CN116445943A - Plasma coupling electrocatalytic carbon dioxide conversion device and method for product phase separation - Google Patents
Plasma coupling electrocatalytic carbon dioxide conversion device and method for product phase separation Download PDFInfo
- Publication number
- CN116445943A CN116445943A CN202310306268.7A CN202310306268A CN116445943A CN 116445943 A CN116445943 A CN 116445943A CN 202310306268 A CN202310306268 A CN 202310306268A CN 116445943 A CN116445943 A CN 116445943A
- Authority
- CN
- China
- Prior art keywords
- carbon dioxide
- plasma
- electrocatalytic
- product
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 76
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 46
- 238000010168 coupling process Methods 0.000 title claims abstract description 31
- 230000008878 coupling Effects 0.000 title claims abstract description 29
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000005191 phase separation Methods 0.000 title claims abstract description 7
- 210000002381 plasma Anatomy 0.000 claims abstract description 87
- 239000000047 product Substances 0.000 claims abstract description 64
- 239000007789 gas Substances 0.000 claims abstract description 62
- 239000012263 liquid product Substances 0.000 claims abstract description 45
- 230000004888 barrier function Effects 0.000 claims abstract description 36
- 238000009792 diffusion process Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000005281 excited state Effects 0.000 claims abstract description 15
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 238000005265 energy consumption Methods 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 230000005764 inhibitory process Effects 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 14
- 239000012071 phase Substances 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229940026085 carbon dioxide / oxygen Drugs 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
- C25B11/032—Gas diffusion electrodes
-
- 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
-
- 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
-
- 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
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention discloses a product phase separation plasma coupling electrocatalytic carbon dioxide conversion device and method, carbon dioxide gas forms active carbon dioxide excited state particles with non-thermodynamic equilibrium under the discharge effect of dielectric barrier plasmas, high-energy carbon-oxygen bonds are effectively broken, the active particles are converted into gas-liquid carbon products under the electrocatalytic effect of a gas diffusion electrode loaded with a catalyst, the reacted gas products are directly discharged from an outlet, the reacted liquid products are temporarily stored in a three-dimensional additive manufacturing pore runner layer between an ion exchange membrane and the catalyst layer for enrichment, and the gas-liquid carbon products are discharged, captured and collected through a pulse water circulation system, so that the liquid products with high concentration and low impurities are convenient for downstream direct utilization. The device is flexible, convenient, modularized and integrated, has high environmental benefit, and realizes the whole-process high-efficiency zero-carbon conversion of carbon dioxide and multiphase physical field design of multiphase carbon dioxide conversion.
Description
Technical Field
The present invention relates to CO 2 The technical field of electrocatalytic and low-temperature plasmas, in particular to a plasma coupling electrocatalytic carbon dioxide conversion device and method with separable gas-liquid products.
Background
With the rapid development of industry in recent years, the emission amount of carbon dioxide is greatly increased, and the electrocatalytic carbon dioxide conversion driven by renewable electric energy can store excessive electric power through chemical energy of high-added-value carbon dioxide products to promote closed natural carbon circulation. However, the industrial application of the electrocatalytic reduction technology of carbon dioxide is still limited by energy efficiency, selectivity, conversion rate and catalytic activity. The inertia of carbon dioxide molecules makes the carbon dioxide molecules inhibited by competitive hydrogen evolution reaction in an aqueous solution environment, so that in the research at present, a gas diffusion electrode is mostly adopted to separate carbon dioxide gas from electrolyte, a reaction area is formed on an electrolyte-catalyst interface through the selective permeability of the gas diffusion electrode, and the reaction device improves the selectivity of the carbon dioxide electrocatalysis.
Nevertheless, the conversion object of the electrocatalytic reduction of carbon dioxide at normal temperature and normal pressure is still gaseous carbon dioxide molecules, in order to break the high activation energy barrier caused by the inherent high-energy carbon-oxygen bond, the current research constructs a plasma-electrocatalytic coupling system, so that the carbon dioxide molecules generate active substances through plasma discharge before electrocatalytic conversion, and then the electrocatalytic interface is used for converting the carbon dioxide-like active substances, and the technology improves the electrochemical activity of the carbon dioxide molecule conversion on the electrode interface and is beneficial to the reaction. However, because of the easy quenching property of the plasma, only the occurrence area of arc breakdown of the plasma can generate excited state particles, so that the traditional plasma-electrocatalytic coupling system is essentially to activate carbon dioxide by the plasma and generate carbon monoxide/carbon dioxide/oxygen composite gas in a stable molecular state, and then to reduce carbon of the stable molecules by the action of a catalyst on an electrocatalytic interface. Therefore, how to organically integrate the plasma phase interface with the electrocatalytic system to realize a plasma-electrocatalytic coupling system in a real sense, and constructing a non-thermodynamic equilibrium carbon oxygen radical excited state particle layer on an electrode interface is a problem to be solved urgently.
