CN110344071A - Electroreduction CO2Device and method - Google Patents
Electroreduction CO2Device and method Download PDFInfo
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- CN110344071A CN110344071A CN201910750320.1A CN201910750320A CN110344071A CN 110344071 A CN110344071 A CN 110344071A CN 201910750320 A CN201910750320 A CN 201910750320A CN 110344071 A CN110344071 A CN 110344071A
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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
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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
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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
- C25B9/17—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
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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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
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A kind of electroreduction CO is provided2Device, comprising: electrochemical reaction unit, including cathode chamber, anode chamber and membrane electrode, the diaphragm of the membrane electrode are anion-exchange membrane；And cathode feed unit, it is connected with the feed inlet of the cathode chamber, Xiang Suoshu cathode chamber input humidification contains CO2Gas.A kind of electroreduction CO is also provided2Method.Apparatus of the present invention and method have many advantages, such as that simple process, environmentally protective, equipment requirement is low, manufacturing cost is low, are applicable in very much industrialized synthesis gas production, can obtain good economic benefit and social benefit.
Description
Technical field
The present invention relates to electrochemical technology fields, and in particular to electroreduction CO2Device and method.
Background technique
With CO and H2It is industrial fischer-tropsch synthesis process production high added value fuel and chemicals for the synthesis gas mainly formed
Basic material.Synthesis gas mainly passes through coal gasification path and prepares, but a large amount of CO of by-product2, both caused sizable carbon resource
Waste, and cause sizable carbon emission reduction pressure.It can be by CO by electrochemical means2It is converted into CO, is both a kind of environmental protection
Clean carbon emission reduction approach and a kind of CO for increasing synthesis gas production capacity2Recycling recycles approach, while a kind of still support
The energy storage mode of renewable energy power generation.But as a kind of attractive new technique, CO2Electrochemical conversion prepares CO's
For mode it is still necessary to will be in many-sided continual exploitation and perfect, being electrochemically transformed technique be one of its emphasis upgrading task.
CO2Being electrochemically transformed and preparing CO has been come by the two chamber-type electrolytic cell with cathode chamber and anode chamber
At.Traditional low temperature conversion mode is two-electrolyte solution feed, and highly basic or bicarbonate solution are walked by anode chamber, and cathode chamber is walked molten
Solve or carry CO2Alkali metal carbonate solution.The major defect of this mode is by CO low in liquid phase2Solubility and electrode
Low CO selective problems caused by internal liquid mass transfer difficulty, by the electrolysis caused by the electrolyte mass transfer between the anode chamber and the cathode chamber
Matter expends and the anode chamber and the cathode chamber electrolyte concentration instability problem, and by electrolyte solution corrosion and wash away caused electrode
Higher problem of the requirement for anticorrosion of long-time stability deficiency and pipeline equipment etc..The presence of these defects make two-electrolyte solution into
Material mode hardly enters large-scale industrial application.
Summary of the invention
In order to overcome drawbacks described above, the present invention provides a kind of electroreduction CO2Device and method.
One aspect of the present invention provides a kind of electroreduction CO2Device, comprising: electrochemical reaction unit, including cathode chamber, anode
Room and membrane electrode, the diaphragm of the membrane electrode are anion-exchange membrane；And cathode feed unit, the charging with the cathode chamber
Mouth is connected, and Xiang Suoshu cathode chamber input humidification contains CO2Gas.
According to an embodiment of the present invention, the humidification contain CO2The relative humidity of gas is 20~90%.
Another embodiment according to the present invention, described device further include anode feed unit, with the anode chamber into
Material mouth is connected, and the anode chamber Xiang Suoshu inputs the carbonate or bicarbonate solution of pure water or the alkali metal of 0.001~2mol/L.
Another aspect of the present invention provides a kind of electroreduction CO2Device, comprising: electrochemical reaction unit, including cathode chamber, sun
Pole room and membrane electrode, the diaphragm of the membrane electrode are cation-exchange membrane；Cathode feed unit, the feed inlet with the cathode chamber
It is connected, the input of Xiang Suoshu cathode chamber contains CO2Gas；And anode feed unit, it is connected with the feed inlet of the anode chamber, to institute
State anode chamber's input pure water.
According to an embodiment of the present invention, described to contain CO2CO in gas2Concentration expressed in percentage by volume be 10~100%；Institute
The concentration expressed in percentage by volume for stating synthesis gas in cathode chamber discharging gas is 10-99%, in synthesis gas CO account for gross product volume basis it is dense
Degree is 10%~99.9%.
Another embodiment according to the present invention, described device further include: gas circulation unit, including synthesis gas segregant
Unit, gas circulator and humidity regulator, upstream separate subelement with the cathode chamber outlet or with synthesis gas and are connected,
Downstream is connected with the cathode feed unit.
Also a kind of electroreduction CO of another aspect of the present invention2Method, comprising: humidification is contained into CO2It is anti-that gas is delivered to electrochemistry
The cathode chamber of unit is answered to be electrochemically reacted, the electrochemical reaction unit includes the cathode chamber, anode chamber and membrane electrode,
The diaphragm of the membrane electrode is anion-exchange membrane.
According to an embodiment of the present invention, the humidification contain CO2The relative humidity of gas is 20~90%.
Another embodiment according to the present invention, the method also includes: by pure water or the alkali metal of 0.001~2mol/L
Carbonate or bicarbonate solution be passed through the anode chamber.
Another embodiment according to the present invention, the method also includes: it does not send out in the electrochemical reaction unit
The gas of raw reaction purges the anode chamber.Purge methods can be it is continuous can also be it is intermittent.
The gas of another embodiment according to the present invention, the purging is selected from CO2、N2、O2, one of Ar or a variety of.
