CN215050734U

CN215050734U - Electrochemical synthesis device based on high-temperature high-pressure electrolysis technology

Info

Publication number: CN215050734U
Application number: CN202120111831.1U
Authority: CN
Inventors: 王建强; 关成志; 王之桀; 万松; 陆越; 解春雨
Original assignee: Shanghai Institute of Applied Physics of CAS
Current assignee: Shanghai Institute of Applied Physics of CAS
Priority date: 2021-01-15
Filing date: 2021-01-15
Publication date: 2021-12-07
Anticipated expiration: 2031-01-15

Abstract

The utility model relates to an electrochemical synthesis device based on high temperature high pressure electrolysis technology, the solid oxide electrolytic cell thereof has an electrolyte layer and a cathode layer and an anode layer which are respectively positioned at the two opposite sides of the electrolyte layer, wherein, the cathode layer and the anode layer are respectively loaded with catalyst components required by the synthesis of chemicals or oils to couple the reaction of high temperature electrolysis water vapor and/or carbon dioxide and the high temperature electrocatalysis reaction, thereby preparing high pressure hydrogen, synthesis gas and oxygen and directly synthesizing the chemicals or the oils; the gas control system is used for controlling the composition, flow and pressure of the gas reactant and the gas product; the thermal management system is used for monitoring and controlling the ambient temperature and the electrode temperature of the solid oxide electrolytic cell. According to the utility model discloses an electrochemical synthesis device based on high temperature high pressure electrolysis technique to water and/or carbon dioxide are as the raw materials, through intermediate products such as high temperature high pressure electrolysis preparation hydrogen, carbon monoxide or synthetic gas, further synthesize high-value chemicals or oil.

Description

Electrochemical synthesis device based on high-temperature high-pressure electrolysis technology

Technical Field

The utility model relates to an electrochemical synthesis, more specifically relates to an electrochemical synthesis device based on high temperature high pressure electrolysis technique.

Background

At present, chemicals such as urea, methanol and synthetic oil and oil products are widely applied in the production and life of human industry, and support the development of the whole world. These products are typically obtained by more traditional chemical industrial processes, such as obtaining hydrogen or syngas (a mixture of hydrogen and carbon monoxide) from coal or natural gas chemical, then preparing urea from the syngas in an ammonia synthesis process, or preparing methanol and other high value oils and chemicals using the fischer-tropsch reaction. Rational utilization of hydrogen and syngas as feedstocks has been demonstrated to produce over 15 different conventional oils and bulk/fine chemicals with market values exceeding trillion dollars.

However, the conventional processes of coal chemical industry or natural gas chemical industry require high investment and investment for preparing hydrogen and synthesis gas, and are mainly suitable for large-scale industrial devices and are not suitable for users with different scale requirements. If a gas generator that can implement a modular design can be developed, user demands on different scales can be met, and a higher profit product can be produced. In addition, the processes of producing hydrogen by using coal, petroleum or natural gas and producing synthesis gas are accompanied by the emission of a large amount of carbon dioxide greenhouse gases, so that great test is brought to the environment. If industrial waste carbon dioxide can be used as the only carbon-based source of chemicals and oil products, the economic value of the industrial waste carbon dioxide can be improved, and zero carbon emission is realized. In addition, the existing process of synthesizing other chemicals and oil products by taking hydrogen or synthesis gas as raw materials is separated from the gas making process, which easily causes overlarge additional energy consumption and simultaneously brings about the problems of storage and transportation of the hydrogen and the synthesis gas. In order to achieve the above objects at the same time, it is necessary to develop an efficient, economical and modular reactor, which can prepare hydrogen or synthesis gas according to the actual scale requirement by using water and carbon dioxide as raw materials, and apply a catalyst for preparing chemicals and oils from hydrogen or synthesis gas to a gas preparation reactor to realize the synthesis of high-value chemicals and oils.

