CN115354345A - Photovoltaic photo-thermal coupling co-electrolysis combined garbage power generation comprehensive energy system and process method thereof - Google Patents
Photovoltaic photo-thermal coupling co-electrolysis combined garbage power generation comprehensive energy system and process method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/04—Purification or separation of nitrogen
- C01B21/0405—Purification or separation processes
- C01B21/0433—Physical processing only
- C01B21/045—Physical processing only by adsorption in solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0488—Processes integrated with preparations of other compounds, e.g. methanol, urea or with processes for power generation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/23—Carbon monoxide or syngas
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/67—Heating or cooling means
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S10/00—PV power plants; Combinations of PV energy systems with other systems for the generation of electric power
- H02S10/10—PV power plants; Combinations of PV energy systems with other systems for the generation of electric power including a supplementary source of electric power, e.g. hybrid diesel-PV energy systems
-
- 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
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- 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
Abstract
The invention provides a photovoltaic photo-thermal coupling co-electrolysis combined garbage power generation comprehensive energy system and a process method thereof. The invention utilizes solar photovoltaic and photo-thermal combined amino thermo-chemical heat pump system to provide electricity and heat for the SOEC electrolysis system, utilizes solar power generation to drive air to be separated into nitrogen and oxygen and drive water to be electrolyzed into hydrogen and oxygen, the oxygen is used as a combustion improver for waste incineration power generation, the waste incineration power generation outputs electric energy, and high-temperature CO generated by the electric energy is generated 2 Can be directly mixed with water vapor and introduced into an SOEC electrolytic cell for co-electrolysis to generate H 2 And CO, and then catalyzing the hydrogen and the carbon monoxide into the methanol through the catalyst. The ammonia is liquid at normal temperature, is convenient for storage and transportation, and not only can be used as an important chemical raw material, but also can be used as a carbon-free fuel and a hydrogen carrier. The invention realizes the CO-production of electricity, methanol, ammonia and the like, and CO 2 High-valued resource utilization is realized, so that the carbon emission reduction cost is offset, and the low-carbon efficient reformation of a fossil fuel power generation system is facilitated.
Description
Technical Field
The invention relates to the field of solar photovoltaic photo-thermal and electrolytic hydrogen production, in particular to an amino chemical heat pump coupling co-electrolysis and garbage combined power generation comprehensive energy system and a process method thereof.
Background
The world's dependence on fossil fuels as a major energy source has led to climate change and global warming. Renewable energy is seen as a key solution to keep global warming below 1.5 ℃. Adverse effects of climate change and global warming have driven the world to deploy renewable energy technologies including wind, solar photovoltaic, concentrated solar, etc. on a large scale over the past decade. However, the intermittency of renewable energy sources, specifically solar radiation and wind speed, makes energy storage technology necessary to meet the energy demands of low or no solar irradiation and wind energy. Excess energy from solar photovoltaic or wind energy can be stored and used at a later time without solar radiation and wind power.
The main drawback of using fossil fuels is that the emissions produced lead to many environmental problems and global warming, so there is a great need today especially to develop new energy technologies to replace traditional fossil energy to reduce today's ever increasing carbon emissions. Solid Oxide Electrolytic Cell (SOEC) technology has attracted attention in recent years to produce H2 by electrolysis of water and synthesis gas by CO-electrolysis of water and CO 2. The high operating temperature of the SOEC can reduce the electric energy requirement in the electrolysis process, thereby reducing the cost of hydrogen production and synthesis gas, improving the dynamic performance of the electrode, reducing the electrolyte resistance of the SOEC, and reducing the performance loss of the battery. SOEC will exhibit higher efficiency in producing hydrogen and syngas than low temperature electrolysis cells. Thermodynamically, high temperature electrolysis can reduce the power consumption in the electrolysis process and can utilize the waste heat of power stations or other industrial processes; in terms of dynamics, high-temperature electrolysis can reduce the internal resistance of the battery and improve the current density, thereby improving the electrolysis efficiency.