Another aspect of the present invention also provides a kind of electroreduction CO2Method, comprising: CO will be contained2Gas is delivered to electrochemical reaction
The cathode chamber of unit, the electrochemical reaction unit include the cathode chamber, anode chamber and membrane electrode, the diaphragm of the membrane electrode
For cation-exchange membrane；Pure water is delivered to the anode chamber；And it is electrochemically reacted.
According to an embodiment of the present invention, described to contain CO2CO in gas2Concentration expressed in percentage by volume be 10~100%.
Another embodiment according to the present invention, the method also includes: the reaction product of the cathode chamber is divided
From by unreacted CO2Gas returns to the cathode chamber and is recycled.
Another embodiment according to the present invention, the electrochemical reaction unit interior reaction temperature are 10 DEG C~90 DEG C, instead
Answering pressure is 0.01MPa~10MPa, and reactive tank pressure is 2~4V.
Electroreduction CO of the invention2Device, by between two Room of electrochemical reaction unit be arranged anion-exchange membrane or
Cation-exchange membrane can be such that entire electrochemical reaction completes in the presence of gas raw material, only consume CO2And H2O, without consuming electricity
Xie Zhi also avoids the numerous negative issues of electrolyte solution bring in traditional handicraft；And CO2With gaseous feed, relieve
CO2Limitation in terms of concentration, gas source, enormously simplifies process flow, has widened technique practicability, has extended electrochemistry
The service life of reaction member.
Electroreduction CO of the invention2Device be not necessarily to complex device, can be used existing electrochemical reaction unit and other
Relevant apparatus or equipment carry out complicated improvement without to each device or equipment, and system can long-time, stable operation.
Electroreduction CO of the invention2The conveniently adjusted CO therein and H of synthesis gas made from method2Ratio obtains type more
More products.
In conclusion apparatus of the present invention and method have, simple process, environmentally protective, equipment requirement is low, manufacturing cost is low
Many advantages, such as, it is applicable in very much industrialized synthesis gas production, good economic benefit and social benefit can be obtained.
Detailed description of the invention
Its example embodiment is described in detail by referring to accompanying drawing, above and other feature of the invention and advantage will become
It is more obvious.
Fig. 1 is the structural schematic diagram of an embodiment of the present invention.
Fig. 2 is the structural schematic diagram of another embodiment of the present invention.
Wherein, the reference numerals are as follows:
R1, electrochemical reaction unit；R101, cathode chamber；R102, anode chamber；R103, diaphragm；R104, DC power supply；
R105, cathode electrode；R106, anode electrode；
T1, cathode humidification tank；T2, synthesis gas knockout drum；T3, synthesis gas desiccant canister；T4, anode fluid reservoir；C1, gas follow
Ring pump；S1, humidity controller；S2, hygronom；E1, heat exchanger；P1, anode circulation pump；
1, inlet manifold's line；2, the first CO2Admission line；3, the 2nd CO2Admission line；4, cathode inlet pipeline；5, cathode
Outlet line；6, synthesis gas product pipeline；7,CO2Pipeloop；8, anode feed liquor or gas pipeline；9, first anode outlet
Line；10, second plate outlet line；12, cathode water supply line；13, anode water supply line；14, anode flowing line；
A, contain CO2Gas；B, synthesis gas product；C, anodic product.
Specific embodiment
It elaborates With reference to embodiment to the present invention.
The electroreduction CO of an embodiment of the present invention2Device, comprising: electrochemical reaction unit, including cathode chamber, anode chamber
And membrane electrode, the diaphragm of membrane electrode are anion-exchange membrane；And cathode feed unit, it is connected with the feed inlet of cathode chamber, to
Cathode chamber input humidification contains CO2Gas.
Specifically, membrane electrode can be coated with anode catalyst or cathod catalyst for the single side of diaphragm, can also be two sides point
Other coated anode catalyst and cathod catalyst.Cathod catalyst includes but is not limited to gold, silver, palladium, tin, zinc, bismuth, indium, nickel, copper
Equal simple substance, alloy, oxide and nitride.Anode catalyst include but is not limited to iridium, ruthenium, palladium, nickel, iron, cobalt, platinum, gold, silver,
Copper etc. is single-phase or multiphase oxide.In the device of the embodiment, the raw material of the cathode chamber of electrochemical reaction unit is CO2With
Water, CO in cathode chamber2And H2O generates CO, H under cathod catalyst effect2With anode chamber Zhong Yin can be moved under electric field action
Ion, anion decompose under anode catalyst effect and release anodic product, including O2、H2O and CO2One of, two kinds or
Three kinds.
In some embodiments, anode chamber does not input any liquid charging stock, and anode chamber's product can be emptied directly, while
The gas not reacted in the electrochemical reaction unit can be used in evacuation procedure to purge anode chamber, Purge methods
Can be it is continuous can also be it is intermittent.During being electrochemically reacted, CO in cathode chamber2With water in cathod catalyst
Effect is lower to generate CO, H2With can move to anion in anode chamber under electric field action, anion is under anode catalyst effect
Decomposition releases anodic product, including O2、H2O and CO2One of, two or three, with gas purge can avoid anode chamber product
The generation of water.In these embodiments, anode chamber's discharging gas bag includes product and purge gas, some embodiment middle-jiao yang, function of the spleen and stomach pole rooms discharging gas
It can directly be discharged by anode export pipeline；It a part of can also discharge, another part continues to be recycled for anode chamber.
In these embodiments, because not supplying water to anode chamber, in order to guarantee the progress of reaction, need during the reaction to yin
Pole room provides CO2And water vapour, not directly with dry CO2Gas feed.The gas of purging, which can be, can take appointing for anode chamber's product out of
What gas includes but is not limited to CO2、N2、O2, one pack systems or the mixed component gas such as Ar.
In some embodiments, anode chamber can be fed with water, can also be with the carbonate or bicarbonate of low concentration alkali metal
Solution feed is electrochemically reacted.CO in cathode chamber2CO, H are generated under cathod catalyst effect with vapor2With can be in electricity
Anion in anode chamber is moved under field action, anion decomposes under anode catalyst effect and releases anodic product, including
O2、H2O and CO2One of, two or three.
