CN114658537A - Based on CO2Co-electrolysis and biocatalysis power generation and substance combined supply system and method - Google Patents
Based on CO2Co-electrolysis and biocatalysis power generation and substance combined supply system and method Download PDFInfo
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 70
- 238000010248 power generation Methods 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000126 substance Substances 0.000 title claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 157
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 79
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 70
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000001301 oxygen Substances 0.000 claims abstract description 69
- 238000002485 combustion reaction Methods 0.000 claims abstract description 42
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 39
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 235000019253 formic acid Nutrition 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 23
- 238000011084 recovery Methods 0.000 claims abstract description 22
- 229920000704 biodegradable plastic Polymers 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- 102000004190 Enzymes Human genes 0.000 claims abstract description 4
- 108090000790 Enzymes Proteins 0.000 claims abstract description 4
- 239000011942 biocatalyst Substances 0.000 claims abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 90
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 29
- 239000003570 air Substances 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000005516 engineering process Methods 0.000 claims description 16
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003546 flue gas Substances 0.000 claims description 11
- 239000002803 fossil fuel Substances 0.000 claims description 11
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical group [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 3
- 238000003487 electrochemical reaction Methods 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 244000005700 microbiome Species 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 239000012080 ambient air Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229920006238 degradable plastic Polymers 0.000 abstract description 3
- 230000002210 biocatalytic effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B63/00—Adaptations of engines for driving pumps, hand-held tools or electric generators; Portable combinations of engines with engine-driven devices
- F02B63/04—Adaptations of engines for driving pumps, hand-held tools or electric generators; Portable combinations of engines with engine-driven devices for electric generators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
-
- 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
-
- 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
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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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
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- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- General Engineering & Computer Science (AREA)
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Abstract
The invention provides a catalyst based on CO2The system comprises a wind power or photovoltaic power generation system, a water electrolysis cell, an air separation device, an ammonia synthesis module, an oxygen-enriched combustion power generation module, a CO2And H2Co-electrolytic cell for preparing methanol from O and CO2And H2Co-electrolytic cell for preparing formic acid from O, biocatalyst and CO2And a recovery module. The system utilizes green low-carbon electric energy generated by wind energy or solar energy as driving force, organically combines oxygen-enriched combustion power generation and CO2And H2The processes of O CO-electrolysis, biological catalysis of methanol and formic acid to generate degradable plastics and the like are adopted to realize thermal power generation and CO2Compatible synergy of carbon emission reduction, CO2Is effectively recycled and converted into biodegradable plastics, and can obviously subsidize the carbon emission reduction cost. Meanwhile, the combined production of substances such as ammonia, methanol, formic acid, biodegradable plastics and the like and electric energy is completed, and the system is a novel substance energy system which meets the development target of the low-carbon society.
Description
Technical Field
The invention belongs to the technical field of comprehensive energy application, and particularly relates to a catalyst based on CO2Co-electrolysis and biocatalysis power generation and substance combined supply system and method.
Background
In order to reduce the greenhouse effect, the energy system is undergoing a green low-carbon transformation, and the reduction of the carbon dioxide emission of the energy system has become a consensus of human society. The carbon dioxide capture, utilization and sequestration technology (CCUS) plays an important role in green low-carbon reformation of an energy system, and particularly for energy intensive industries such as thermal power generation, cement, steel and the like, the CCUS technology can be well combined with the existing equipment, so that large-scale reconstruction of infrastructure is avoided.
However, the CCUS technology requires a new investment and is expensive to operate. For example, the current technology for reducing carbon emission in thermal power generation mainly absorbs and separates carbon dioxide in the combusted flue gas by a chemical absorption or physical adsorption method, but because the volume fraction of the carbon dioxide in the flue gas is low, such a capture system is large, and the energy consumption for separation and analysis is high (the power supply efficiency is reduced by 10-15%). Therefore, the high carbon emission reduction cost brings great difficulty to low-carbon clean reform in the fields of thermal power generation and the like.