Aiming at the heat energy grade (600-1200 ℃) required by the SOEC operation and the nonuniformity of the solar energy resource distribution in China, the solar energy grade can only be met by a large-scale tower type or disc type heat collector. Therefore, the photovoltaic photo-thermal coupling high-temperature electrolyzed water is often restricted by factors such as regions, land areas and the like. Among the four traditional solar heat collectors, the linear Fresnel solar condenser has feasibility in distributed solar photo-thermal utilization due to compact structure, low cost and high land coverage rate. But the defects of light condensing ratio and low operation temperature (300-400 ℃) are caused, so that the linear Fresnel heat collector cannot directly provide the high-grade heat energy required by the SOEC. The chemical heat pump utilizes reversible thermochemical reaction
The chemical heat pump is a device for improving the grade of heat energy through reversible reaction, wherein the amino thermochemical heat pump based on ammonia decomposition/synthesis reaction has the advantages of no by-product in reaction, good reversibility, abundant reaction raw materials and the like, and can easily realize the temperature of 500-700 DEG CThe grade of heat energy is raised. The high-temperature water electrolysis hydrogen production system has the disadvantage of higher temperature dependence, and the more 75 percent of considerable electrolysis efficiency can be obtained when the temperature is 600-800 ℃. And the energy grade coupling of the linear Fresnel heat collector and the SOEC is realized by utilizing an amino chemical heat pump. Realizes a new path for producing hydrogen by using solar photo-heat, efficiently utilizes and stably stores solar energy, reduces energy consumption and CO 2 The discharge is of great significance.
In addition, in the municipal waste treatment process, a large amount of oxygen is required to be consumed as a combustion improver, a large amount of carbon dioxide is generated in the combustion process, the carbon emission reduction treatment is required to be carried out before the carbon emission reduction treatment is carried out, and the expensive carbon emission reduction cost is required to be increased, so that the development of the comprehensive energy system combining the municipal waste treatment and the SOEC electrolysis system is of great significance.
Disclosure of Invention
The invention aims to provide an amino chemical heat pump coupling co-electrolysis and garbage combined power generation comprehensive energy system and a process method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a photovoltaic and photo-thermal coupling co-electrolysis and garbage power generation combined comprehensive energy system comprises an amino thermochemical heat pump system, a linear Fresnel heat collection system, a photovoltaic power generation system, an SOEC electrolysis system, a garbage power generation module, a PSA nitrogen production system, an ammonia synthesis module and a methanol synthesis module, wherein the SOEC electrolysis system comprises a first SOEC electrolysis system and a second SOEC electrolysis system; the linear Fresnel heat collecting system is connected with the amino thermochemical heat pump system to provide an ammonia decomposition heat source; the amino thermochemistry heat pump system and the photovoltaic power generation system are both connected with the SOEC electrolysis system to provide heat and electric quantity required by electrolysis; the first SOEC electrolysis system is provided with an oxygen flow channel and a hydrogen flow channel, the oxygen flow channel is connected with the garbage power generation module, and the hydrogen flow channel and a nitrogen flow channel of the PSA nitrogen production system are both connected with the ammonia synthesis module; and a carbon dioxide runner of the garbage power generation module is communicated with a second SOEC electrolysis system, the second SOEC electrolysis system is provided with an oxygen runner and a mixed gas runner, the oxygen runner is communicated with the garbage power generation module, and the mixed gas runner is communicated with the methanol synthesis module.
Furthermore, the garbage power generation module is also respectively communicated with the first SOEC electrolysis system and the second SOEC electrolysis system to provide heat and electric quantity generated by garbage power generation treatment and further provide energy for electrolysis, and meanwhile, the garbage power generation module is also communicated with the PSA nitrogen production system to provide electric quantity required by the PSA nitrogen production system.
Further, the amino thermochemical heat pump system comprises an ammonia decomposition reactor, a turbine compressor, a gas storage tank and an ammonia synthesis reactor; the gas storage tank is used for storing the mixed gas generated by the ammonia decomposition reactor and the liquid ammonia generated by the ammonia synthesis reactor, and respectively delivering the liquid ammonia and the mixed gas to the ammonia decomposition reactor and the ammonia synthesis reactor through a turbine compressor for ammonia decomposition and ammonia synthesis; the ammonia synthesis reactor is connected with the first SOEC electrolysis system to provide ammonia synthesis heat release; the linear Fresnel heat collecting system is communicated with the ammonia decomposition reactor to provide heat energy required by ammonia decomposition.
Further, the first SOEC electrolytic system and the second SOEC electrolytic system are respectively composed of a cathode layer, an electrolyte layer, an anode layer and a gas flow channel, wherein the cathode layer is made of a nickel-cerium oxide based metal ceramic material or a nickel-zirconium oxide metal ceramic material; the anode layer is made of doped lanthanum cobaltate, strontium lanthanum ferrite, barium-cobalt-iron-niobium oxide and barium-strontium-cobalt-iron oxide; the electrolyte layer is doped lanthanum gallate and scandia-stabilized zirconia.
Further, the first SOEC electrolysis system performs a single electrolysis reaction, and the total cell reaction formula is: 2H 2 O→2H 2 +O 2 (ii) a The second SOEC electrolysis system undergoes a double electrolysis reaction, and the total cell reaction formula is: h 2 O+CO 2 →H 2 +CO+O 2 。
Furthermore, a reflector of the linear Fresnel heat collecting system can automatically adjust a certain angle along with the sun, and provides energy required by ammonia decomposition for an ammonia decomposition reactor of the amino thermochemical heat pump system through reflection of sunlight; the turbo compressor comprises turbine and booster compressor, relies on the mutual effort between rotatory impeller and the air current to improve gas pressure in the booster compressor, in the turbine, because the impeller rotation in the gaseous step-down flow drive turbine, makes turbine and booster compressor be connected through the axle, provides the booster compressor with the axle power of booster compressor, reduces the energy consumption of booster compressor.
