
所述热力供应***3的温度在500℃-800℃之间。为热化学反应***4热化学反应提高较佳地温度条件，具有较高的产气效率。The temperature of the heat supply system 3 is between 500°C and 800°C. Improve the better temperature conditions for the thermochemical reaction of the thermochemical reaction system 4, and have higher gas production efficiency.
一种光热耦合热化学制氢方法，应用于上述的光热耦合热化学制氢***，包括如下步骤：A photothermal coupling thermochemical hydrogen production method, applied to the above photothermal coupling thermochemical hydrogen production system, comprising the following steps:
通过光热***1将太阳能转化为热能并储存在储热***2的储热介质中；Convert solar energy into thermal energy through the photothermal system 1 and store it in the heat storage medium of the heat storage system 2;
将储热***2中储热介质泵入热力供应***3；Pumping the heat storage medium in the heat storage system 2 into the heat supply system 3;
以热力供应***3为热源将热化学反应***4进行加热，热化学反应***4中的生物质发生热化学反应并产出气体，其中，所述热化学反应***同时投入反应物料与催化剂。The thermochemical reaction system 4 is heated with the heat supply system 3 as a heat source, and the biomass in the thermochemical reaction system 4 undergoes a thermochemical reaction to produce gas, wherein the thermochemical reaction system is input with reaction materials and catalysts at the same time.
所述热化学反应为碱热反应。碱热反应后的气体产物不含碳氧化物，可以在热化学制氢的过程中实现碳减排的目标。The thermochemical reaction is an alkali-thermal reaction. The gas product after the alkali-thermal reaction does not contain carbon oxides, which can achieve the goal of carbon emission reduction in the process of thermochemical hydrogen production.
在所述碱热反应中，催化剂为碱金属氢氧化物。在碱热反应中，碱催化剂可以为以氢氧化钠为代表的第一主族碱金属氢氧化物，或者以氢氧化钙为代表的第二主族碱金属氢氧化物，催化剂的活性高，具有较高的催化效率。In the base thermal reaction, the catalyst is an alkali metal hydroxide. In the alkali-thermal reaction, the alkali catalyst can be the first main group alkali metal hydroxide represented by sodium hydroxide, or the second main group alkali metal hydroxide represented by calcium hydroxide, the activity of the catalyst is high, It has high catalytic efficiency.
需要说明的是，在本申请的描述中，术语“第一”、“第二”等仅用于描述目的，而不能理解为指示或暗示相对重要性。此外，在本申请的描述中，除非另有说明，“多个”的含义是两个或两个以上。It should be noted that in the description of the present application, terms such as "first" and "second" are used for description purposes only, and should not be understood as indicating or implying relative importance. In addition, in the description of the present application, unless otherwise specified, "plurality" means two or more.
流程图中或在此以其他方式描述的任何过程或方法描述可以被理解为，表示包括一个或更多个用于实现特定逻辑功能或过程的步骤的可执行指令的代码的模块、片段或部分，并且本申请的优选实施方式的范围包括另外的实现，其中可以不按所示出或讨论的顺序，包括根据所涉及的功能按基本同时的方式或按相反的顺序，来执行功能，这应被本申请的实施例所属技术领域的技术人员所理解。Any process or method descriptions in flowcharts or otherwise described herein may be understood to represent modules, segments or portions of code comprising one or more executable instructions for implementing specific logical functions or steps of the process , and the scope of preferred embodiments of the present application includes additional implementations in which functions may be performed out of the order shown or discussed, including in substantially simultaneous fashion or in reverse order depending on the functions involved, which shall It should be understood by those skilled in the art to which the embodiments of the present application belong.
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本申请的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。In the description of this specification, descriptions referring to the terms "one embodiment", "some embodiments", "example", "specific examples", or "some examples" mean that specific features described in connection with the embodiment or example , structure, material or characteristic is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
尽管上面已经示出和描述了本申请的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本申请的限制，本领域的普通技术人员在本申请的范围内可以对上述实施例进行变化、修改、替换和变型。Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limitations on the present application, and those skilled in the art can make the above-mentioned The embodiments are subject to changes, modifications, substitutions and variations.