In some embodiments, anode chamber is not required to the introducing of the raw materials such as any salt, alkali with pure water feed in reaction process；
In further embodiments, it is fed with the carbonate of alkali metal or bicarbonate, also only needs constantly to be added in starting up, instead
Subsequent introducing is no longer needed in answering.Consumption raw material needed for entire synthetic route also only has water and carbon dioxide.Alkali metal lithium, sodium, potassium,
Rubidium, caesium, preferably potassium and sodium, but not limited to this.The molar concentration of salt is in the carbonate or bicarbonate solution of alkali metal
0.001-2mol/L.Because the carbonate of low concentration alkali metal or the alkalinity of bicarbonate solution are weaker, therefore greatly reduce pair
The corrosion of reaction member and associated ping improves reaction member and associated ping service life.
In some embodiments, CO can be contained by adjusting humidification2The humidity of gas forms to adjust synthesis gas.Electrification
H in synthesis gas can directly be increased by learning reaction member cathode chamber feeding gas relative humidity height2Concentration expressed in percentage by volume, the low meeting of relative humidity
Increase CO concentration expressed in percentage by volume in synthesis gas.It should be noted that easily leading to and joining in cathode chamber when feeding gas relative humidity is too low
With the H of reduction reaction2O is insufficient, relatively low so as to cause kinetic current, and when feeding gas relative humidity is excessively high, liberation of hydrogen is anti-
What is strained is serious, even seeping phenomenon occurs in cathode chamber.So the present invention is too low or excessively high in order to solve feeding gas humidity
Brought negative effect increases humidity regulation link.It specifically can be the only simple temperature by conditioning moisturer to control
CO processed2The relative humidity of gas is also possible to the CO of above-mentioned humidification2Gas and dry CO2Gas is mixed, by adjusting between the two
Volume form to control, to obtain the gaseous mixture of certain humidity, even switch between.Wherein humidifier
Temperature between 20~80 DEG C, the relative humidity of humidifier is 20~90%, and the relative humidity of gaseous mixture is 20~90%.
In some embodiments, electroreduction CO2Device can also include gas circulation unit, including synthesis gas segregant list
Member, gas circulator and hygronom, upstream are connected with cathode chamber outlet, and downstream is connected with cathode feed unit, gas circulation
Pump provides power for cycling element and gas is promoted to flow.By the discharging of cathode chamber through synthesis gas separative unit by the discharging of cathode chamber
Gas carries out respectively obtaining synthesis gas and unreacted CO2Gas, wherein the CO isolated2Gas, which can continue to recycle for cathode chamber, to be made
With being greatly improved CO2The utilization rate of gas.Specifically, cathode chamber discharging gas can be first straight through synthesis gas separation subelement
It connects and isolates unreacted CO2, this CO2Cathode feed unit is returned to be recycled；It can also be a part warp of cathode chamber discharging gas
Synthesis gas separation subelement is directly separated out unreacted CO2, another part cathode chamber discharging gas directly with the CO that isolates2It is mixed
It closes and returns to the recycling of cathode feed unit；It is even switched on initial stage, cathode discharging gas fully enters cathode feed unit circulation
It uses.The concentration expressed in percentage by volume of synthesis gas is 10-99% in cathode chamber discharging gas, and CO accounts for the volume basis of gross product in synthesis gas
Concentration is 10%~99.9%.
In some embodiments, anode chamber's product can enter after circulating tank is separated and be discharged, can also going out from anode chamber
Material mouth is expelled directly out.
In some embodiments, electrochemical reaction unit can be monolithic, can also be multi-disc serial or parallel connection combined running.Its
Middle monolithic refers to an anode chamber and a cathode chamber combined running, and multi-disc refers to multiple anodes and multiple cathode alternate combinations fortune
Row.Electrochemical reaction cell temperature is 10 DEG C~90 DEG C in some embodiments, and reaction pressure is 0.01MPa~10MPa, reaction
Slot pressure is 2~4V.
Utilize above-mentioned electroreduction CO2Device restores CO2Method, comprising: by humidification contain CO2Gas is delivered to electrochemistry
The cathode chamber of reaction member is electrochemically reacted.
In some embodiments, the product of cathode chamber is separated, and obtains synthesis gas (CO and H2) and unreacted CO2Gas,
In unreacted CO2Gas returns to cathode chamber and is recycled.The volume hundred of synthesis gas in the cathode chamber discharging gas of electrochemical reactor
Dividing concentration is 10-99%, and it is 10%~99.9% that CO, which accounts for the concentration expressed in percentage by volume of gross product, in synthesis gas.
In some embodiments, humidification contain CO2The relative humidity of gas is 20~90%.
In some embodiments, the anode chamber of electrochemical reaction unit does not pass through any liquid charging stock, and anodic product can
Emptying, while the gas purging anode not reacted in the electrochemical reaction unit can be used in direct evacuation procedure
Room, Purge methods can be it is continuous can also be it is intermittent, to prevent anode chamber from ponding situation occur.The gas of purging can
To be selected from CO2、N2、O2, one of Ar or a variety of.
In some embodiments, the anode chamber of electrochemical reaction unit can also be passed through pure water or 0.001~2mol/L
The carbonate or bicarbonate solution of alkali metal.
The electroreduction CO of another embodiment of the present invention2Device, comprising: electrochemical reaction unit, including cathode chamber, anode
Room and membrane electrode, the diaphragm of membrane electrode are cation-exchange membrane；Cathode feed unit is connected with the feed inlet of cathode chamber, Xiang Yin
Pole room input contains CO2Gas；And anode feed unit, it is connected with the feed inlet of anode chamber, inputs pure water to anode chamber.