CCUS technology can be carried out by CO2The carbon is converted into high value-added raw materials, so that the wide market of the modern chemical high value-added raw materials is fully utilized to reduce the carbon emission reduction cost. For example, formic acid, methanol and the like are important chemical raw materials and have high market value, but the sources of the formic acid, the methanol and the like are fossil fuels at present, are extracted from petroleum, belong to high-carbon chemical processes, and if a new low-carbon production method of the formic acid and the methanol can be explored, the formic acid and the methanol are applied to chemical engineeringThe carbon emission reduction of the industry can play a certain role.
On the whole, the current carbon dioxide trapping, utilization and sealing technologies have high cost and bring difficulties for carbon emission reduction of thermal power generation. Meanwhile, the dependence of the production process of modern chemical raw materials (such as plastics) on fossil fuels is strong.
Disclosure of Invention
The invention aims to provide a catalyst based on CO2A co-electrolysis and biocatalysis power generation and substance combined supply system and method aim to solve the problems that the carbon dioxide trapping, utilization and sealing technology in the prior art is high in cost, brings difficulties for carbon emission reduction of thermal power generation, and the dependence of the modern chemical raw material production process on fossil fuels is high.
The invention is realized by the following steps of2The CO-electrolysis and biocatalysis power generation and substance combined supply system comprises a wind power or photovoltaic power generation system, a water electrolysis cell, an air separation device, an ammonia synthesis module, an oxygen-enriched combustion power generation module and CO2And H2Co-electrolytic cell for preparing methanol from O and CO2And H2Co-electrolytic cell for preparing formic acid from O, biocatalyst and CO2A recovery module;
the electric energy output by the electric energy output port of the wind power or photovoltaic power generation system is divided into 4 strands which are respectively connected to the electric energy input port of the water electrolytic cell, the electric energy input port of the air separation device, the CO2And H2Electric energy input port and CO of O-methanol CO-electrolysis cell2And H2An electric energy input port of the O-made formic acid co-electrolytic cell;
the water electrolysis cell is used for carrying out water electrolysis reaction on water to obtain hydrogen and oxygen, a water input port of the water electrolysis cell is connected with an external water source, a hydrogen output port of the water electrolysis cell is connected with a hydrogen input port of the ammonia synthesis module, and an oxygen output port of the water electrolysis cell is connected with an oxygen input port of the oxygen-enriched combustion power generation module;
the air separation device sucks external ambient air and separates the air into oxygen and nitrogen; the nitrogen output port of the oxygen-enriched combustion power generation module is connected to the nitrogen input port of the ammonia synthesis module, and the oxygen output port of the oxygen-enriched combustion power generation module is connected to the oxygen input port of the oxygen-enriched combustion power generation module; the ammonia synthesis module comprises a nitrogen synthesis module, a hydrogen synthesis module and a biological catalyst, wherein the nitrogen and the hydrogen in the ammonia synthesis module are used for synthesizing ammonia, ammonia at a product output port is divided into two parts, one part is used as one of system products and is output outwards, and the other part is connected to an ammonia input port of the biological catalyst;
the fuel input port of the oxygen-enriched combustion power generation module is a fossil fuel adding port, the generated power can be output outwards as two products of the system, and the high-temperature CO at the tail gas output port of the oxygen-enriched combustion power generation module2And H2O gas with CO from2CO recovery module2After the gas is converged, the gas is divided into two flows, one of which flows into the CO2And H2The raw material input port of the O-to-methanol CO-electrolytic cell is connected with the CO inlet port, and the other stream of the raw material flows into the CO CO-electrolytic cell2And H2A raw material input port of the O-formic acid co-electrolytic cell;
the CO is2And H2The water inlet of the CO-electrolytic cell for preparing methanol from O is connected with an external water source, CO2And H2The O is co-electrolyzed to generate methanol, the methanol at the output port of the product is divided into two parts, one part is taken as a third product of the system to be output outwards, and the other part is connected with the methanol input port of the biological catalyst;
the CO is2And H2The water inlet of the O-formic acid CO-electrolysis cell is connected with an external water source, CO2And H2The O is co-electrolyzed to generate formic acid, the formic acid at the output port of the product is divided into two parts, one part is taken as the four of the system products and is output outwards, and the other part is connected with the formic acid input port of the biological catalyst;
the biodegradable plastic produced in the biological catalyst is output from a product port of the biological catalyst and is output outwards as a fifth product of a system, and tail gas generated in the catalytic reaction process is introduced into the CO2Recovering the module; the CO is2CO obtained by purifying tail gas in the recovery module2And mixing and converging with the tail gas output by the oxygen-enriched combustion power generation module.