Solid oxide high temperature electrolytic cells (SOECs), which can combine the electricity of renewable energy sources with industrial waste heat, electrochemically reduce carbon dioxide and water efficiently to carbon monoxide, hydrogen and syngas, are considered to be one of the most promising energy conversion devices. The SOEC electrolytic cell also has the characteristics of full solid ceramic structure, high reaction rate and corresponding rate, no use of noble metal and the like. Moreover, SOEC electrolysis of water to produce hydrogen has been demonstrated to be able to be used for higher scale hydrogen and carbon monoxide production, with a substantial reduction in equipment investment in SOEC-based electrochemical plants on a mass production scale, of between about 50-70% of conventional thermochemical plants, compared to conventional thermochemical plants (such as coal or natural gas to syngas). On the other hand, the existing SOEC electrolytic cell structure is used, and through optimization, the electrolytic efficiency can be improved, the cost can be reduced, and the per-pass conversion rate of water and carbon dioxide which is more than 50% can be realized. Meanwhile, based on the SOEC electrolytic cell, the independent regulation and control of carbon monoxide/hydrogen in the synthesis gas can be realized by regulating and controlling process parameters, so that the synthesis gas directly enters a subsequent ammonia, methanol or Fischer-Tropsch reactor according to the requirements of products (oil products or chemicals), further hydrogen-carbon ratio regulation is not needed, the comprehensive cost of the chemicals and the oil products is remarkably reduced, and the synthesis cost is about 70 percent of the products produced by a conventional thermochemical plant. However, the conventional SOEC electrolytic cell belongs to a low-pressure (<3bar) electrolysis technology, can only obtain hydrogen or synthesis gas with lower pressure, and is not suitable for the preparation process of chemicals such as synthetic ammonia or fischer-tropsch reaction. On the other hand, the electrode material of the SOEC electrolytic cell mainly plays a catalytic role in dissociation of water and carbon dioxide and oxygen evolution reaction, and has no significant catalytic activity for the chemical preparation process. Therefore, the conventional SOEC electrolytic cell is not suitable for direct electrochemical synthesis of high-value chemicals and oils.

SUMMERY OF THE UTILITY MODEL

In order to solve the problem that the conventional SOEC electrolytic cell in the prior art is not suitable for directly synthesizing high-value chemicals and oils by electrochemistry, the utility model provides an electrochemical synthesis device based on high-temperature high-pressure electrolysis technology.

According to the utility model discloses an electrochemical synthesis device based on high temperature high pressure electrolysis technique, it includes solid oxide electrolytic cell, gas control system and thermal management system, wherein, solid oxide electrolytic cell has electrolyte layer and the cathode layer and the anode layer that are located the relative both sides of electrolyte layer respectively, wherein, carry the required catalyst component of chemicals or oil synthesis in cathode layer and the anode layer respectively with coupling high temperature electrolysis vapor and/or carbon dioxide reaction and high temperature electrocatalysis reaction to prepare high pressure hydrogen, synthetic gas and oxygen and directly synthesize chemicals or oil; the gas control system is used for controlling the composition, flow and pressure of the gas reactant and the gas product; the thermal management system is used for monitoring and controlling the ambient temperature and the electrode temperature of the solid oxide electrolytic cell.

For conventional solid oxide electrolytic cell, the utility model discloses a improve the feed gas pressure of electrolytic cell both sides simultaneously and can directly prepare hydrogen, synthetic gas and the oxygen that has higher pressure, especially, also play the effect of "hydrogen pump" or "oxygen pump" as the electrolyte layer of SOEC electrolytic cell, improve the pressure of product gas under the electric current effect of exerting. For example, the gas pressure of the conventional SOEC electrolytic cell is normal pressure (1-3 bar), while the gas pressure of the utility model can reach 5-100 bar. Furthermore, the utility model discloses can directly utilize hydrogen, synthetic gas and oxygen preparation high value chemicals or oil on the electrode, reduce carbon dioxide and discharge when promoting efficiency and economic nature.

Preferably, the electrolyte layer can be used as a separate membrane which is not easy to break, and can be sintered together with the cathode layer and/or the anode layer to realize the pressure-resistant function as a support structure of the solid oxide electrolytic cell.

Preferably, the electrolyte layer is made of an inorganic oxide and/or carbonate capable of conducting one or more charge carriers of oxygen ions, protons and carbonate ions, depending on the reaction process at the cathode layer and/or the anode layer. In a preferred embodiment, the electrolyte layer is made of yttria-stabilized zirconia (YSZ) having oxygen ion conductivity only, barium zirconium cerium oxide (BZCY) having both oxygen ion and proton conductivity, or samarium oxide doped ceria (SDC) having higher oxygen ion conductivity and a carbonate.

Preferably, the cathode layer and/or the anode layer have a porous ceramic skeleton. In a preferred embodiment, the cathode layer is made of Ni-YSZ composite ceramic, Ni-BZCY composite ceramic or a mixture of NiO and composite electrolyte. In a preferred embodiment, the anode layer is made of a mixture of lanthanum strontium cobalt iron (LSCF) and gadolinium oxide doped cerium oxide (GDC) (LSCF/GDC), praseodymium barium strontiumCobalt iron (PBSCF), or LiNiO₂And a composite electrolyte.