The invention also provides a process method of the photovoltaic photo-thermal coupling co-electrolysis combined garbage power generation comprehensive energy system, which comprises the following steps:
the linear Fresnel heat collection system promotes ammonia decomposition in the amino thermochemical heat pump system through heat collection, and releases a large amount of high-grade heat energy through ammonia synthesis to supply heat to the SOEC electrolysis system, the photovoltaic power generation system provides electric energy for the SOEC electrolysis system, and the first SOEC electrolysis system generates hydrogen and oxygen through electrolysis water; oxygen is used as a combustion improver to be supplied to the garbage power generation module, and hydrogen is mixed with nitrogen generated by the PSA nitrogen production system to be supplied to the ammonia synthesis system as 'raw material gas'; the garbage power generation module takes carbon dioxide and water generated by combustion as raw materials to carry out CO-electrolysis on a second SOEC electrolysis system, and CO and H generated by CO-electrolysis 2 Then the methanol is synthesized into methanol by the methanol synthesis module, and oxygen generated by co-electrolysis is continuously supplied to the garbage power generation module.
Further, an ammonia decomposition reactor of the amino thermochemical heat pump system absorbs a large amount of solar heat energy, and then releases the heat energy through an ammonia synthesis reactor, so that the heat energy at 400 ℃ is improved to 700 ℃; preheating reaction gas generated by ammonia decomposition reaction and liquid ammonia generated by ammonia synthesis reaction, then flowing into a normal-temperature pressure gas storage tank for automatically performing gas-liquid separation and stable storage, and respectively conveying the liquid ammonia and the reaction gas to an ammonia decomposition reactor and an ammonia synthesis reactor through a turbine compressor for ammonia decomposition and ammonia synthesis, and sequentially using; when the endothermic process is carried out, the ammonia decomposition reaction gas is absorbed by the ammonia decomposition reactor from the normal-temperature pressure gas storage tank to carry out the ammonia decomposition reaction by solar energy; when the heat release process is carried out, the synthetic ammonia reaction gas also flows through the heat exchanger from the normal-temperature pressure gas storage tank to be preheated and then enters the SOEC electrolysis system for synthetic ammonia reaction to release energy.
Further, the ammonia synthesis module is used for synthesizing nitrogen generated by the PSA nitrogen production system and hydrogen generated by the first SOEC electrolysis system into liquid ammonia, heat released by the synthetic ammonia further provides heat for the SOEC electrolysis system, and the generated liquid ammonia is transported and conveyed to an ammonia fuel cell for power generation or stored as power fuel to be used as chemical raw materials for directly producing liquid ammonia.
Furthermore, part of electric energy required by the PSA nitrogen production system and the SOEC electrolysis system is provided by the garbage power generation module; the heat energy required by the SOEC electrolysis system and the methanol synthesis module is provided by the garbage power generation module and the ammonia synthesis module. And combustion improver oxygen required by the garbage power generation module is provided by the first SOEC electrolysis system and the PSA nitrogen production system, and when the oxygen is insufficient, air in the environment can be used for supplying oxygen for garbage power generation.
Compared with the prior art, the invention utilizes solar energy collection and garbage power generation, and combines the traditional energy with the new energy to generate electricity or methanol and ammonia. The carbon dioxide generated by garbage power generation can be absorbed by utilizing the great advantage of the mode of combining new energy with traditional energy, and zero carbon emission can be realized. In addition, the oxygen generated after water electrolysis can be used as a combustion improver for garbage power generation. Waste heat generated after the garbage power generation can be supplied to the SOEC, and the waste heat and the SOEC are complementary and mutually beneficial. The method not only converts a high-carbon process into a low-carbon process, but also realizes high-valued resource utilization of carbon dioxide, thereby offsetting the high cost of carbon emission reduction and being beneficial to low-carbon efficient reformation of a fossil fuel power generation system.