Claims (15)

  1. 一种光热耦合热化学制氢***，包括光热***、储热***、热力供应***和热化学反应***，其中所述光热***围绕设置在所述储热***的周围，所述光热***聚光太阳能照射到所述储热***中的储热介质上，所述储热介质吸收太阳辐射能，所述热力供应***套设于所述热化学反应***外侧，所述热力供应***用于向所述热化学反应***供热，所述储热***与所述热力供应***通过供热管道和回流管道双向连接形成循环流路，所述热力供应***的上端具有分别与所述供热管道和所述回流管道连接的第一接口和第二接口，所述储热***用于提供高温储热介质到所述热力供应***中，同时收集所述热力供应***中回流的低温储热介质。A photothermal coupled thermochemical hydrogen production system, including a photothermal system, a heat storage system, a heat supply system and a thermochemical reaction system, wherein the photothermal system is arranged around the heat storage system, and the photothermal The concentrated solar energy of the system irradiates the heat storage medium in the heat storage system, and the heat storage medium absorbs solar radiation energy. The heat supply system is set outside the thermochemical reaction system, and the heat supply system uses In order to supply heat to the thermochemical reaction system, the heat storage system is bidirectionally connected with the heat supply system through a heat supply pipe and a return pipe to form a circulation flow path, and the upper end of the heat supply system has a The pipeline is connected to the first interface and the second interface of the return pipeline, and the heat storage system is used to provide high-temperature heat storage medium to the heat supply system, and at the same time collect the low-temperature heat storage medium returning from the heat supply system .
  2. 如权利要求1所述的光热耦合热化学制氢***，其中所述光热***为槽式***、菲涅尔式***、盘式***或者塔式***中的一种或多种的组合。The photothermal coupled thermochemical hydrogen production system according to claim 1, wherein the photothermal system is a combination of one or more of a trough system, a Fresnel system, a disk system or a tower system.
  3. 如权利要求1或2所述的光热耦合热化学制氢***，其中所述储热***为煅烧炉。The photothermal coupled thermochemical hydrogen production system according to claim 1 or 2, wherein the heat storage system is a calciner.
  4. 如权利要求1至3中任一项所述的光热耦合热化学制氢***，其中所述热化学反应***为气化炉、热解炉、立式炉、卧式炉、两段炉、三段炉中的一种或多种的组合。The photothermal coupling thermochemical hydrogen production system according to any one of claims 1 to 3, wherein the thermochemical reaction system is a gasification furnace, a pyrolysis furnace, a vertical furnace, a horizontal furnace, a two-stage furnace, One or more combinations of three-stage furnaces.
  5. 如权利要求1至4中任一项所述的光热耦合热化学制氢***，其中所述热化学反应***的上端具有进料口，所述进料口用于投入生物质和/或生物质废物。The photothermal coupling thermochemical hydrogen production system according to any one of claims 1 to 4, wherein the upper end of the thermochemical reaction system has a feed port, and the feed port is used to input biomass and/or biomass material waste.
  6. 如权利要求5所述的光热耦合热化学制氢***，其中所述进料口进一步用于投入催化剂。The light-thermal coupled thermochemical hydrogen production system according to claim 5, wherein the feed inlet is further used for inputting a catalyst.
  7. 如权利要求1至6中任一项所述的光热耦合热化学制氢***，还包括气体纯化***，其中所述热化学反应***的上端具有出气口，所述气体纯化***与所述热化学反应***的出气口连通，所述气体纯化***用于对所述热化学反应***产出的气体进行纯化。The photothermal coupling thermochemical hydrogen production system according to any one of claims 1 to 6, further comprising a gas purification system, wherein the upper end of the thermochemical reaction system has a gas outlet, and the gas purification system is connected to the thermal The gas outlet of the chemical reaction system is connected, and the gas purification system is used to purify the gas produced by the thermochemical reaction system.