In addition, the electrocatalytic reduction product of carbon dioxide has gas-liquid phases (gas phase: carbon monoxide, methane and the like; liquid phase: methanol, ethanol and the like), and the separation and collection of multi-component products are also a difficult problem for pushing electrocatalytic carbon dioxide conversion to industrialization. The gaseous product is generally discharged along with the introduced reaction gas at a gas outlet and subjected to purification treatment at the downstream, however, due to the characteristics of an electrocatalytic system, the liquid product can be transported from a cathode chamber to an anode chamber (crospover) across an anion exchange membrane under the conditions of high current density and high product concentration, so that the liquid product is oxidized into carbonate at the anode, and the yield and selectivity of a carbon dioxide reduction system are greatly reduced. Therefore, the contradiction between the continuous energy consumption of the liquid flow system, the requirement of a large amount of electrolyte and the collection and separation of the electrolyte still restricts the large current and the electrocatalytic conversion of industrial carbon dioxide.
Disclosure of Invention
Aiming at the defect that the liquid-phase product separation is difficult and the plasma-electrocatalytic coupling process is imperfect in the prior art, the invention provides a device and a method for converting carbon dioxide by coupling plasma and electrocatalytic with product phase separation, and the device and the method adopt a low-temperature dielectric barrier discharge plasma technology to realize the efficient conversion of carbon dioxide and the product separation.
The aim of the invention is realized by the following technical scheme: a product phase separated plasma coupled electrocatalytic carbon dioxide conversion device, the device comprising: the device comprises a renewable energy modulation module and a plasma coupling electrocatalytic module;
the renewable energy modulation module is used for being connected into renewable energy sources to supply power, and the renewable energy sources meet the power requirement of the plasma coupling electrocatalytic module through voltage-current conversion;
the plasma coupling electrocatalytic module comprises a dielectric barrier discharge array submodule, an electrocatalytic submodule and a product separation submodule;
the dielectric barrier discharge array submodule is used for dissociating and activating carbon-oxygen bonds in carbon dioxide, introducing gaseous carbon dioxide into the plasma reactor array, generating gas breakdown discharge to form a non-thermodynamic equilibrium plasma phase environment by adjusting physical characteristics of the plasma array such as input voltage and discharge frequency parameters, and realizing carbon dioxide activation to form carbon dioxide excited state particles of a plasma phase;
the electro-catalytic submodule is used for directly carrying out electro-catalytic conversion on carbon dioxide excited state particles of a plasma phase on the gas diffusion electrode, and different products are generated directionally by adjusting the types of the catalysts;
the product separation module is used for directionally separating gas and liquid products during collection, wherein the gas products are directly discharged from a gas outlet, the liquid products are temporarily stored in a pore flow channel constructed by additive manufacturing on a catalyst interface, and the liquid products are periodically taken out by the pulse water circulation device; the pore flow channel is constructed on the catalyst interface of the gas diffusion electrode by a three-dimensional additive manufacturing method, and a micron-sized cavity is formed on the gas diffusion electrode-ion exchange membrane interface after the electrocatalytic device is assembled and is used for temporarily storing liquid products.
Further, the renewable energy source modulation module is used for carrying out fluctuation energy input to supply power for the plasma coupling electrocatalytic module.
Further, the dielectric barrier discharge array submodule is connected with a plasma power supply to realize that reactive gas breaks down to generate low-temperature plasmas with different physical characteristics by modulating the output voltage and the output frequency parameters of the power supply.
Further, the micron-sized pore flow channel is designed as a labyrinth type, and mass transfer efficiency and product uniformity are improved to the maximum extent.
Further, products are collected through periodic pulse water circulation, concentrated liquid products are stored in the flow channel for a short time and collected through pulse water circulation after enrichment, so that the product collection efficiency is improved, the product inhibition catalytic efficiency is prevented, and the energy consumption is reduced.