Drawings
FIG. 1 is a schematic diagram of the overall process flow structure of the present invention;
FIG. 2 is a diagram of the cell reaction of a hydrogen electrode and an oxygen electrode in a single electrolysis;
FIG. 3 is a diagram of the cell reaction of a hydrogen electrode and an oxygen electrode in double electrolysis;
in the figure: 1. a linear Fresnel heat collection system; 2. a photovoltaic power generation system; 3. a garbage power generation module; 4. a PSA nitrogen generation system; 5. an ammonia synthesis module; 6. a methanol synthesis module; 7. a first SOEC electrolysis system; 8. a second SOEC electrolysis system; 9. an ammonia decomposition reactor; 10. a turbine compressor; 11. a gas storage tank; 12. an ammonia synthesis reactor; 13. an ammonia fuel cell.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
As shown in fig. 1, the photovoltaic photo-thermal coupling co-electrolysis combined waste power generation comprehensive energy system comprises an amino thermochemical heat pump system, a linear fresnel heat collection system 1, a photovoltaic power generation system 2, an SOEC electrolysis system, a PSA nitrogen generation system 4, a waste power generation module 3, an ammonia synthesis module 5 and a methanol synthesis module 6. The SOEC electrolysis system comprises a first SOEC electrolysis system 7 and a second SOEC electrolysis system 8; the linear Fresnel heat collecting system 1 is connected with an amino thermochemical heat pump system to provide an ammonia decomposition heat source; the amino thermochemistry heat pump system and the photovoltaic power generation system 2 are both connected with the SOEC electrolysis system to provide heat and electric quantity required by electrolysis; the first SOEC electrolysis system 7 is provided with an oxygen flow channel and a hydrogen flow channel, the oxygen flow channel is connected with the garbage power generation module 3, and the hydrogen flow channel and a nitrogen flow channel of the PSA nitrogen making system 4 are both connected with the ammonia synthesis module 5; the carbon dioxide runner of the garbage power generation module 3 is communicated with the second SOEC electrolysis system 8, the second SOEC electrolysis system 8 is provided with an oxygen runner and a mixed gas runner, the oxygen runner is communicated with the garbage power generation module 3, and the mixed gas runner is communicated with the methanol synthesis module 6.
The garbage power generation module 3 is also respectively communicated with the first SOEC electrolysis system 7 and the second SOEC electrolysis system 8 to provide heat and electric quantity generated by garbage power generation treatment and further provide energy for electrolysis, and meanwhile, the garbage power generation module 3 is also communicated with the PSA nitrogen production system 4 to provide electric quantity required by the PSA nitrogen production system.
The amino thermochemical heat pump system of the present invention comprises an ammonia decomposition reactor 9, a turbo compressor 10, a gas tank 11, and an ammonia synthesis reactor 12; the gas storage tank 11 is used for storing the mixed gas generated by the ammonia decomposition reactor 9 and the liquid ammonia generated by the ammonia synthesis reactor 12, and respectively delivering the liquid ammonia and the mixed gas to the ammonia decomposition reactor 9 and the ammonia synthesis reactor 12 through the turbo compressor 10 for ammonia decomposition and ammonia synthesis; the ammonia synthesis reactor 12 is connected to the first SOEC electrolysis system 7, providing an ammonia synthesis exotherm; the linear Fresnel heat collecting system 1 is communicated with the ammonia decomposition reactor 9 to provide heat energy required by ammonia decomposition.
During specific work, the linear Fresnel heat collecting system 1 promotes ammonia decomposition in the amino thermochemical heat pump system through heat collection, a large amount of high-grade heat energy is released through ammonia synthesis to supply heat to the SOEC electrolysis system, and the first SOEC electrolysis system 7 generates hydrogen and oxygen through electrolysis of water. The oxygen is mainly used as combustion improver to supply the domestic garbage for incineration power generation, and the hydrogen is mixed with the nitrogen generated by the PSA nitrogen production system 4 to supply the hydrogen as 'raw material gas' to the ammonia synthesis module 5. The system can also use carbon dioxide and water generated by the combustion of the garbage power generation module 3 as raw materials to carry out CO-electrolysis on the second SOEC electrolysis system 8, and CO and H are obtained as products after the CO-electrolysis 2 And then synthesized into methanol by a methanol synthesis module 6.
The garbage in the garbage power generation module 3 generates power through combustion of combustion-supporting gas oxygen, and the power of the garbage is used for supplying normal operation of single electrolysis and double electrolysis of the SOEC electrolysis system and operation of the PSA nitrogen production system 4. A large amount of waste heat generated by power generation is about 360 ℃ to continuously supply heat to the SOEC electrolysis system, and then high-grade heat energy is continuously provided for the SOEC through the amino thermochemical heat pump and the ammonia synthesis module 5.
The SOEC electrolysis system needs an external water source, the first SOEC electrolysis system 7 on the left side is single electrolysis, the second SOEC electrolysis system 8 on the right side is common electrolysis, the hydrogen outlet end of the first SOEC electrolysis system 7 for single electrolysis is connected with the hydrogen inlet end of the ammonia synthesis module 5, and the oxygen outlet end is connected with the oxygen inlet end of the garbage power generation module 3. CO of the Co-electrolysed second SOEC Electrolysis System 8 2 The inlet end is connected with garbage power CO 2 And at the outlet end, the outlet ends of hydrogen and carbon monoxide are connected with the inlet end of the raw material gas of the methanol synthesis module 6.