In order to achieve the purpose, the invention also provides a catalyst based on CO2A co-electrolysis and biocatalytic power generation and material co-supply method comprising the steps of:
respectively connecting electric energy generated by a wind power or photovoltaic power generation system into a water electrolytic cell and an air separation device, wherein water generates electrochemical reaction in the water electrolytic cell to generate hydrogen and oxygen, and air is separated in the air separation device to generate nitrogen and oxygen; the generated oxygen is converged and enters the oxygen-enriched combustion power generation module to be used as a combustion improver;
introducing hydrogen and nitrogen into an ammonia synthesis module to synthesize ammonia, and outputting the ammonia as one of products;
oxygen in the oxygen-enriched combustion power generation module and fossil fuel are subjected to oxygen-enriched combustion, chemical energy is converted into mechanical energy and then converted into electric energy to be output, and the electric energy is used as a product to be output outwards; simultaneously generating high-temperature flue gas, wherein the main components of the high-temperature flue gas comprise carbon dioxide and water vapor;
high temperature flue gas and CO2Return CO of recovery module2After confluence, the mixture is divided into two parts, one part is introduced with CO2And H2CO-electrolyzing in a CO-electrolytic cell for preparing methanol from O, and introducing the other stream of the CO-electrolytic cell into CO2And H2Performing co-electrolysis in an O-formic acid co-electrolysis cell, wherein the co-electrolysis electric energy is from a wind power or photovoltaic power generation system; in the CO2And H2Co-electrolytic cell for preparing methanol from O and CO2And H2In the O-formic acid co-electrolytic cell, carbon dioxide and water vapor are respectively converted into methanol and formic acid, and the methanol and the formic acid are output as a third product and a fourth product; in CO2And H2Co-electrolytic cell for preparing methanol from O and CO2And H2All the O-formic acid co-electrolytic cells are externally connected with water sources, and H can be adjusted2O and CO2Proportional control hydrocarbon generation process;
the generated methanol and formic acid enter a biological catalyst according to a certain proportion, and biodegradable plastics are generated under the catalysis of microorganisms and are output as the fifth product;
the tail gas generated in the biological catalyst enters into CO2CO recovery in a recovery Module2Purifying and purifying the obtained CO2And the tail gas generated by the oxygen-enriched combustion power generation module is converged and then co-electrolyzed again.
Further, the chemical reaction in the ammonia synthesis module is:
N2+3H2 ↔2NH3
the CO is2And H2In an O-methanol co-electrolytic cell:
the catalyst is cobalt phthalocyanine, and the chemical reaction for generating the methanol is as follows:
CO2+5H2O+6e- → CH3OH + 6OH-
the CO is2And H2In an O-methanol co-electrolytic cell:
the catalyst is tin oxide, and the chemical reaction for generating formic acid is as follows:
CO2+H2O+2e- → HCOO- + OH-
the chemical reaction in the biological catalyst is as follows:
aCH3OH+bHCOO-+cNH3+dO2→eCO2+fH2O+gC3.67H6.4N0.47 O2.2。
further, the air separation device adopts a low-temperature air separation technology.
Furthermore, the water electrolysis cell adopts alkaline electrolysis water, proton exchange membrane electrolysis water or high-temperature solid oxide electrolysis water technology.
Further, said CO2The recovery module adopts PSA pressure swing adsorption technology.
Further, by regulating the introduction of CO2And H2Co-electrolytic cell for preparing methanol from O and CO2And H2H in O-formic acid co-electrolytic cell2O, to regulate CO which undergoes a CO-electrolysis reaction2And H2The proportion of O, and further controlling the generated product.