Further, the liquid product collected from the circulating water is fractionated to obtain a pure carbon product.
In another aspect, the invention also provides a method for product phase separation by plasma coupled electrocatalytic carbon dioxide conversion, comprising the steps of:
(1) The renewable energy source is converted through voltage and current to meet the power requirement of the dielectric barrier discharge array and the electrocatalysis;
(2) The carbon-oxygen bond in the carbon dioxide is dissociated and activated through the dielectric barrier discharge array, and the method specifically comprises the following steps: introducing gaseous carbon dioxide into a plasma reactor array, and generating gas breakdown discharge to form a non-thermodynamic equilibrium plasma phase environment by adjusting physical characteristics of the plasma array such as input voltage and discharge frequency parameters, so as to realize carbon dioxide activation and form carbon dioxide excited state particles of a plasma phase;
(3) The carbon dioxide excited state particles of the plasma phase are directly subjected to electrocatalytic conversion on a gas diffusion electrode, and different products are directionally generated by adjusting the types of the catalysts;
(4) Directionally separating gas and liquid products during collection, wherein the gas products are directly discharged from a gas outlet, the liquid products are temporarily stored in a pore flow channel constructed by additive manufacturing on a catalyst interface, and the liquid products are periodically taken out by a pulse water circulation device; the pore flow channel is constructed on the catalyst interface of the gas diffusion electrode by a three-dimensional additive manufacturing method, and a micron-sized cavity is formed on the gas diffusion electrode-ion exchange membrane interface after the electrocatalytic device is assembled and is used for temporarily storing liquid products.
The invention has the beneficial effects that:
(1) The reaction conditions are mild. By utilizing the non-equilibrium state characteristic of low-temperature plasma, the carbon-oxygen double bond can be broken at normal temperature and normal pressure, so that the high-efficiency carbon dioxide conversion and utilization under mild conditions are possible;
(2) The product selectivity is high. The plasma phase carbon-oxygen active particles are directionally converted on the electrode, the reaction energy barrier is reduced, and the local concentration-circulation separation process of the liquid product is beneficial to reducing the energy consumption and coupling application of the subsequent process;
(3) And (5) upgrading the coupling process. The three-step process of steady-state excitation state steady-state electrocatalytic conversion of carbon dioxide molecules in a traditional plasma-electrocatalytic coupling system is converted into the three-step process of steady-state excitation state electrocatalytic conversion, so that the reaction rate is further improved;
(4) The environmental benefit is high. The whole device completely utilizes renewable energy sources to supply energy sources, and the whole process of zero carbon dioxide conversion and utilization can be realized.
Drawings
FIG. 1 is a schematic diagram of the operation of a product phase separated plasma coupled electrocatalytic carbon dioxide conversion device, wherein 1 is a solar photovoltaic panel; 2 is a voltage modulation module; 3 is a plasma coupling electrocatalytic module; 4 is a pulse water circulation system; and 5 is a liquid product collecting tank.
FIG. 2 is a schematic diagram of a plasma coupled electrocatalytic module, wherein 3-1 is a dielectric barrier discharge low temperature plasma array; 3-2 is a gas diffusion catalytic layer; 3-3 is a micron-sized pore flow channel constructed by additive manufacturing; 3-4 is an ion exchange membrane; 3-5 is anode catalytic layer; 3-6 is an anolyte; 3-7 are bipolar plates; 3-8 are pulse water circulation inlets; 3-9 is a pulse water circulation outlet; 3-10 is an anolyte inlet; 3-11 is an anolyte outlet; 3-12 is carbon dioxide inlet; 3-13 is a carbon dioxide outlet.
FIG. 3 is a schematic diagram of a single-body enlargement of a dielectric barrier discharge low temperature plasma array, wherein 3-1-1 is an electrode; 3-1-2 is a blocking medium; 3-1-3 is the generated plasma.
FIG. 4 is a micro-scale pore flow channel constructed by additive manufacturing, wherein 3-3-1 is a gas diffusion layer; 3-3-2 is an interlayer liquid product; 3-3-3 is an ion exchange membrane.
Fig. 5 is a cross section of a micron-sized pore flow channel constructed by additive manufacturing.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to the drawings.