Since in the device of the embodiment, anode chamber passes through pure water, cathode can contain CO always with humidification in reaction process2
Gas feed；Can also be in starting up, cathode is passed through humidification containing CO2Gas, during the reaction, as anode proton is past
The transmitting of cathode, the entrained water of meeting associated proton migration, therefore cathode chamber can be switched to dry CO after booting2Gas and wet CO2Gas is mixed
Close charging or the intermittent mutual switch mode of charging.
Specifically, membrane electrode can be coated with anode catalyst or cathod catalyst for the single side of diaphragm, can also be two sides point
Other coated anode catalyst and cathod catalyst.Cathod catalyst includes but is not limited to gold, silver, palladium, tin, zinc, bismuth, indium, nickel, copper
Equal simple substance, alloy, oxide and nitride.Anode catalyst include but is not limited to iridium, ruthenium, palladium, nickel, iron, cobalt, platinum, gold, silver,
Copper etc. is single-phase or multiphase oxide.In the device of the embodiment, the anode chamber of electrochemical reaction unit is with pure water or low concentration
Alkali metal carbonate or bicarbonate solution charging.CO in cathode chamber2And H2O generates CO, H under cathod catalyst effect2
And anion；The water of anode chamber is decomposed into proton and oxygen under anode catalyst effect, and proton is transmitted by anode exchange membrane
The anion generated to cathode chamber and cathode chamber neutralizes, and releases H2O or CO2One or both of.In these embodiments, alkali
The carbonate or bicarbonate of metal only need constantly to be added in starting up, and subsequent introducing is no longer needed in reaction.Entire synthesis
Consumption raw material needed for route also only has water and carbon dioxide.Alkali metal lithium, sodium, potassium, rubidium, caesium, preferably potassium and sodium, but be not limited to
This.The molar concentration of salt is 0.001-2mol/L in the carbonate or bicarbonate solution of alkali metal.Because of low concentration alkali metal
The alkalinity of carbonate or bicarbonate solution is weaker, therefore greatly reduces the corrosion to reaction member and associated ping, mentions
High reaction member and associated ping service life.
In some embodiments, cathode chamber is passed through in device contains CO2CO in gas2The total gas volume percentage concentration of Zhan exists
10%~100%, preferably 50%~100%, this can widen the scope of application of unstripped gas significantly.Humidification contains CO2Gas
Relative humidity is 20~90%.
In some embodiments, the discharging of cathode chamber is separated through product separation system, respectively obtain synthesis gas and
Unreacted CO2Gas, wherein the CO isolated2Gas can continue to be recycled for cathode chamber, substantially increase CO2The utilization of gas
Rate.Specifically, electroreduction CO2Device can also include gas circulation unit, including synthesis gas separation subelement, gas circulation
Pump and humidity regulator, upstream are connected with cathode chamber outlet, and downstream is connected with cathode feed unit.Synthesis gas separative unit will
The unreacted CO that the product of cathode chamber is isolated2Gas and by unreacted CO2Gas is back to the recycling of cathode feed unit.
Gas circulator provides power for cycling element and gas is promoted to flow, and hygronom is used to detect the humidity for introducing charging.
In some embodiments, anode chamber's product can enter after circulating tank is separated and be discharged, can also going out from anode chamber
Material mouth is expelled directly out.
In some embodiments, electrochemical reaction unit can be monolithic, can also be multi-disc serial or parallel connection combined running.Its
Middle monolithic refers to an anode chamber and a cathode chamber combined running, and multi-disc refers to multiple anodes and multiple cathode alternate combinations fortune
Row.Electrochemical reaction cell temperature is 10 DEG C~90 DEG C in some embodiments, and reaction pressure is 0.01MPa~10MPa, reaction
Slot pressure is 2~4V.
Utilize above-mentioned electroreduction CO2Device restores CO2Method, comprising: CO will be contained2Gas is delivered to electrochemical reaction list
The cathode chamber of member, electrochemical reaction unit include cathode chamber, anode chamber and membrane electrode, and the diaphragm of membrane electrode is cation exchange
Film；The carbonate or bicarbonate solution of pure water or the alkali metal of 0.001~2mol/L are delivered to anode chamber；And carry out electricity
Chemical reaction.
In some embodiments, contain CO2CO in gas2Concentration expressed in percentage by volume be 10~100%.
In some embodiments, the reaction product of cathode chamber can be separated, by unreacted CO2Gas returns to cathode
Room is recycled, to greatly improve CO2Utilization rate.Cathode chamber discharging gas can be first directly separated through synthesis gas separation subelement
Unreacted CO out2, this CO2Cathode feed unit is returned to be recycled；Cathode chamber discharges gas can also be a part of first through synthesis gas point
Ion unit is directly separated out unreacted CO2, then another part cathode chamber discharging gas directly with the CO that isolates2Mixing is returned
Cathode feed unit is returned to be recycled.The concentration expressed in percentage by volume of synthesis gas is 10- in the cathode chamber discharging gas of electrochemical reactor
99%, it is 10%~99.9% that CO, which accounts for the concentration expressed in percentage by volume of gross product, in synthesis gas.
By the above-mentioned description to apparatus and method of the present invention it is found that either anode chamber with pure water feed, with alkali gold
Carbonate or the bicarbonate solution charging of category still do not feed anode chamber and direct ingress of air, in entire production process
The raw material of consumption is only limitted to carbon dioxide and water.Anode chamber avoids required for conventional gas-phase mode because of the consumption of not no salt
The processes such as subsequent benefit salt, desalination and brine waste processing, so that operating process is simplified, CO2Reduction process clean and environmental protection；Simultaneously
The risk that impurity is corroded in the accumulation of reaction member and equipment is also reduced, reaction member and equipment are substantially increased
Performance and used life.
It is explained in detail below by way of specific embodiment and illustrates inventive concept of the invention, those skilled in the art can manage
Following embodiments are solved to be not intended to limit the present invention.