Compared with the prior art, the invention has the beneficial effects that:
the power generation and matter combined supply system and method of the invention use green low-carbon electric energy generated by wind energy or solar energy as driving force, organically combine oxygen-enriched combustion power generation and CO2And H2The processes of O CO-electrolysis, biological catalysis of methanol and formic acid to generate degradable plastics and the like are adopted to realize thermal power generation and CO2Compatible synergy of carbon emission reduction, CO2Is effectively recycledThe biodegradable plastic is a biodegradable plastic with higher market value, and can obviously subsidize the carbon emission reduction cost. Meanwhile, the production of substances such as ammonia, methanol, formic acid, biodegradable plastics and the like and electric energy is completed, the dependence on fossil fuels is reduced, and the system is a novel substance energy system which meets the development target of low-carbon society.
Drawings
FIG. 1 shows a CO-based system according to an embodiment of the present invention2A structural block diagram of a co-electrolysis and biocatalysis power generation and substance combined supply system.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention; the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; furthermore, unless expressly stated or limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, as they may be fixedly connected, detachably connected, or integrally connected, for example; the two components can be directly connected or indirectly connected through an intermediate medium, and the two components can be communicated with each other. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Referring to fig. 1, a CO-based system provided in this embodiment is shown2Co-electrolysis and biocatalysis power generation and material combined supply system comprising windAn electricity or photovoltaic power generation system 1, a water electrolysis cell 2, an air separation device 3, an ammonia synthesis module 4, an oxygen-enriched combustion power generation module 5, and CO2And H2Co-electrolytic cell 6 for preparing methanol from O and CO2And H2O-formic acid CO-electrolytic cell 7, biocatalyst 8, and CO2And a recovery module 9.
The electric energy output by the electric energy output port of the wind power or photovoltaic power generation system 1 is divided into 4 strands which are respectively connected to the electric energy input port of the water electrolysis cell 2, the electric energy input port of the air separation device 3 and the CO2And H2Electric energy input port and CO of O-methanol CO-electrolysis cell 62And H2And an electric energy input port of the O-made formic acid co-electrolysis cell 7.
The water electrolysis cell 2 is used for electrolyzing water to obtain hydrogen and oxygen, a water input port of the water electrolysis cell is connected with an external water source, a hydrogen output port of the water electrolysis cell is connected with a hydrogen input port of the ammonia synthesis module, and an oxygen output port of the water electrolysis cell is connected with an oxygen input port of the oxygen-enriched combustion power generation module 5.
The air separation device 3 is used for sucking external air and separating the air into oxygen and nitrogen; the nitrogen output port of the oxygen-enriched combustion power generation module is connected to the nitrogen input port of the ammonia synthesis module 4, and the oxygen output port of the oxygen-enriched combustion power generation module is connected to the oxygen input port of the oxygen-enriched combustion power generation module 5; the ammonia is synthesized by the nitrogen and the hydrogen in the ammonia synthesis module 4, the ammonia at the product output port is divided into two streams, one stream is output outwards as one of the system products, and the other stream is connected to the ammonia input port of the biological catalyst 8.
The fuel input port of the oxygen-enriched combustion power generation module 5 is used as a fossil fuel adding port, the generated power is output outwards as two products of the system, and the high-temperature CO at the tail gas output port of the system2And H2O gas and CO gas2CO of recovery module 92After the gas is converged, the gas is divided into two flows, one of which flows into CO2And H2The raw material input port of the O-to-methanol CO-electrolysis cell 6 is connected with the CO inlet of the other stream2And H2A raw material input port of the O-made formic acid co-electrolytic cell 7.
CO2And H2The water inlet of the O-methanol CO-electrolysis cell 6 is connected with an external water source, CO2And H2Co-electrolysis generation of OThe methanol at the product output port is divided into two streams, one stream is output outwards as a third product of the system, and the other stream is connected with the methanol input port of the biological catalyst 8.