The pressure swing adsorption air separation apparatus of the present invention is not limited to the pressure swing adsorption PSA nitrogen production system, and various nitrogen production methods such as cryogenic air separation nitrogen production, membrane separation nitrogen production, and the like may be used. Considering the multiple aspects of energy consumption, process maturity and the like, the nitrogen is prepared by preferentially considering the nitrogen preparation method by PSA pressure swing adsorption,
the ammonia synthesis module 5 below synthesizes the input nitrogen and hydrogen into ammonia, outputs the ammonia as one of the system products, stores the liquid ammonia, and introduces the ammonia into the ammonia fuel cell 14 (DAFC) to generate electricity when needed. Because ammonia is easy to liquefy at normal temperature, liquid ammonia can be transported to a place where electric power is needed to generate electricity through pipelines and ships.
The power generation raw material of the garbage power generation module 3 is not limited to municipal domestic garbage, and can be wood, fossil raw material and the like. The garbage is incinerated to generate power after being treated, and heat energy is converted into electric energy. The generated electric energy can be supplied to power consumption equipment such as an SOEC electrolysis system, a PSA nitrogen making system 4 and the like. Oxygen required by the garbage power generation is supplied by oxygen generated after the SOEC electrolysis system and the PSA nitrogen production module 4. In addition, waste heat (360 ℃) generated by power generation can be provided for the SOEC electrolysis system.
SOEC electrolysis systems operate by absorbing the thermal energy given off by ammonia synthesis and the electrical energy of the photovoltaic module. The SOEC electrolysis system can perform single electrolysis to electrolyze water to generate hydrogen and oxygen, and can also perform double electrolysis to electrolyze carbon dioxide and water to generate carbon monoxide, hydrogen and oxygen. The working principle of the SOEC electrolysis system is shown as follows, and water vapor and CO can be electrolyzed simultaneously in double electrolysis 2 Generation of synthesis gas (H) 2 + CO). At a higher temperature (600-1000 deg.C), applying a certain DC voltage H to the electrodes at both sides of the second SOEC electrolytic system 2 O and CO 2 Reduction reaction at hydrogen electrode to produce O 2- ，O 2- Passes through the dense solid oxide electrolyte layer to reach the oxygen electrode where oxidation occurs to obtain pure O2.
The cell reaction of the hydrogen electrode and the oxygen electrode in the single electrolysis is shown in fig. 2:
the half-cell reaction of the cathode and anode is:
cathode: 2H 2 O+4e-→2H 2 +2O 2-
Anode: 2O 2- →4e-+O 2
The cell reaction of the hydrogen electrode and the oxygen electrode in double electrolysis is shown in fig. 3:
hydrogen electrode reaction: 2CO 2 +4e→2CO+2O 2- (1)
2H 2 O+4e→2H 2 +2O 2- (2)
Oxygen electrode reaction: 4O 2- →2O 2 +8e (3)
Overall cell reaction: h 2 O+CO 2 →H 2 +CO+O 2 (4)
During CO-electrolysis, the greenhouse gas CO can be introduced 2 Converting into fuel gas CO, and has the advantages of high efficiency, cleanness and environmental protection.
In terms of material selection of the SOEC of the high-temperature solid oxide electrolytic cell, the SOEC generally adopts a dense oxygen ion conductor yttria-stabilized zirconia (YSZ) as an electrolyte, a nickel-zirconia (Ni-YSZ) cermet as a hydrogen electrode, and a lanthanum manganate (LSM) composite YSZ of a perovskite structure as an oxygen electrode. In recent years, various electrolyte materials and electrode materials have also been developed to replace conventional materials, such as: the electrolyte material is doped lanthanum gallate (LSGM) and scandia-stabilized zirconia (ScSZ); the hydrogen electrode material comprises a nickel-cerium oxide based metal ceramic material (Ni-GDC); the oxygen electrode material comprises doped lanthanum cobaltite (LSCF), strontium lanthanum ferrite (LSF), barium cobalt iron niobium oxide (BCFN), barium strontium cobalt iron oxide (BSCF) and the like.