  8. 如权利要求7所述的光热耦合热化学制氢***，其中所述气体纯化***为变压吸附制氢装置、低温吸附法制氢工业装置、膜分离法制氢装置和用金属氢化物提取超纯氢装置中的一种或多种的组合。The photothermal coupling thermochemical hydrogen production system according to claim 7, wherein the gas purification system is a pressure swing adsorption hydrogen production device, a low-temperature adsorption hydrogen production industrial device, a membrane separation method hydrogen production device, and a metal hydride extraction ultra-pure hydrogen production system. One or more combinations of hydrogen devices.
  9. 如权利要求1至8中任一项所述的光热耦合热化学制氢***，其中所述储热介质为熔融碳酸盐、氯化钾、氟化钠或氯化钠中的一种或多种的组合。The photothermal coupling thermochemical hydrogen production system according to any one of claims 1 to 8, wherein the heat storage medium is one of molten carbonate, potassium chloride, sodium fluoride or sodium chloride or Various combinations.
  10. 如权利要求1至9中任一项所述的光热耦合热化学制氢***，其中所述热力供应***的温度在500℃至800℃之间。The photothermal coupling thermochemical hydrogen production system according to any one of claims 1 to 9, wherein the temperature of the heat supply system is between 500°C and 800°C.
  11. 一种光热耦合热化学制氢方法，应用于上述权利要求1至10中任一项所述的光热 耦合热化学制氢***，其中所述方法包括如下步骤：A photothermal coupling thermochemical hydrogen production method, applied to the photothermal coupling thermochemical hydrogen production system described in any one of the above claims 1 to 10, wherein the method comprises the following steps:
    通过所述光热***将太阳能转化为热能并储存在所述储热***的所述储热介质中；converting solar energy into heat energy through the photothermal system and storing it in the heat storage medium of the heat storage system;
    将所述储热***中的所述储热介质泵入所述热力供应***；pumping the heat storage medium in the heat storage system into the heat supply system;
    以所述热力供应***为热源对所述热化学反应***进行加热，所述热化学反应***中的生物质材料发生热化学反应并产出气体，其中，所述热化学反应***同时投入反应物料与催化剂。The thermochemical reaction system is heated by using the heat supply system as a heat source, and the biomass material in the thermochemical reaction system undergoes a thermochemical reaction and produces gas, wherein the thermochemical reaction system simultaneously inputs reaction materials with catalyst.
  12. 如权利要求11所述的光热耦合热化学制氢方法，其中所述热化学反应为碱热反应。The photothermal coupled thermochemical hydrogen production method according to claim 11, wherein the thermochemical reaction is an alkali-thermal reaction.
  13. 如权利要求12所述的光热耦合热化学制氢方法，其中在所述碱热反应中，所述催化剂为碱金属氢氧化物。The photothermal coupling thermochemical hydrogen production method according to claim 12, wherein in the alkali thermal reaction, the catalyst is an alkali metal hydroxide.
  14. 如权利要求13所述的光热耦合热化学制氢方法，其中所述碱金属氢氧化物为第一主族碱金属氢氧化物或第二主族碱金属氢氧化物中的任一种或它们的混合物。The photothermal coupling thermochemical hydrogen production method according to claim 13, wherein the alkali metal hydroxide is any one of the first main group alkali metal hydroxide or the second main group alkali metal hydroxide or their mixture.
  15. 如权利要求11至14中任一项所述的光热耦合热化学制氢方法，其中当所述光热耦合热化学制氢***包括所述纯化***时，纯化方式为变压吸附、变温吸附、膜分离法和金属氢化物法中的一种或多种的组合。The photothermal coupling thermochemical hydrogen production method according to any one of claims 11 to 14, wherein when the photothermal coupling thermochemical hydrogen production system includes the purification system, the purification method is pressure swing adsorption and temperature swing adsorption , a combination of one or more of the membrane separation method and the metal hydride method.
PCT/CN2021/140597 2021-09-15 2021-12-22 Photothermal coupled thermochemical hydrogen production system and method WO2023040110A1 (en)

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