CO2And H2The water inlet of the O-formic acid CO-electrolysis cell 7 is connected with an external water source, CO2And H2The O is co-electrolyzed to generate formic acid, the formic acid at the output port of the product is divided into two parts, one part is taken as the four of the system products and is output outwards, and the other part is connected with the formic acid input port of the biological catalyst 8. The biodegradable plastics produced in the biological catalyst 8 are output from the product port and are output as the five products of the system, and the tail gas generated in the catalytic reaction process is introduced with CO2In the recovery module 9; CO 22CO obtained by purifying tail gas in the recovery module 92And the tail gas is mixed and converged with the tail gas output by the oxygen-enriched combustion power generation module 5.
The embodiment also provides a method based on CO2A co-electrolysis and biocatalytic power generation and material co-supply method comprising the steps of:
s1, respectively inputting electric energy generated by the wind power or photovoltaic power generation system 1 into the water electrolytic cell 2 and the air separation device 3, wherein the water generates electrochemical reaction in the water electrolytic cell 2 to generate hydrogen and oxygen, and the air generates nitrogen and oxygen in the air separation device 3; the generated oxygen is converged and enters the oxygen-enriched combustion power generation module 5 to be used as a combustion improver.
And S2, introducing the hydrogen and the nitrogen into an ammonia synthesis module 4 to synthesize ammonia, and outputting the ammonia as one of the multi-connected products of the system.
S3, carrying out oxygen-enriched combustion on oxygen in the oxygen-enriched combustion power generation module 5 and fossil fuel, converting chemical energy into mechanical energy and then converting the mechanical energy into electric energy to be output as two types of multi-connected products of the system; simultaneously generating high-temperature flue gas; the high-temperature flue gas comprises carbon dioxide and water vapor.
S4, mixing the high-temperature flue gas with CO2Recycling of the returned CO of the module 92After confluence, the mixture is divided into two parts, one part is introduced with CO2And H2CO-electrolysis is carried out in a CO-electrolysis cell 6 for preparing methanol from O, and CO is introduced into the other side2And H2The O-made formic acid co-electrolysis cell 7 carries out co-electrolysisThe co-electrolysis electric energy is from a wind power or photovoltaic power generation system 1; in CO2And H2Co-electrolytic cell 6 for preparing methanol from O and CO2And H2In the O-formic acid co-electrolytic cell 7, carbon dioxide and water vapor are respectively converted into methanol and formic acid, and the methanol and the formic acid are output as a third product and a fourth product of a system. In CO2And H2Co-electrolytic cell for preparing methanol from O and CO2And H2All the O-formic acid co-electrolytic cells are externally connected with water sources, and H can be adjusted2O and CO2The ratio controls the hydrocarbon generation process.
S5, introducing the generated methanol and formic acid into the biological catalyst 8 according to a certain proportion, generating biodegradable plastics under the catalysis of microorganisms, and outputting the biodegradable plastics as a multi-connected product of the system.
S6, introducing CO into the tail gas generated in the biological catalyst 82CO recovery in the recovery Module 92Purifying and purifying the obtained CO2Reflows, and is converged with tail gas generated by the oxygen-enriched combustion power generation module 5, and then participates in co-electrolysis again.
Wherein the chemical reaction in the ammonia synthesis module is:
N2+3H2↔2NH3
the CO is2And H2In an O-methanol co-electrolytic cell:
the catalyst is cobalt phthalocyanine, and the chemical reaction for generating the methanol is as follows:
CO2+5H2O+6e- → CH3OH + 6OH-
the CO is2And H2In an O-methanol co-electrolytic cell:
the catalyst is tin oxide, and the chemical reaction for generating formic acid is as follows:
CO2+H2O+2e- → HCOO- + OH-
the chemical reaction in the biological catalyst is as follows:
aCH3OH+bHCOO-+cNH3+dO2→eCO2+fH2O+gC3.67H6.4N0.47 O2.2。
in the present embodiment, the air separation unit 3 may employ cryogenic air separation technology; the water electrolysis cell 2 can adopt alkaline electrolysis water, proton exchange membrane electrolysis water or high-temperature solid oxide electrolysis water technology. CO 22The recovery module 8 may employ PSA pressure swing adsorption technology.