Embodiment 1
The diaphragm R103 of membrane electrode is anion-exchange membrane in the present embodiment device, and the two sides of diaphragm is coated with respectively by receiving
The cathod catalyst and the black anode catalyst of Ir of rice silver powder, carbon dust composition.Electrochemical reactor membrane electrode effective active area is
2500cm2。
As shown in Figure 1, electroreduction CO2Device includes electrochemical reaction unit R 1 (including R101 cathode chamber, anode chamber
R102；Diaphragm 103, cathode electrode R105, anode electrode R106), cathode humidification tank T1, cathode drying chamber T2, synthesis gas separation
Device T3, anode can T4, gas circulator C1, humidity regulation controller S1, hygronom S2, heat exchanger E1, anode circulation pump P1, into
Gas main pipe line 1, the first CO2Admission line 2, the 2nd CO2Admission line 3, cathode inlet pipeline 4, cathode outlet line 5, product close
At gas pipeline 6, contain CO2Gas pipeloop 7, anode feed liquor pipeline 8, first anode outlet line 9, second plate outlet line
10, cathode water supply line 12, anode water supply line 13 and DC power supply 104.
When DC power supply R104 goes into operation to electrochemical reactor R1 energization, contain CO using dry2Gas A is as gas source, A warp
It is 80% humidification CO that obtaining after the entrance cathode humidification tank T1 humidification of inlet manifold's line 1, which has relative humidity,2Gas humidifies CO2Gas is again
Successively through the 2nd CO2Admission line 3 and cathode inlet pipeline 4 enter the cathode chamber R101 of electrochemical reactor R1.By A after going into operation
Contain CO with pipeloop 72After gas mixing, obtaining relative humidity after humidified tank T1 humidification is 80% gaseous mixture, then successively
Through the 2nd CO2The cathode chamber R101 that admission line 3 and cathode inlet pipeline 4 enter electrochemical reactor R1 is recycled, at this time through following
The CO of endless tube line 72Gas internal circulating load is equivalent to the CO that reaction is had neither part nor lot in cathode discharging gas2.Entire cathode chamber R101 feed inlet into
Gas humidity control and management are completed by the humidity controller S1 on cathode inlet pipeline 4.CO, H of synthesis gas knockout drum T22It is mixed
It closes gas to enter in synthesis gas desiccant canister T3, synthesis gas product B is obtained after dehumidifying by 6 discharge system of synthesis gas product pipeline.
At the same time, pure liquid water is added in anode can T4, the water in anode can T4 is through anode feed liquor pipeline 8 by anode
Circulating pump P1 squeezes into the anode chamber R102 of electrochemical reactor R1, generates O in anode chamber R1022、H2O and CO2, by the first sun
Pole outlet line 9 returns in anode can T4, and then anodic gas product is discharged by second plate outlet line 10.
Water of the above-mentioned apparatus in the process of running in cathode humidification tank T1 can be supplemented by cathode water supply line 12, anode can T4
In water can be supplemented by anode water supply line 13, extra water can be discharged by anode flowing line.Cathode chamber R101 feed inlet
Inlet relative humidity control is 60%, by heat exchanger E1 by the electrolysis temperature control of electrochemical reactor at 46 DEG C, reactor pressure
Power maintains 0.01MPa, and voltage operating range is controlled in 2~4V, is electrolysed by way of constant current.Pass through party's legal system
The concentration expressed in percentage by volume of synthesis gas is 10-99% in standby cathode chamber discharging gas, and CO accounts for the volume basis of gross product in synthesis gas
Concentration is 10%~99.9%.
Table 1 is gas phase electroreduction CO of the embodiment 1 under different total currents2Preparing synthetic gas electrolytic parameter.
Embodiment 2
The present embodiment uses Fig. 1 shown device, wherein diaphragm R103 selects cation-exchange membrane, the two sides difference of diaphragm
It is coated with the cathod catalyst and the black anode catalyst of Ir being made of nano-silver powder, carbon dust.Electrochemical reactor membrane electrode is effective
Active area is 2500cm2。
The process that device operation prepares synthesis gas is as follows:
Contain CO using dry or wet2Gas A is with embodiment 1, feeding gas relative humidity as gas source, A air inlet pre-treatment
60%.Pure liquid water is passed through to anode chamber R102 also according to 1 mode of embodiment.With DC power supply R104 to electrochemical reactor
R1 is powered, and pure water releases anodic product C (O under the anode electrode R106 catalytic action of anode chamber R1022)。O2By the first sun
Pole outlet line 9 returns in anode can T4, is then discharged by second plate outlet line 10.CO2And H2O is in cathode chamber R101
Reaction generates synthesis gas.And the discharging gas bag of cathode chamber R101 includes CO, H2, water and unreacted CO2Gas.Cathode chamber R101's
Discharging gas enters synthesis gas knockout drum T2 and isolates unreacted CO2, then through CO2Pipeloop 7 and air source A are mixed into yin
To relative humidity up to after 60%, the cathode chamber R101 for being again introduced into electrochemical reactor R1 is recycled pole humidifying pot T1 humidification.
CO, H of synthesis gas knockout drum T22Gaseous mixture and water enter in synthesis gas desiccant canister T3, obtained after dehumidifying synthesis gas product B by
6 discharge system of synthesis gas product pipeline.
Water of the above-mentioned apparatus in the process of running in cathode humidification tank T1 can be supplemented by cathode water supply line 12, anode can T4
In water can be supplemented by anode water supply line 13, extra water can be discharged by anode flowing line.It is reacted in entire reaction process
Device carries out under the conditions of 0.01MPa at 46 DEG C.Voltage operating range is controlled in 2~4V, is electrolysed by way of constant current.