Water electrolysis is a process of separating water molecules into hydrogen and oxygen using electrical energy. In short, one of the most basic electrolysis cells consists of an anode, a cathode and an electrolyte or membrane, while an electrolytic cell consists of a plurality of electrolysis cells. Water electrolysis is an electrochemical reaction that occurs in an electrolytic cell, with water being separated into hydrogen and oxygen molecules. The produced hydrogen is stored as an output as compressed gas for transport at gas stations, power stations, etc. Typically, oxygen is released into the atmosphere. The amount of power required for electrolysis depends on the water temperature. Increasing the low water temperature requires more electricity to produce hydrogen. In contrast, less power is required at high water temperatures. Low temperature electrolysis may be carried out in alkaline cells, the electrolysis being carried out in the presence of a liquid electrolyte solution or a Proton Exchange Membrane (PEM). High temperature electrolysis, also known as steam electrolysis, uses Solid Oxide Electrolysis Cells (SOECs) operating at higher temperatures (600 to 1000 ℃) to separate water. Low cost steam can be used as a fuel, further reducing the power requirements compared to direct electrolysis.
The amino thermochemical heat pump system is composed of an ammonia decomposition reactor 9, a turbo compressor 10, a gas storage tank 11 and an ammonia synthesis reactor 12. Ammonia decomposition reaction 3H 2 +N 2 +ΔH＝2NH 3 (endothermic), ammonia synthesis reaction 2NH 3 ＝3H 2 +N 2 + Δ H (exothermic). The ammonia decomposition reactor 9 absorbs a large amount of solar heat energy and releases the heat energy through the ammonia synthesis reactor 12, thereby elevating the heat energy of 400 c to 700 c. When the heat absorption process is carried out, the ammonia decomposition reaction gas is depressurized by a normal-temperature pressure gas storage tank 11 through a turbine compressor 10 and then enters an ammonia decomposition reactor 9 to absorb concentrated solar energy to carry out ammonia decomposition reaction; when the heat release process is carried out, the synthetic ammonia reaction gas is pressurized by a normal-temperature pressure gas storage tank 11 through a turbine compressor 10 and then enters an ammonia synthesis reactor 12 to carry out synthetic ammonia reaction to release high-grade heat; and gas generated by ammonia decomposition and synthesis reaction flows back to the gas storage tank to automatically perform gas-liquid separation and stable storage.
The linear Fresnel heat collecting system 1 adopts compact arrangement, and can focus solar radiation on a heat absorbing pipe by tracking the movement of the sun and adjusting a strip-shaped reflector so as to provide heat for ammonia decomposition. The Fresnel light-gathering heat collector converts the collected solar energy into heat energy and generates high temperature. The amino thermochemical heat pump absorbs the heat of the collector by ammonia decomposition and releases high grade heat energy (700 degrees celsius) by ammonia synthesis.
Further, the chemical reaction in the methanol synthesis module is as follows:
in summary, the present embodiment utilizes solar energy collection and garbage power generation, and combines the traditional energy source with the new energy source to generate electricity or methanol and ammonia. The carbon dioxide generated by garbage power generation can be absorbed by utilizing the great advantage of the mode of combining new energy with traditional energy, and zero carbon emission can be realized. In addition, the oxygen generated after water electrolysis can be used as a combustion improver for garbage power generation. Waste heat generated after the garbage power generation can be supplied to an SOEC electrolysis system, and the two can complement each other. The method not only converts a high-carbon process into a low-carbon process, but also realizes high-valued resource utilization of carbon dioxide, thereby offsetting the high cost of carbon emission reduction and being beneficial to low-carbon efficient reformation of a fossil fuel power generation system.
The invention uses large-scale process flow simulation software Aspen Plus to verify the theoretical feasibility of the system through the energy grade coupling and the energy flow process among all subsystems in the whole system. The ammonia production energy consumption is 256MJ/Kg, although the energy consumption is improved compared with the traditional ammonia production method by coal or natural gas, a plurality of hydrogen purification reactions are saved in the ammonia production process, and no carbon is discharged in the ammonia production process, thereby providing a green ammonia production method.
The first embodiment is as follows:
the linear Fresnel heat collector provides heat for the ammonia decomposition reactor through heat collection of sunlight, ammonia in the storage tank flows into the ammonia decomposition reactor through the turbine compressor in a pressure reduction mode, and the ammonia decomposes the absorbed heat into hydrogen and nitrogen and then flows back into the storage tank. The hydrogen and the nitrogen in the storage tank enter an ammonia synthesis reactor for synthesizing ammonia through the pressurization of a turbine compressor, simultaneously release a large amount of heat (700 ℃), and the synthesized ammonia flows back to the storage tank and circulates in sequence. The SOEC electrolysis system needs heat energy and electric energy for electrolyzing water, the photovoltaic power generation system 2 provides electric energy for the SOEC electrolysis system, the garbage power generation module 3 further provides electric energy and heat energy for the SOEC electrolysis system, and ammonia synthesis provides heat energy for the SOEC. The water will be electrolyzed in the first SOEC electrolysis system 7 reactor to hydrogen and oxygen, wherein the hydrogen is provided as "feed gas" to the ammonia synthesis module, wherein the PSA nitrogen generation system 4 also provides nitrogen to the ammonia synthesis reactor. In the ammonia synthesis module 5, hydrogen and nitrogen react to synthesize ammonia. This is a complete ammonia production process, since ammonia can also be used as a fuel carrier, and transported to a large city for power generation by the ammonia fuel cell 13.