Can also be adjusted by introducing CO2And H2Co-electrolytic cell 6 for preparing methanol from O and CO2And H2H in O-formic acid co-electrolytic cell 72O, to regulate CO which undergoes a CO-electrolysis reaction2And H2The proportion of O, and further controlling the generated product.
In summary, the present embodiment utilizes the green low-carbon electric energy generated by wind energy or solar energy as the driving force, organically combines the oxygen-enriched combustion power generation and the CO generation2And H2The processes of O CO-electrolysis, biological catalysis of methanol and formic acid to generate degradable plastics and the like are adopted to realize thermal power generation and CO2Compatible synergy of carbon emission reduction, CO2Is effectively recycled and converted into biodegradable plastic with higher market value, and can obviously subsidize the carbon emission reduction cost. Meanwhile, the production of substances such as ammonia, methanol, formic acid, biodegradable plastics and the like and electric energy is completed, the dependence on fossil fuels is reduced, and the system is a novel substance energy system which meets the development target of low-carbon society.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. Based on CO2The CO-electrolysis and biocatalysis power generation and substance combined supply system is characterized by comprising a wind power or photovoltaic power generation system, a water electrolysis cell, an air separation device, an ammonia synthesis module, an oxygen-enriched combustion power generation module, CO2And H2Co-electrolytic cell for preparing methanol from O and CO2And H2Co-electrolytic cell for preparing formic acid from O, biocatalyst and CO2A recovery module;
electric energy output port of wind power or photovoltaic power generation systemThe output electric energy is divided into 4 strands which are respectively connected to an electric energy input port of the water electrolysis cell, an electric energy input port of the air separation device and CO2And H2Electric energy input port and CO of O-methanol CO-electrolysis cell2And H2An electric energy input port of the O-made formic acid co-electrolytic cell;
the water electrolysis cell is used for carrying out water electrolysis reaction on water to obtain hydrogen and oxygen, a water input port of the water electrolysis cell is connected with an external water source, a hydrogen output port of the water electrolysis cell is connected with a hydrogen input port of the ammonia synthesis module, and an oxygen output port of the water electrolysis cell is connected with an oxygen input port of the oxygen-enriched combustion power generation module;
the air separation device sucks in external ambient air and separates the air into oxygen and nitrogen; the nitrogen output port of the oxygen-enriched combustion power generation module is connected to the nitrogen input port of the ammonia synthesis module, and the oxygen output port of the oxygen-enriched combustion power generation module is connected to the oxygen input port of the oxygen-enriched combustion power generation module; the ammonia synthesis module comprises a nitrogen synthesis module, a hydrogen synthesis module and a biological catalyst, wherein the nitrogen and the hydrogen in the ammonia synthesis module are used for synthesizing ammonia, ammonia at a product output port is divided into two parts, one part is used as one of system products and is output outwards, and the other part is connected to an ammonia input port of the biological catalyst;
the fuel input port of the oxygen-enriched combustion power generation module is a fossil fuel adding port, the generated power can be output outwards as two products of the system, and the high-temperature CO at the tail gas output port of the oxygen-enriched combustion power generation module2And H2O gas with CO from2CO recovery module2After the gas is converged, the gas is divided into two flows, one of which flows into the CO2And H2The raw material input port of the O-to-methanol CO-electrolytic cell is connected with the CO inlet port, and the other stream of the raw material flows into the CO CO-electrolytic cell2And H2A raw material input port of the O-formic acid co-electrolytic cell;
the CO is2And H2The water inlet of the CO-electrolytic cell for preparing the methanol from the O is connected with an external water source, CO2And H2The O is co-electrolyzed to generate methanol, the methanol at the output port of the product is divided into two parts, one part is taken as a third product of the system to be output outwards, and the other part is connected with the methanol input port of the biological catalyst;
the CO is2And H2The water inlet of the O-formic acid CO-electrolysis cell is connected with an external water source, CO2And H2The O is co-electrolyzed to generate formic acid, the formic acid at the output port of the product is divided into two parts, one part is taken as the four of the system products and is output outwards, and the other part is connected with the formic acid input port of the biological catalyst;
the biodegradable plastic produced in the biological catalyst is output from a product port of the biological catalyst and is output outwards as a fifth product of a system, and tail gas generated in the catalytic reaction process is introduced into the CO2Recovering the module; the CO is2CO obtained by purifying tail gas in the recovery module2And mixing and converging with the tail gas output by the oxygen-enriched combustion power generation module.