Preferably, the surface of the cathode layer is prepared with a cathode collector layer for charge collection and reduction of contact resistance. In a preferred embodiment, the material selected for the cathode collector layer is pure Ni.

Preferably, the cathode layer and the cathode collector layer contain, in addition to the component having electrocatalytic activity for dissociation of water vapor and/or carbon dioxide, an active catalyst capable of catalyzing the synthesis of a chemical or oil, such as ammonia (example 1), methanol (examples 2 and 3), or methane. The adding technology of the related active catalyst comprises post-treatment technologies such as in-situ generation and an impregnation method. In a preferred embodiment, the active catalyst is an Fe catalyst, CuO-ZnO-ZrO₂Catalyst, or CuO-ZnO-Al₂O₃A catalyst.

Preferably, the surface of the anode layer is prepared with an anode current collector layer for charge collection and reduction of contact resistance. In a preferred embodiment, the material selected for the anode current collecting layer is LSCF.

Preferably, the anode layer and the anode collector layer contain, in addition to the component having the electrocatalytic activity for the oxygen evolution reaction, an active catalyst capable of performing a catalytic oxidation process of a chemical or an oil product, such as a saturated alkane, such as carbon, methane, ethane, or an unsaturated alkene, an alkyne, and other chemicals, such as ethane electrochemical oxidative dehydrogenation of example 1 to produce ethylene, the alkene epoxidation reaction of example 2, and the alkane oxidative coupling reaction of example 3. The adding technology of the related active catalyst comprises post-treatment technologies such as in-situ generation and an impregnation method. In a preferred embodiment, the active catalyst is Al₂O₃Catalyst, Ag catalyst, or LiNiO₂A catalyst.

Preferably, the gas control system includes a flow meter and pressure sensors to regulate and control the flow and pressure of the reactant gases and the product gases to the cathode and anode, respectively, to ensure a balance of pressures at the two electrode sides.

Preferably, the gas control system further comprises a purification unit for purifying the reactant gas and a separation unit for separating the product gas from unreacted reactant components.

Preferably, the thermal management system comprises a solid oxide electrolytic cell control unit, which is used for monitoring and regulating the ambient temperature, the cathode layer temperature and the anode layer temperature of the solid oxide electrolytic cell, feeding back the temperature difference between the cathode layer and the anode layer to the gas control system, and then adjusting the temperature by adjusting the gas flow of the reactant, so as to ensure that the temperatures at the two sides are kept the same.

Preferably, the thermal management system further comprises a preheating unit for preheating the reactant gas and a recovery unit for recovering waste heat of the product gas.

According to the utility model discloses an electrochemical synthesis device based on high temperature high pressure electrolysis technique to water and/or carbon dioxide are as the raw materials, through intermediate products such as high temperature high pressure electrolysis preparation hydrogen, carbon monoxide or synthetic gas to further synthesize high-value chemicals or oil. The technology has the characteristics of wide application range, sufficient raw material resources and the like, and can be used for directly carrying out process optimization and production device construction aiming at users with different products and scale requirements. Especially to the abundant areas of clean energy such as nuclear power, water and electricity, wind-powered electricity generation, solar energy, through the utility model discloses in the device can extensively realize the high-efficient conversion storage of the energy, reduce carbon and discharge. Additionally, the utility model discloses still have system module ization and constitute, easy operation, security height, characteristics such as investment are little.

Drawings

Fig. 1 is a schematic structural diagram of an electrochemical synthesis apparatus based on high-temperature high-pressure electrolysis technology according to a preferred embodiment of the present invention.

Detailed Description

The following description of the preferred embodiments of the present invention will be made with reference to the accompanying drawings.

Example 1

As shown in fig. 1, an electrochemical synthesis apparatus based on high-temperature and high-pressure electrolysis technology according to a preferred embodiment of the present invention includes a solid oxide electrolytic cell 1, a gas management system 2, and a thermal management system 3.