The concentration expressed in percentage by volume of synthesis gas is 10-99% in the cathode chamber discharging gas prepared by this method, and CO accounts for total yield in synthesis gas
The concentration expressed in percentage by volume of object is 10%~99.9%.
Table 2 is gas phase electroreduction CO of the embodiment 2 under different total currents2Preparing synthetic gas electrolytic parameter.
Embodiment 3
The present embodiment uses Fig. 1 shown device, and diaphragm R103 is the same as embodiment 1.The two sides of diaphragm is coated with respectively by nanometer
The cathod catalyst and the black anode catalyst of Ir of silver powder, carbon dust composition.Electrochemical reactor membrane electrode effective active area is
2500cm2。
Contain CO using dry or wet2Gas A is as gas source, and A air inlet pre-treatment is the same as embodiment 1.
The potassium bicarbonate solution that molar concentration is 0.02mol/L is added in anode can T4 and substitutes liquid water, other steps
With embodiment 1.Device is not necessarily to supplement potassium bicarbonate solution to anode can T4 during running, and can optionally pass through anode water supply line
The 13 appropriate pure water of supplement.The inlet relative humidity of cathode chamber R101 feed inlet is controlled 60%.Reactor in entire reaction process
It is carried out under the conditions of 46 DEG C, 0.01MPa.Voltage operating range is controlled in 2~4V, is electrolysed by way of constant current.It is logical
The concentration expressed in percentage by volume for crossing synthesis gas in the cathode chamber discharging gas of this method preparation is 10-99%, and CO accounts for gross product in synthesis gas
Concentration expressed in percentage by volume be 10%~99.9%.
Table 3 is gas phase electroreduction CO of the embodiment 3 under different total currents2Preparing synthetic gas electrolytic parameter.
Embodiment 4
The diaphragm R103 of membrane electrode is anion-exchange membrane in the present embodiment, and the two sides of diaphragm is coated with respectively by nano silver
The cathod catalyst and the black anode catalyst of Ir of powder, carbon dust composition.Electrochemical reactor membrane electrode effective active area is
2500cm2.Using Fig. 2 shown device.
As shown in Fig. 2, electroreduction CO2Device includes electrochemical reaction unit R 1 (including R101 cathode chamber, anode chamber
R102；Diaphragm 103, cathode electrode R105, anode electrode R106), cathode humidifier 1, cathode drying chamber T2 synthesizes gas separating device
T3, humidity regulation controller S1, hygronom S2, inlet manifold's line 1, the first CO2Admission line, the 2nd CO2Admission line 3, cathode
Admission line 4, cathode outlet line 5, product synthesis gas pipeline 6 contain CO2Gas pipeloop 7, anode admission line 8, the first sun
Pole outlet line 9, cathode water supply line 12 and DC power supply 104.
With containing CO2Gas A is as gas source, and A air inlet pre-treatment is the same as embodiment 1.Device is not necessarily to be passed through to anode during running
Any liquid charging stock is only passed through N to anode admission line2Gas purges anode chamber, and anode chamber's product directly empties.Cathode
The inlet relative humidity of room R101 feed inlet is controlled 80%.Reactor is under the conditions of 60 DEG C, 0.01MPa in entire electrolytic process
It carries out.Voltage operating range is controlled in 2~4V, is electrolysed by way of constant current.The cathode chamber prepared by this method
The concentration expressed in percentage by volume of synthesis gas is 10-99% in discharging gas, and it is 10% that CO, which accounts for the concentration expressed in percentage by volume of gross product, in synthesis gas
~99.9%.
Table 4 is gas phase electroreduction CO of the embodiment 4 under different total currents2Preparing synthetic gas electrolytic parameter.
In the present invention, the cathode chamber of electrochemical reaction unit can humidify or not humidify CO2Charging, anode chamber can be low
Concentration alkali metal carbonate or bicarbonate solution charging, even can not also input any raw material with pure water feed.In cathode
Under the conditions of gas-phase feed, no matter anode chamber is with pure water feed or not feed, and raw material consumed by entire electrochemical process only has
Water and carbon dioxide.Flat in cathode, anode drops under conditions of concentration alkali metal carbonate or bicarbonate solution, anode institute
The salt needed need to only be added in booting, and substantially without subsequent supplement, thus raw material consumed by entire electrochemical process is also only
There are water and carbon dioxide.Therefore for raw materials requirement, the present invention provides a kind of carbon dioxide electricity of electroless matter consumption also
Original prepares the process for cleanly preparing of synthesis gas, both economically and environmentally beneficial.
Electroreduction CO provided by the invention2Device and method are effectively improved or thoroughly solve because using for electrolyte is spread out
Raw various problems, relieve liquid media to CO2Solubility limit, improve the mass transfer effect inside catalyst layer, advise
The instability problem for having kept away the anode chamber and the cathode chamber electrolyte concentration realizes the optimization and stabilization of pH environment locating for cathod catalyst, Du
The consumption for reducing electrolytic salt absolutely or substantially reduces the requirement for anticorrosion to equipment pipeline, and simplifies process flow.This hair
The method of bright offer had not only improved that CO is selectively low, but also improved the long-time stability of reaction member work, thus from performance
Meet the basic demand of industry amplification application.
Electroreduction CO provided by the invention2Device and method can achieve very high CO selectivity, but maximum lower than CO
Free adjusting can be carried out to the selectivity of CO in the range of selectivity, therefore can be flexibly matched with when coal gasification prepares synthesis gas
Distribution needs.Due to the use of cathode gas-phase feed mode, CO provided by the invention2The technique that electrochemical conversion prepares synthesis gas
Extend permitted unstripped gas CO2Concentration range, simultaneously because the use of circulation of tail gas mode, CO in gas source2Conversion ratio
It greatly improves, therefore reduces the requirement to unstripped gas, widened the source of unstripped gas, improve the utilization rate of unstripped gas, reduce
The carbon capture cost of carbon emission reduction enterprise.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention
Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (15)
1. a kind of electroreduction CO2Device characterized by comprising
Electrochemical reaction unit, including cathode chamber, anode chamber and membrane electrode, the diaphragm of the membrane electrode are anion-exchange membrane；
And
Cathode feed unit is connected with the feed inlet of the cathode chamber, and Xiang Suoshu cathode chamber input humidification contains CO2Gas.