The invention provides a product phase separation plasma coupling electrocatalytic carbon dioxide conversion device, which is used for coupling renewable energy sources to generate power, so that the defects of severe reaction conditions, complex process facilities, carbon emission amplification, heavy environmental pollution and the like of the existing process can be overcome, the carbon dioxide at the rear end of carbon capture of a high-carbon emission factory can be utilized, and renewable clean power is introduced while high-value chemicals of the carbon dioxide are utilized and converted, so that the zero-carbon conversion in the whole process is realized. The invention solves the defects of difficult product collection and separation and large energy consumption in downstream industrial utilization in the prior art, enables the liquid carbon reduction product with high concentration and high added value to be directly recovered, and is directly connected into the downstream chemical synthesis process after simple treatment, and has the characteristics of simple reaction conditions, convenient and fast process facility equipment, modularized integration, high environmental benefit and the like.
The device provided by the invention comprises: the device comprises a renewable energy source modulation module, a plasma coupling electrocatalytic module 3, a pulse water circulation system 4 and a liquid product collection tank 5;
wherein the renewable energy source modulation module comprises a solar photovoltaic panel 1 and a voltage modulation module 2; the solar photovoltaic panel 1 (which can be replaced by other renewable energy sources) is used for collecting solar energy and then transmitting the solar energy to the voltage modulation module 2, the voltage modulation module 2 integrates voltage and current and then outputs the integrated voltage and current to the plasma coupling electrocatalytic module 3 and the pulse water circulation device 4, the plasma coupling electrocatalytic module 3 is used for converting carbon dioxide, and liquid/gaseous carbon products are synthesized during operation, wherein the liquid carbon products are transmitted to the liquid product storage tank 5 for storage and use through the pulse water circulation device 4. The pulse water circulation device 4 collects products through periodic pulse water circulation, and concentrated liquid products stored in the flow channel for a short time are collected through pulse water circulation after enrichment, so that the product collection efficiency is improved, the product inhibition catalysis efficiency is prevented, and the energy consumption is reduced. The liquid product collected by the circulating water is fractionated to obtain pure carbon product, and the pure carbon product is conveyed to a liquid product storage tank 5 for storage.
The plasma coupling electrocatalytic module 3 consists of the following parts: (1) the dielectric barrier discharge array submodule consists of a plurality of groups of dielectric barrier discharge plasma small reactors, wherein the small reactors are provided with an air inlet pipeline and an air outlet pipeline and are used for inputting raw gas and outputting product gas; the dielectric barrier discharge plasma array is connected with a high-frequency alternating current power supply, and high-voltage high-frequency electric energy output by the power supply breaks down the gas in the reaction area to generate dielectric barrier discharge plasma arc; (2) the electrocatalytic submodule consists of a gas diffusion catalytic layer, an ion exchange membrane, an anode plate catalytic layer and an anode plate; (3) the product separation module is used for constructing a labyrinth micron-sized pore flow channel by a three-dimensional additive manufacturing method on the basis of a traditional gas diffusion electrode by the gas diffusion catalytic layer, and storing liquid products in a gas diffusion electrode-ion exchange membrane interface; the liquid product stored temporarily is carried out periodically by a pulse-type water circulation device for downstream use.