The solid oxide electrolytic cell 1 is used for preparing high-pressure hydrogen, synthesis gas and oxygen and directly synthesizing chemicals or oil products, and consists of a compact electrolyte layer 11, a cathode layer 12, a cathode current collecting layer 13, an anode layer 14 and an anode current collecting layer 15. The dense electrolyte layer 11 is a stable dense electrolyte layer, and the selected material is yttria-stabilized zirconia (YSZ) having only oxygen ion conductivity. The cathode layer 12 is a porous layer, the selected material is Ni-YSZ composite ceramic, the cathode collector layer 13 is pure Ni, and the formed and sintered cathode layer 12 and cathode collector layer 13 can simultaneously adopt a solution impregnation method to introduce a Fe catalyst for ammonia synthesis reaction. The anode layer 14 is a porous layer, the selected material is a mixture (LSCF/GDC) of lanthanum strontium cobalt iron (LSCF) and gadolinium oxide doped cerium oxide (GDC), the material used for the anode current collecting layer 15 is LSCF, and the materials used for the anode layer 14 and the anode current collecting layer 15 can be doped with a proper amount of Al generated by the reaction of preparing ethylene through electrochemical oxidative dehydrogenation of ethane by a mechanical mixing method₂O₃A catalyst.

The gas management system 2, which is used to control the composition, flow rate and pressure of the reactant gas and the product gas, includes a gas flow rate and pressure control unit 21, a purification unit 22 for purifying the reactant gas, and a separation unit 23 for separating the product gas from unreacted reactant components. The gas flow and pressure control unit 21 includes a flow meter and a pressure sensor, and respectively adjusts and controls the flow and pressure of the reactant gas and the product gas to the cathode and the anode, thereby ensuring the balance of the pressures at the two electrodes.

The thermal management system 3 comprises a solid oxide electrolysis cell control unit 31, a preheating unit 32 for preheating the reactant gas and a recovery unit 33 for recovering the residual heat of the product gas. The solid oxide electrolytic cell control unit 31 is configured to monitor and regulate the ambient temperature, the cathode layer temperature, and the anode layer temperature of the solid oxide electrolytic cell 1, and feed back the cathode layer and anode layer temperature difference to the gas management system 2 to regulate the temperature by adjusting the reactant gas flow, thereby ensuring that the temperatures at the two sides are kept the same.

The reactions taking place at the cathode are mainly: h₂O+2e^-→H₂+O^2-And 3H₂+N₂→2NH₃. The reactions taking place at the anode are mainly: 2O^2--4e^-→O₂、C₂H₆+0.5O₂→C₂H₄+H₂O、C₂H₆+O^2-→C₂H₄+H₂O+2e^-. The pressure on the cathode and anode sides was 100bar, and the reaction temperature was 1000 ℃.

Example 2

In contrast to example 1, the material of the dense electrolyte layer 11 was selected to be barium zirconium cerium oxide (BZCY) having both oxygen ion and proton conductivity. The cathode layer 12 is made of Ni-BZCY composite ceramic, and CuO-ZnO-ZrO obtained by the reaction of preparing methanol from synthesis gas is doped into the cathode layer 12 and the cathode collector layer 13₂A catalyst. The anode layer 14 is made of praseodymium barium strontium cobalt iron (PBSCF), and an Ag catalyst for olefin epoxidation is added to the anode layer 14 and the anode current collector layer 15.

The reactions taking place at the cathode are mainly: 2H⁺+-2e^-→H₂、CO+2H₂→CH₃OH、CO₂+3H₂→CH₃OH+H₂O、CO₂+2e^-→CO+O^2-And H₂O+2e^-→H₂+O^2-. The reactions taking place at the anode are mainly: 2H₂O-4e^-→4H⁺+O₂And C₂H₄+0.5O₂→C₂H₄And O. The pressure at the cathode and anode side was 1bar, and the reaction temperature was 500 ℃.

Example 3

Unlike examples 1 and 2, the material of the dense electrolyte layer 11 is selected to be a samarium oxide doped cerium oxide (SDC) and carbonate composite material having a higher oxygen ion conductivity. The cathode layer 12 is made of NiO and composite electrolyte mixture, and CuO-ZnO-Al of methanol preparation reaction by synthesis gas is doped into the cathode layer 12 and the cathode collector layer 13₂O₃A catalyst. Anode layer 14 is selected from the group consisting of LiNiO₂A mixture with a composite electrolyte, and a composite electrolyte,and LiNiO of alkane oxidative coupling reaction is added to the anode layer 14 and the anode current collecting layer 15₂A catalyst.

The reactions taking place at the cathode are mainly: CO 2₂+2e^-→CO+O^2-、H₂O+2e^-→H₂+O^2-、CO+2H₂→CH₃OH and CO₂+3H₂→CH₃OH+H₂And O. The reactions taking place at the anode are mainly: 2O^2--4e^-→O₂And 2CH₄+O₂→C₂H₄+2H₂And O. The pressure on the cathode and anode sides was 10bar, and the reaction temperature was 750 ℃.