Example two:
on the basis of the first embodiment, oxygen generated by electrolyzing the SOEC is supplied to the garbage power module 3. The garbage power generation module carries out incineration power generation after municipal garbage is treated, the generated power is returned to SOEC electrolysis and other equipment needing power utilization, the waste heat after power generation is returned to an SOEC electrolysis system, the waste-burnt by-product carbon dioxide is used as a raw material and is mixed with water to be led to a second SOEC electrolysis system 8 on the right side for co-electrolysis, and the water and the carbon dioxide are electrolyzed into hydrogen and carbon monoxide. And then the hydrogen and the carbon monoxide react in the methanol synthesis module 6 to synthesize the methanol.
Claims (10)
1. The comprehensive energy system for photovoltaic and photothermal coupling co-electrolysis combined garbage power generation is characterized by comprising an amino thermochemical heat pump system, a linear Fresnel heat collection system (1), a photovoltaic power generation system (2), an SOEC electrolysis system, a garbage power generation module (3), a PSA nitrogen generation system (4), an ammonia synthesis module (5) and a methanol synthesis module (6), wherein the SOEC electrolysis system comprises a first SOEC electrolysis system (7) and a second SOEC electrolysis system (8); the linear Fresnel heat collecting system (1) is connected with an amino thermochemical heat pump system to provide an ammonia decomposition heat source; the amino thermochemical heat pump system and the photovoltaic power generation system (2) are connected with the SOEC electrolysis system to provide heat and electric quantity required by electrolysis; the first SOEC electrolysis system (7) is provided with an oxygen flow channel and a hydrogen flow channel, the oxygen flow channel is connected with the garbage power generation module (3), and the hydrogen flow channel and a nitrogen flow channel of the PSA nitrogen production system (4) are both connected with the ammonia synthesis module (5); the carbon dioxide flow channel of the garbage power generation module (3) is communicated with the second SOEC electrolysis system (8), the second SOEC electrolysis system (8) is provided with an oxygen flow channel and a mixed gas flow channel, the oxygen flow channel is communicated with the garbage power generation module (3), and the mixed gas flow channel is communicated with the methanol synthesis module (6).
2. The integrated energy system combining photovoltaic photo-thermal coupling co-electrolysis and garbage power generation as claimed in claim 1, wherein the garbage power generation module (3) is further respectively communicated with the first SOEC electrolysis system (7) and the second SOEC electrolysis system (8) to provide heat and electricity generated by garbage power generation treatment, and further provide energy for electrolysis, and meanwhile, the garbage power generation module (3) is further communicated with the PSA nitrogen generation system (4) to provide electricity required by the PSA nitrogen generation system (4).
3. The integrated energy system for photovoltaic, photothermal coupling and co-electrolysis combined with garbage power generation according to claim 1, wherein the amino thermochemical heat pump system comprises an ammonia decomposition reactor (9), a turbo compressor (10), a gas storage tank (11), an ammonia synthesis reactor (12); the gas storage tank (11) is used for storing the mixed gas generated by the ammonia decomposition reactor (9) and the liquid ammonia generated by the ammonia synthesis reactor (12), and respectively delivering the liquid ammonia and the mixed gas to the ammonia decomposition reactor (9) and the ammonia synthesis reactor (12) through a turbine compressor (10) for ammonia decomposition and ammonia synthesis; the ammonia synthesis reactor (12) is connected with the first SOEC electrolysis system (7) and provides ammonia synthesis heat release; the linear Fresnel heat collecting system (1) is communicated with the ammonia decomposition reactor (9) to provide heat energy required by ammonia decomposition.
4. The integrated energy system for photovoltaic photo-thermal coupling co-electrolysis combined with garbage power generation as claimed in claim 1, wherein the first SOEC electrolysis system (7) and the second SOEC electrolysis system (8) are respectively composed of a cathode layer, an electrolyte layer, an anode layer and a gas flow channel, the cathode layer is made of nickel-cerium oxide based cermet material, nickel-zirconium oxide cermet material; the anode layer is made of doped lanthanum cobaltate, strontium lanthanum ferrite, barium-cobalt-iron-niobium oxide and barium-strontium-cobalt-iron oxide; the electrolyte layer is doped lanthanum gallate and scandia-stabilized zirconia.