As shown in fig. 2, the plasma coupling electrocatalyst module 3 comprises a dielectric barrier discharge low-temperature plasma array 3-1, a gas diffusion catalytic layer 3-2, a micron-sized pore flow channel 3-3 constructed by additive manufacturing, an ion exchange membrane 3-4, an anode catalytic layer 3-5, an anode electrolyte 3-6, a bipolar plate 3-7, a pulse water circulation inlet 3-8, a pulse water circulation outlet 3-9, an anode electrolyte inlet 3-10, an anode electrolyte outlet 3-11, a carbon dioxide inlet 3-12 and a carbon dioxide outlet 3-13; as shown in fig. 3, the monomer of the dielectric barrier low-temperature plasma array 3-1 comprises an electrode 3-1-1, a barrier medium 3-1-2 and generated plasmas 3-1-3, wherein the barrier medium 3-1-2 is positioned between the two electrodes 3-1-1, the generated plasmas 3-1-3 are arranged between the electrodes and the barrier medium, the plasmas can directly react on the catalyst layer, and the monomer is combined into the dielectric barrier plasma array. The medium barrier low-temperature plasma array 3-1 is tightly connected with the gas diffusion catalytic layer 3-2, carbon dioxide active particles in an excited state are formed on the gas diffusion catalytic layer 3-2, a micron-sized pore flow channel 3-3 constructed by an additive manufacturing method is arranged on the gas diffusion catalytic layer 3-2 and is used for temporarily storing liquid products, as shown in fig. 4 and 5, the micron-sized pore flow channel 3-3 constructed by the additive manufacturing method comprises a gas diffusion layer 3-3-1, an interlayer liquid product 3-3-2 and an ion exchange membrane 3-3, a flow channel is constructed on the gas diffusion layer 3-3-1, the flow channel is designed as a labyrinth to enhance mass transfer dynamics, mass transfer efficiency and product uniformity are improved to the maximum extent, and the interlayer liquid product 3-3-2 can be temporarily stored and is carried out by a water circulation device; the micron-sized pore flow channel 3-3 constructed by the additive manufacturing method is contacted with the ion exchange membrane 3-4, the ion exchange membrane 3-4 is contacted with the anode catalytic layer 3-5, the anode catalytic layer 3-5 is connected with the anode electrolyte 3-6, and then is connected with the bipolar plate 3-7; the micro-pore flow channel 3-3 is connected with a pulse water circulation inlet 3-8 and a pulse water circulation outlet 3-9, the bipolar plate 3-7 is provided with an anolyte inlet 3-10 and an anolyte outlet 3-11, and the dielectric barrier discharge low-temperature plasma array 3-1 is provided with a carbon dioxide inlet 3-12 and a carbon dioxide outlet 3-13.
The renewable energy modulation module is used for being connected into various renewable energy sources to input fluctuation energy and supply power for the plasma coupling electrocatalytic module, and the renewable energy modulation module is used for converting and conveying voltage, so that the renewable energy modulation module can meet the power requirement (200W) of the dielectric barrier discharge array sub-module and the power requirement (240W) of the electrocatalytic sub-module (100W) at the same time, and the operation is shown in figure 1: the photovoltaic panel or other renewable energy sources are supplied to a voltage modulation module, and the voltage module outputs electric energy required by the electrocatalytic electrode, the water circulation system and the plasma generator;
the dielectric barrier discharge array submodule is used for dissociating and activating carbon-oxygen bonds in carbon dioxide, a dielectric barrier discharge plasma array is constructed between the gas diffusion layer and the gas inlet and outlet, and the dielectric barrier discharge array submodule is connected with a plasma power supply to realize that reactive gas breaks down to generate low-temperature plasmas with different physical characteristics by modulating output voltage and output frequency parameters of the power supply. As shown in fig. 2, dielectric barrier plasmas are broken down and discharged after carbon dioxide is introduced into the dielectric barrier plasmas to form a non-thermodynamic equilibrium plasma generation area, the area is directly contacted with the surface of a gas diffusion electrode, and the surface of the electrode (catalyst) directly reduces and converts non-thermodynamic equilibrium plasma phase carbon dioxide excited state particles, so that the process characteristics of a traditional two-stage coupling system in which plasmas form stable intermediate products and electrocatalytic intermediate products react are upgraded, the defects of the original process of the plasma-electrocatalytic coupling system are overcome, the energy consumption of the system is effectively reduced, and the conversion efficiency is improved;
parameters such as input voltage (9000 kV) and discharge frequency (9500 Hz) of the dielectric barrier discharge plasma array are regulated, as shown in fig. 3, dielectric barrier discharge arc is generated, and construction of carbon dioxide excited state particles, and dissociation rate and selectivity of carbon dioxide molecules are promoted.
The electro-catalytic submodule is used for directly carrying out electro-catalytic conversion on carbon dioxide excited state particles of a plasma phase on the gas diffusion electrode, and different products are generated directionally by adjusting the types of the catalysts;
the product separation module is used for directionally separating gas-liquid products during collection, and the gaseous products are carried and discharged by continuously introduced carbon dioxide gas and collected through the gas outlet for downstream conversion and utilization; the storage and collection of the liquid product are realized by constructing a micron-sized pore flow channel through a three-dimensional additive manufacturing mode, as shown in fig. 4 and 5, a pulse water circulation system is adopted to periodically bring out the carbon dioxide liquid product (such as formic acid) in the pore flow channel, particularly, a cathode cavity is static when the device performs electrocatalytic operation, a micron-sized cavity chamber is formed between a gas diffusion electrode and an ion exchange membrane, the flow channel realizes the local storage of the liquid product when the liquid carbon product is generated, the liquid product is gradually concentrated and enriched along with the continuous product of the electrocatalytic time, the pulse water circulation system is set to be opened at intervals according to the current density and the device size, the enriched liquid product is periodically brought out of the reactor, the current density is prevented from being reduced by improving the product concentration or the electric energy consumption for lifting, meanwhile, the timely collection of the product and the long-time utilization of the catalyst are realized, and the brought-out liquid product can form the high-concentration liquid carbon product through simple fractionation and other methods for direct downstream utilization.