2. electroreduction CO according to claim 12Device, which is characterized in that the humidification contains CO2Gas it is relatively wet
Degree is 20~90%.
3. electroreduction CO according to claim 12Device, which is characterized in that further include anode feed unit, with the sun
The feed inlet of pole room is connected, and the anode chamber Xiang Suoshu inputs the carbonate or bicarbonate of pure water or the alkali metal of 0.001~2mol/L
Salting liquid.
4. a kind of electroreduction CO2Device characterized by comprising
Electrochemical reaction unit, including cathode chamber, anode chamber and membrane electrode, the diaphragm of the membrane electrode are cation-exchange membrane；
Cathode feed unit is connected with the feed inlet of the cathode chamber, and the input of Xiang Suoshu cathode chamber contains CO2Gas；And
Anode feed unit is connected with the feed inlet of the anode chamber, and the anode chamber Xiang Suoshu inputs pure water.
5. according to claim 1 with electroreduction CO described in 42Device, which is characterized in that described to contain CO2CO in gas2Volume
Percentage concentration is 10~100%.
6. electroreduction CO according to claim 1 or 42Device, which is characterized in that further include:
Gas circulation unit, including synthesis gas separation subelement, gas circulator and hygronom, upstream go out with the cathode chamber
Mouth is connected, and downstream is connected with the cathode feed unit.
7. a kind of electroreduction CO2Method characterized by comprising
Humidification is contained into CO2The cathode chamber that gas is delivered to electrochemical reaction unit is electrochemically reacted, the electrochemical reaction
Unit includes the cathode chamber, anode chamber and membrane electrode, and the diaphragm of the membrane electrode is anion-exchange membrane.
8. electroreduction CO according to claim 72Method, which is characterized in that the humidification contains CO2Gas it is relatively wet
Degree is 20~90%.
9. electroreduction CO according to claim 72Method, which is characterized in that further include:
The carbonate or bicarbonate solution of pure water or the alkali metal of 0.001~2mol/L are passed through the anode chamber.
10. electroreduction CO according to claim 72Method, which is characterized in that further include: it is used in the electrochemical reaction list
The gas not reacted in member purges the anode chamber.
11. electroreduction CO according to claim 102Method, which is characterized in that the gas of the purging is selected from CO2、N2、
O2, one of Ar or a variety of.
12. a kind of electroreduction CO2Method characterized by comprising
CO will be contained2Gas is delivered to the cathode chamber of electrochemical reaction unit, the electrochemical reaction unit include the cathode chamber,
Anode chamber and membrane electrode, the diaphragm of the membrane electrode are cation-exchange membrane；
Pure water is delivered to the anode chamber；And
It is electrochemically reacted.
13. electroreduction CO according to claim 122Method, which is characterized in that described to contain CO2CO in gas2Volume hundred
Dividing concentration is 10~100%.
14. the electroreduction CO according to claim 7 or 122Method, which is characterized in that further include:
The reaction product of the cathode chamber is separated, by unreacted CO2Gas returns to the cathode chamber and is recycled.
15. according to electroreduction method described in claim 7 and 12, which is characterized in that reaction in the electrochemical reaction unit
Temperature is 10 DEG C~90 DEG C, and reaction pressure is 0.01MPa~10MPa, and reactive tank pressure is 2~4V.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113120866A (en) * | 2021-03-31 | 2021-07-16 | 中南大学 | Method for preparing elemental sulfur by using sulfur dioxide |
| CN115074758A (en) * | 2021-03-11 | 2022-09-20 | 本田技研工业株式会社 | Power generation device |
| EP4060086A1 (en) * | 2021-03-18 | 2022-09-21 | Kabushiki Kaisha Toshiba | Carbon dioxide electrolytic device |
Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020105082A1 (en) * | 2001-01-04 | 2002-08-08 | International Business Machines Corporation | Method for forming interconnects on semiconductor substrates and structures formed |
| CN101657568A (en) * | 2005-10-13 | 2010-02-24 | 曼得拉能源替代有限公司 | Continuous co-current electrochemical reduction of carbon dioxide |
| CN102181876A (en) * | 2011-03-30 | 2011-09-14 | 昆明理工大学 | Method and device for preparing carbon monoxide through electrochemical catalytic reduction of carbon dioxide |
| CN102812158A (en) * | 2011-03-09 | 2012-12-05 | 松下电器产业株式会社 | Method for reducing carbon dioxide |
| US9217202B2 (en) * | 2011-12-12 | 2015-12-22 | Tsinghua University | Membrane reactor |
| CN105297067A (en) * | 2015-11-16 | 2016-02-03 | 昆明理工大学 | Multi-room diaphragm electrolysis method and device for electroreduction of carbon dioxide into carbon monoxide |
| CN105316700A (en) * | 2014-07-29 | 2016-02-10 | 中国科学院大连化学物理研究所 | Electrolytic tank and application for electrochemical reduction reaction of carbon dioxide |