5. The integrated energy system of photovoltaic-photothermal coupling co-electrolysis combined with garbage power generation according to claim 4, wherein the first SOEC electrolysis system (7)) A single electrolysis reaction occurs, and the overall cell reaction formula is: 2H 2 O→2H 2 +O 2 (ii) a The second SOEC electrolysis system (8) undergoes a double electrolysis reaction, and the total cell reaction formula is: h 2 O+CO 2 →H 2 +CO+O 2 。
6. The integrated energy system for photovoltaic, photothermal coupling and co-electrolysis combined garbage power generation according to claim 3, wherein the reflector of the linear Fresnel heat collecting system (1) can automatically adjust a certain angle along with the sun, and provides energy required for ammonia decomposition for the ammonia decomposition reactor (9) of the amino thermochemical heat pump system through reflection of sunlight;
turbo compressor (10) comprise turbine and booster compressor, rely on the mutual effort between rotatory impeller and air current to improve gas pressure in the booster compressor, in the turbine, because the impeller rotation in the gaseous decompression flow drives the turbine, make turbine and booster compressor connect through the axle, provide the booster compressor with the axle work of booster compressor, reduce the energy consumption of pressure boost.
7. A process method of the integrated energy system for generating electricity by combining photovoltaic and photothermal coupling and co-electrolysis with garbage according to any one of claims 3 to 6, which comprises the following processes:
the linear Fresnel heat collection system (1) promotes ammonia decomposition in the amino thermochemical heat pump system through heat collection, and releases a large amount of high-grade heat energy through ammonia synthesis to supply heat to the SOEC electrolysis system, the photovoltaic power generation system (2) provides electric energy for the SOEC electrolysis system, and the first SOEC electrolysis system (7) generates hydrogen and oxygen through electrolyzed water; oxygen is used as combustion improver to be supplied to the garbage power generation module (3), and hydrogen is mixed with nitrogen generated by the PSA nitrogen production system (4) to be supplied to the ammonia synthesis system (5) as raw material gas; the garbage power generation module (3) takes carbon dioxide and water generated by combustion as raw materials to carry out CO-electrolysis on a second SOEC electrolysis system (8), and CO and H generated by CO-electrolysis 2 Then the methanol is synthesized into methanol by the methanol synthesis module (6), and oxygen generated by co-electrolysis is continuously supplied to the garbage power generation module (3).
8. The process method of the comprehensive energy system for photovoltaic, photothermal coupling and co-electrolysis combined with garbage power generation as claimed in claim 7, wherein the ammonia decomposition reactor (9) of the amino thermochemical heat pump system absorbs a large amount of solar heat energy, and releases the heat energy through the ammonia synthesis reactor (12), so as to raise the heat energy at 400 ℃ to 700 ℃; preheating reaction gas generated by ammonia decomposition reaction and liquid ammonia generated by ammonia synthesis reaction, then flowing into a normal-temperature pressure gas storage tank (11) for automatically performing gas-liquid separation and stable storage, and respectively conveying the liquid ammonia and the reaction gas to an ammonia decomposition reactor and an ammonia synthesis reactor through a turbine compressor (10) for ammonia decomposition and ammonia synthesis for sequential use; when the endothermic process is carried out, the ammonia decomposition reaction gas is absorbed by the normal-temperature pressure gas storage tank (11) through the ammonia decomposition reactor (9) to carry out the ammonia decomposition reaction; when the heat release process is carried out, the synthetic ammonia reaction gas also flows through the heat exchanger from the normal-temperature pressure gas storage tank (11) to be preheated and then enters the synthetic ammonia reaction to release energy to the SOEC electrolysis system.
9. The process method of the integrated energy system combining photovoltaic photo-thermal coupling co-electrolysis and garbage power generation as claimed in claim 7, wherein the ammonia synthesis module (5) is used for synthesizing nitrogen produced by the PSA nitrogen production system (4) and hydrogen produced by the first SOEC electrolysis system (7) into liquid ammonia, the heat released by the synthetic ammonia further provides heat for the SOEC electrolysis system, and the generated liquid ammonia is transported to the ammonia fuel cell (13) for power generation or stored as power fuel to be used as chemical raw materials for directly producing liquid ammonia.
10. The integrated energy system for photovoltaic photo-thermal coupling co-electrolysis combined with garbage power generation as claimed in claim 7, wherein part of the electric energy required by the PSA nitrogen production system (4) and the SOEC electrolysis system is provided by the garbage power generation module (3); the heat energy required by the SOEC electrolysis system and the methanol synthesis module (6) is provided by the garbage power generation module (3) and the ammonia synthesis module (5). And the combustion improver oxygen required by the garbage power generation module (3) is provided by the first SOEC electrolysis system (7) and the PSA nitrogen production system (4), and when the oxygen is insufficient, the air in the environment can be used for supplying oxygen for garbage power generation.
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