The high-temperature and high-pressure water electrolysis and/or carbon dioxide reaction of the utility model belongs to endothermic reaction, and the endothermic quantity is related to the current magnitude of the electrolytic reaction and the environmental temperature. The reactions such as the synthesis of ammonia from hydrogen or the synthesis of methanol from synthesis gas, which take place at the cathode, and the reactions such as the partial oxidation of alkane, which take place at the anode, are exothermic reactions. Therefore, the speed of catalytic reaction is controlled by adjusting the gas flow rate on the two electrodes, and the current of high-temperature and high-pressure electrolytic reaction and the ambient temperature are adjusted, so that the heat balance in the whole electrochemical synthesis device can be finally realized, and the energy utilization efficiency of the whole system is improved.

The machinery, electrical parts, electronic components, materials and the like used in the electrochemical synthesis apparatus based on the high-temperature high-pressure electrolysis technology according to the present invention are commercially available.

What has been described above is only the preferred embodiment of the present invention, not for limiting the scope of the present invention, but various changes can be made to the above-mentioned embodiment of the present invention. All the simple and equivalent changes and modifications made according to the claims and the content of the specification of the present invention fall within the scope of the claims of the present invention. The present invention is not described in detail in the conventional technical content.

Claims

1. An electrochemical synthesis device based on high-temperature and high-pressure electrolysis technology is characterized by comprising a solid oxide electrolytic cell, a gas control system and a thermal management system,

the solid oxide electrolytic cell is provided with an electrolyte layer, and a cathode layer and an anode layer which are respectively positioned at two opposite sides of the electrolyte layer, wherein catalyst components required by the synthesis of chemicals or oils are respectively loaded in the cathode layer and the anode layer so as to couple the reaction of high-temperature electrolytic water vapor and/or carbon dioxide and the high-temperature electrocatalysis reaction, thereby preparing high-pressure hydrogen, synthesis gas and oxygen and directly synthesizing the chemicals or the oils;

the gas control system for controlling the composition, flow and pressure of the gas reactant and the gas product comprises a flow meter and a pressure sensor, and respectively adjusts and controls the flow and pressure of the reactant gas and the product gas which are led to the cathode and the anode, so as to ensure the balance of the pressure of the two electrode sides;

the thermal management system for monitoring and controlling the ambient temperature and the electrode temperature of the solid oxide electrolytic cell comprises a solid oxide electrolytic cell control unit, is used for monitoring and regulating the ambient temperature, the cathode layer temperature and the anode layer temperature of the solid oxide electrolytic cell, feeds back the temperature difference between the cathode layer and the anode layer to a gas control system, and then adjusts the temperature by adjusting the gas flow of reactants, thereby ensuring that the temperatures at two sides are kept the same.

2. An electrochemical synthesis apparatus based on high-temperature and high-pressure electrolysis technology according to claim 1, characterized in that the electrolyte layer is made of inorganic oxide and/or carbonate capable of conducting one or more charge carriers selected from oxygen ions, protons and carbonate ions according to the reaction process on the cathode layer and/or the anode layer.

3. The electrochemical synthesis device based on high-temperature high-pressure electrolysis technology according to claim 1, characterized in that the surface of the cathode layer is provided with a cathode collector layer for charge collection and reduction of contact resistance.

4. The electrochemical synthesis apparatus based on high-temperature high-pressure electrolysis technology according to claim 3, characterized in that the cathode layer and the cathode collector layer contain active catalyst capable of catalytically synthesizing chemicals or oil products in addition to the component having electrocatalytic activity for dissociation of water vapor and/or carbon dioxide.

5. The electrochemical synthesis device based on high temperature and high pressure electrolysis technology of claim 1, wherein the anode collector layer is prepared on the surface of the anode layer for charge collection and reduction of contact resistance.

6. The electrochemical synthesis device based on high-temperature high-pressure electrolysis technology according to claim 5, characterized in that the anode layer and the anode collector layer contain active catalyst capable of realizing chemicals or oil products in addition to the components with electrocatalytic activity for oxygen evolution reaction.

7. The electrochemical synthesis apparatus based on high temperature and high pressure electrolysis technology according to claim 1, wherein the gas control system further comprises a purification unit for purifying reactant gas and a separation unit for separating product gas from unreacted reactant components.

8. The electrochemical synthesis apparatus based on high-temperature high-pressure electrolysis technology according to claim 1, wherein the heat management system further comprises a preheating unit for preheating reactant gas and a recovery unit for recovering waste heat of product gas.