The above-described embodiments are intended to illustrate the present invention, not to limit it, and any modifications and variations made thereto are within the spirit of the invention and the scope of the appended claims.
Claims (7)
1. A product phase separated plasma coupled electrocatalytic carbon dioxide conversion device, comprising: the device comprises a renewable energy modulation module and a plasma coupling electrocatalytic module;
the renewable energy source modulation module is used for being connected into various renewable energy sources to supply power, and the renewable energy source modulation module can meet the power requirement of the plasma coupling electrocatalytic module through voltage-current conversion;
the plasma coupling electrocatalytic module comprises a dielectric barrier discharge array submodule, an electrocatalytic submodule and a product separation submodule;
the dielectric barrier discharge array submodule is used for dissociating and activating carbon-oxygen bonds in carbon dioxide, introducing gaseous carbon dioxide into the plasma reactor array, generating gas breakdown discharge to form a non-thermodynamic equilibrium plasma phase environment by adjusting physical characteristics of the plasma array such as input voltage and discharge frequency parameters, and realizing carbon dioxide activation to form carbon dioxide excited state particles of a plasma phase;
the electro-catalytic submodule is used for directly carrying out electro-catalytic conversion on carbon dioxide excited state particles of a plasma phase on the gas diffusion electrode, and different products are generated directionally by adjusting the types of the catalysts;
the product separation module is used for directionally separating gas and liquid products during collection, wherein the gas products are directly discharged from a gas outlet, the liquid products are temporarily stored in a pore flow channel constructed by additive manufacturing on a catalyst interface, and the liquid products are periodically taken out by the pulse water circulation device; the pore flow channel is constructed on the catalyst interface of the gas diffusion electrode by a three-dimensional additive manufacturing method, and a micron-sized cavity is formed on the gas diffusion electrode-ion exchange membrane interface after the electrocatalytic device is assembled and is used for temporarily storing liquid products.
2. The product phase separated plasma coupled electrocatalytic carbon dioxide conversion device as claimed in claim 1, wherein the renewable energy modulation module is configured to provide fluctuating energy input to power the plasma coupled electrocatalytic module.
3. The plasma coupling electrocatalytic carbon dioxide conversion device with separated product phase according to claim 1, wherein the dielectric barrier discharge array submodule is connected with a plasma power supply to realize that reactive gas breaks down to generate low-temperature plasmas with different physical characteristics by modulating output voltage and output frequency parameters of the power supply.
4. The apparatus of claim 1, wherein the micron-sized pore flow channels are designed as labyrinthine to maximize mass transfer efficiency and product uniformity.
5. The apparatus of claim 4, wherein the product is collected by periodic pulsed water circulation, concentrated liquid product is collected by pulsed water circulation after short storage in the flow channel, and product collection efficiency is improved, product inhibition and catalysis efficiency is prevented, and energy consumption is reduced.
6. The apparatus of claim 5, wherein the liquid product collected from the circulating water is fractionated to obtain pure carbon product.