2. Based on CO2The co-electrolysis and biocatalysis power generation and substance combined supply method is characterized by comprising the following steps of:
respectively connecting electric energy generated by a wind power or photovoltaic power generation system into a water electrolytic cell and an air separation device, wherein water generates electrochemical reaction in the water electrolytic cell to generate hydrogen and oxygen, and air is separated in the air separation device to generate nitrogen and oxygen; the generated oxygen is converged and enters the oxygen-enriched combustion power generation module to be used as a combustion improver;
introducing hydrogen and nitrogen into an ammonia synthesis module to synthesize ammonia, and outputting the ammonia as one of products;
oxygen in the oxygen-enriched combustion power generation module and fossil fuel are subjected to oxygen-enriched combustion, chemical energy is converted into mechanical energy and then converted into electric energy to be output, and the electric energy is used as a product to be output outwards; simultaneously generating high-temperature flue gas, wherein the main components of the high-temperature flue gas comprise carbon dioxide and water vapor;
high temperature flue gas and CO2Refluxing CO of recovery module2After confluence, the mixture is divided into two parts, one part is introduced with CO2And H2CO-electrolyzing in a CO-electrolytic cell for preparing methanol from O, and introducing the other stream of the CO-electrolytic cell into CO2And H2Performing co-electrolysis in an O-formic acid co-electrolysis cell, wherein the co-electrolysis electric energy is from a wind power or photovoltaic power generation system; in the CO2And H2Co-electrolytic cell for preparing methanol from O and CO2And H2In the O-formic acid co-electrolytic cell, carbon dioxide and water vapor are respectively convertedThe methanol and the formic acid are converted into the third product and the fourth product which are output outwards; in CO2And H2Co-electrolytic cell for preparing methanol from O and CO2And H2All the O-formic acid co-electrolytic cells are externally connected with water sources for regulating H2O and CO2Proportional, control hydrocarbon generation process;
the generated methanol and formic acid enter a biological catalyst according to a certain proportion, and biodegradable plastics are generated under the catalysis of microorganisms and are output as five products;
introducing CO into tail gas generated in the biological catalyst2CO recovery in a recovery Module2Purifying and purifying the obtained CO2And the tail gas generated by the oxygen-enriched combustion power generation module is converged and then co-electrolyzed again.
3. The combined power and material generation process of claim 2,
the chemical reactions in the ammonia synthesis module are:
N2+3H2 ↔2NH
the CO is2And H2In an O-methanol co-electrolytic cell:
the catalyst is cobalt phthalocyanine, and the chemical reaction for generating the methanol is as follows:
CO2+5H2O+6e- → CH3OH + 6OH-
the CO is2And H2In an O-methanol co-electrolytic cell:
the catalyst is tin oxide, and the chemical reaction for generating formic acid is as follows:
CO2+H2O+2e- → HCOO- + OH-
the chemical reaction in the biological catalyst is as follows:
aCH3OH+bHCOO-+cNH3+dO2→eCO2+fH2O+gC3.67H6.4N0.47 O2.2。
4. the combined power and material generation process of claim 2 wherein the air separation plant employs cryogenic air separation technology.
5. The combined power and material generation method of claim 2, wherein the water electrolysis cell adopts alkaline electrolysis water, proton exchange membrane electrolysis water or high-temperature solid oxide electrolysis water technology.
6. The combined power and material generation process of claim 2, wherein the CO is2The recovery module adopts PSA pressure swing adsorption technology.
7. The combined power and material generation process of claim 2, wherein CO is introduced by regulating the introduction of CO2And H2Co-electrolytic cell for preparing methanol from O and CO2And H2H in O-formic acid co-electrolytic cell2O, to regulate CO which undergoes a CO-electrolysis reaction2And H2The proportion of O, and further controlling the generated product.
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