| CN205329170U (en) * | 2015-11-16 | 2016-06-22 | 昆明理工大学 | Multi -chambered diaphragm electrolysis device that is carbon dioxide electroreduction carbon monoxide |
| CN106715760A (en) * | 2014-09-08 | 2017-05-24 | 3M创新有限公司 | Ionic polymer membrane for a carbon dioxide electrolyzer |
| CN107208284A (en) * | 2015-02-09 | 2017-09-26 | 西门子公司 | Restoring method and electrolysis system that electrochemistry for carbon dioxide is utilized |
| CN107250438A (en) * | 2015-02-06 | 2017-10-13 | 西门子公司 | The method and electrolysis system utilized for carbon dioxide |
| CN107735512A (en) * | 2015-07-03 | 2018-02-23 | 西门子公司 | For electrochemistry using carbon dioxide, prepare the electrolysis system and restoring method of alkali carbonate and alkali metal hydrogencarbonate |
| CN107849713A (en) * | 2015-07-03 | 2018-03-27 | 西门子公司 | The reducing process and electrolysis system of carbon dioxide are utilized for electrochemistry |
| CN108004563A (en) * | 2016-10-27 | 2018-05-08 | 株式会社东芝 | Electrochemical reaction appts |
| CN108570690A (en) * | 2017-03-14 | 2018-09-25 | 株式会社东芝 | Carbon dioxide electrolysis unit |
| CN108624896A (en) * | 2017-03-21 | 2018-10-09 | 株式会社东芝 | Electrochemical reaction appts |
| CN108624905A (en) * | 2017-03-21 | 2018-10-09 | 株式会社东芝 | Carbon dioxide electrolysis unit and carbon dioxide electrolytic method |
| CN108699709A (en) * | 2016-02-24 | 2018-10-23 | 西门子股份公司 | The method and apparatus for utilizing carbon dioxide for electrochemistry |
| CN108779564A (en) * | 2016-03-10 | 2018-11-09 | 西门子股份公司 | The method and apparatus for utilizing carbon dioxide for electrochemistry |
-
2019
- 2019-08-14 CN CN201910750320.1A patent/CN110344071B/en active Active
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020105082A1 (en) * | 2001-01-04 | 2002-08-08 | International Business Machines Corporation | Method for forming interconnects on semiconductor substrates and structures formed |
| CN101657568A (en) * | 2005-10-13 | 2010-02-24 | 曼得拉能源替代有限公司 | Continuous co-current electrochemical reduction of carbon dioxide |
| CN102812158A (en) * | 2011-03-09 | 2012-12-05 | 松下电器产业株式会社 | Method for reducing carbon dioxide |
| CN102181876A (en) * | 2011-03-30 | 2011-09-14 | 昆明理工大学 | Method and device for preparing carbon monoxide through electrochemical catalytic reduction of carbon dioxide |
| US9217202B2 (en) * | 2011-12-12 | 2015-12-22 | Tsinghua University | Membrane reactor |
| CN105316700A (en) * | 2014-07-29 | 2016-02-10 | 中国科学院大连化学物理研究所 | Electrolytic tank and application for electrochemical reduction reaction of carbon dioxide |
| CN106715760A (en) * | 2014-09-08 | 2017-05-24 | 3M创新有限公司 | Ionic polymer membrane for a carbon dioxide electrolyzer |
| CN107250438A (en) * | 2015-02-06 | 2017-10-13 | 西门子公司 | The method and electrolysis system utilized for carbon dioxide |
| CN107208284A (en) * | 2015-02-09 | 2017-09-26 | 西门子公司 | Restoring method and electrolysis system that electrochemistry for carbon dioxide is utilized |
| CN107735512A (en) * | 2015-07-03 | 2018-02-23 | 西门子公司 | For electrochemistry using carbon dioxide, prepare the electrolysis system and restoring method of alkali carbonate and alkali metal hydrogencarbonate |
| CN107849713A (en) * | 2015-07-03 | 2018-03-27 | 西门子公司 | The reducing process and electrolysis system of carbon dioxide are utilized for electrochemistry |
| CN205329170U (en) * | 2015-11-16 | 2016-06-22 | 昆明理工大学 | Multi -chambered diaphragm electrolysis device that is carbon dioxide electroreduction carbon monoxide |
| CN105297067A (en) * | 2015-11-16 | 2016-02-03 | 昆明理工大学 | Multi-room diaphragm electrolysis method and device for electroreduction of carbon dioxide into carbon monoxide |
| CN108699709A (en) * | 2016-02-24 | 2018-10-23 | 西门子股份公司 | The method and apparatus for utilizing carbon dioxide for electrochemistry |
| CN108779564A (en) * | 2016-03-10 | 2018-11-09 | 西门子股份公司 | The method and apparatus for utilizing carbon dioxide for electrochemistry |
| CN108004563A (en) * | 2016-10-27 | 2018-05-08 | 株式会社东芝 | Electrochemical reaction appts |
| CN108570690A (en) * | 2017-03-14 | 2018-09-25 | 株式会社东芝 | Carbon dioxide electrolysis unit |
| CN108624896A (en) * | 2017-03-21 | 2018-10-09 | 株式会社东芝 | Electrochemical reaction appts |
| CN108624905A (en) * | 2017-03-21 | 2018-10-09 | 株式会社东芝 | Carbon dioxide electrolysis unit and carbon dioxide electrolytic method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115074758A (en) * | 2021-03-11 | 2022-09-20 | 本田技研工业株式会社 | Power generation device |
| EP4060086A1 (en) * | 2021-03-18 | 2022-09-21 | Kabushiki Kaisha Toshiba | Carbon dioxide electrolytic device |
| CN115110102A (en) * | 2021-03-18 | 2022-09-27 | 株式会社东芝 | Carbon dioxide electrolysis device |
| CN115110102B (en) * | 2021-03-18 | 2023-12-15 | 株式会社东芝 | Carbon dioxide electrolysis device |
| US11851774B2 (en) | 2021-03-18 | 2023-12-26 | Kabushiki Kaisha Toshiba | Carbon dioxide electrolytic device |
| CN113120866A (en) * | 2021-03-31 | 2021-07-16 | 中南大学 | Method for preparing elemental sulfur by using sulfur dioxide |
| CN113120866B (en) * | 2021-03-31 | 2022-04-22 | 中南大学 | Method for preparing elemental sulfur by using sulfur dioxide |
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