7. A process for the conversion of carbon dioxide by plasma coupled electrocatalysis with product phase separation, comprising the steps of:
(1) The renewable energy source is converted through voltage and current to meet the power requirement of the dielectric barrier discharge array and the electrocatalysis;
(2) The carbon-oxygen bond in the carbon dioxide is dissociated and activated through the dielectric barrier discharge array, and the method specifically comprises the following steps: introducing gaseous carbon dioxide into a plasma reactor array, and generating gas breakdown discharge to form a non-thermodynamic equilibrium plasma phase environment by adjusting physical characteristics of the plasma array such as input voltage and discharge frequency parameters, so as to realize carbon dioxide activation and form carbon dioxide excited state particles of a plasma phase;
(3) The carbon dioxide excited state particles of the plasma phase are directly subjected to electrocatalytic conversion on a gas diffusion electrode, and different products are directionally generated by adjusting the types of the catalysts;
(4) Directionally separating gas and liquid products during collection, wherein the gas products are directly discharged from a gas outlet, the liquid products are temporarily stored in a pore flow channel constructed by additive manufacturing on a catalyst interface, and the liquid products are periodically taken out by a pulse water circulation device; the pore flow channel is constructed on the catalyst interface of the gas diffusion electrode by a three-dimensional additive manufacturing method, and a micron-sized cavity is formed on the gas diffusion electrode-ion exchange membrane interface after the electrocatalytic device is assembled and is used for temporarily storing liquid products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310306268.7A CN116445943A (en) | 2023-03-27 | 2023-03-27 | Plasma coupling electrocatalytic carbon dioxide conversion device and method for product phase separation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310306268.7A CN116445943A (en) | 2023-03-27 | 2023-03-27 | Plasma coupling electrocatalytic carbon dioxide conversion device and method for product phase separation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116445943A true CN116445943A (en) | 2023-07-18 |
Family
ID=87132957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310306268.7A Pending CN116445943A (en) | 2023-03-27 | 2023-03-27 | Plasma coupling electrocatalytic carbon dioxide conversion device and method for product phase separation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116445943A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117919907A (en) * | 2024-02-29 | 2024-04-26 | 三碳(安徽)科技研究院有限公司 | Carbon dioxide electrocatalytic reduction device for multiple-effect water removal |
-
2023
- 2023-03-27 CN CN202310306268.7A patent/CN116445943A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117919907A (en) * | 2024-02-29 | 2024-04-26 | 三碳(安徽)科技研究院有限公司 | Carbon dioxide electrocatalytic reduction device for multiple-effect water removal |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Younas et al. | An overview of hydrogen production: current status, potential, and challenges | |
| CN111663150B (en) | Wave type power input hydrogen production method by electrolyzing water and device thereof | |
| CN105084311A (en) | Zero-carbon-emission hydrogen production system by methanol water reforming as well as application and hydrogen production method thereof | |
| US20230203686A1 (en) | Systems and methods of ammonia synthesis | |
| CN105024628A (en) | Energy complementation self power supply system and power supply method | |
| CN205222680U (en) | Methanol -water reformation hydrogen production system that zero carbon discharged and fuel cell car thereof | |
| CN116445943A (en) | Plasma coupling electrocatalytic carbon dioxide conversion device and method for product phase separation | |
| CN115970448A (en) | Flue gas CO 2 Carbon-loading method and system integrating trapping and electrolysis | |
| WO2012144960A1 (en) | A combined magnetohydrodynamic and electrochemical method and facility for namely electric power generation | |
| CN218561635U (en) | Solar-driven microbial electrolysis hydrogen production synchronous organic sewage treatment system | |
| CN214572257U (en) | Hydrogen recovery device system for hydrogen production by renewable energy sources | |
| CN216756382U (en) | Methanol preparation and cyclic utilization system | |
| CN113026042B (en) | Micro electrochemical reactor based on micro-fluidic technology | |
| CN212810358U (en) | Clean energy power supply system | |
| JP2021530620A (en) | Renewable natural gas from renewable electricity using biological methanogenesis | |
| CN117771903A (en) | Plasma-electrocatalytic series grading system and application | |
| CN117144414A (en) | Plasma coupling electrocatalytic nitrogen fixation device and method capable of regulating and controlling product | |
| US20240072339A1 (en) | Renewable energy integration with natural-gas based combined hydrogen and electricity production (chep) system and method | |
| CN217962496U (en) | Negative corona discharge reaction device for ammonia decomposition | |
| CN117563523A (en) | Plasma catalyzed CO 2 Green electricity digestion system and method for synthesizing methanol through hydrogenation | |
| CN117210835A (en) | Gas-liquid separation double-layer flow passage electrolytic cell for preparing methanol by electrolysis and application thereof | |
| CN117604542A (en) | Electrolysis system and electrolysis method for preparing formic acid by coupling flue gas treatment with methanol oxidation in power plant | |
| Khoobroo et al. | On the efficiency of the fuel cell vehicles with onboard hydrogen generation | |
| WO2024011285A1 (en) | Ammonia production | |
| CN117385381A (en) | Membrane separation and electrochemical hydrogen pump coupling hydrogen extraction and CO for hydrogen-doped natural gas 2 System and method for preparing formic acid through hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |