CN205329170U - Multi -chambered diaphragm electrolysis device that is carbon dioxide electroreduction carbon monoxide - Google Patents

Multi -chambered diaphragm electrolysis device that is carbon dioxide electroreduction carbon monoxide Download PDF

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CN205329170U
CN205329170U CN201520909237.1U CN201520909237U CN205329170U CN 205329170 U CN205329170 U CN 205329170U CN 201520909237 U CN201520909237 U CN 201520909237U CN 205329170 U CN205329170 U CN 205329170U
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carbon dioxide
cathode chamber
chamber
anode
electrolyte
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施锦
李青远
沈风霞
贾友见
王琴
杨冬伟
李露
胡玉琪
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Kunming University of Science and Technology
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    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70Assemblies comprising two or more cells
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70Assemblies comprising two or more cells
    • C25B9/73Assemblies comprising two or more cells of the filter-press type
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The utility model relates to a multi -chambered diaphragm electrolysis device that is carbon dioxide electroreduction carbon monoxide belongs to carbon dioxide utilization technical field. This device electrolytic bath passes through perfluor sulfonic acid amberplex and separates into a plurality of electrode chambers, constitute the alternate multi -chambered diaphragm electrolysis pond of arranging with the anode chamber of cathode chamber, the bottom of cathode chamber and anode chamber is equipped with negative pole and positive pole respectively, the anode chamber top is equipped with the entry of water, what flow out in the gaseous absorption tower dissolves the bottom that the pipeline that has a large amount of carbon dioxide's organic compound electrolyte to pass through cathodic electrolysis liquid circulating device flowed into the cathode chamber, dissolving of cathode chamber upper portion has lower concentration carbon dioxide's organic compound electrolyte to return the top on gaseous absorption tower through cathodic electrolysis liquid circulating device, the side on gaseous absorption tower is equipped with the carbon dioxide entry, pipeline and gas tank connection are passed through to the top of cathode chamber. The multi -chambered diaphragm electrolysis device that utilizes this utility model to provide can be carbon monoxide with the continuous high -efficient ground electroreduction of carbon dioxide.

Description

A kind of by multicell diaphragm electrolysis apparatus that carbon dioxide electroreduction is carbon monoxide
Technical field
This utility model relates to a kind of by the multicell diaphragm electrolysis apparatus that carbon dioxide electroreduction is carbon monoxide, belongs to Resources of Carbon Dioxide and utilizes technical field。
Background technology
It is useful chemicals by carbon dioxide conversion, it is achieved carbon resource recycles, is field of energy environment realistic problem in the urgent need to address。Synthesis gas is a kind of widely used basic chemical industry raw material, and its Main Ingredients and Appearance is carbon monoxide and hydrogen。At present, synthesis gas is mainly produced by Fossil fuel, but, Fossil fuel is non-renewable, and in use also to give off substantial amounts of carbon dioxide, cause greenhouse gases effect and global warming, therefore, explore the production method of non-fossil fuel source synthesis gas, become an important research topic。This utility model adopts carbon dioxide and water to be that synthesis gas prepared by raw material, with Reproduceable electricity for electrolysis electric energy, carbon dioxide, water electrolysis are reduced to carbon monoxide, hydrogen, then the carbon monoxide of acquisition and hydrogen are mixed, preparing synthesis gas, gained synthesis gas is used for producing the downstream chemical products such as methanol, paraffin, polyurethane。
Synthesis gas is prepared for fundamental, it is necessary to the key problem of solution is: be carbon monoxide by carbon dioxide continuously and efficiently electroreduction with carbon dioxide, water and Reproduceable electricity。
Summary of the invention
In order to be carbon monoxide by carbon dioxide continuously and efficiently electroreduction, this utility model provides the multicell diaphragm electrolysis apparatus that a kind of carbon dioxide electroreduction is carbon monoxide, as shown in Figure 1, this utility model is achieved through the following technical solutions: divide the cell into multiple electrode chamber with perfluorinated sulfonic acid ion exchange membrane, constitute the multicell diaphragm cell of cathode chamber and anode chamber's interphase distribution, adopting the organic composite electrolyte dissolved with great amount of carbon dioxide is catholyte, aqueous solution containing supporting electrolyte is anolyte, it is negative electrode that electrolysis carbon dioxide carbon monoxide is had high selective electrode material by employing, inert electrode is anode, collectively form multicell diaphragm cell。In cell reaction process, there is oxidation reaction in water on anode, generates hydrion and oxygen, and hydrion moves in cathode chamber electrolyte through mass transport process, participates in carbon dioxide electro-reduction reaction, generates carbon monoxide。Owing to carbon dioxide electro-reduction reaction itself has water to generate, can there is electro-reduction reaction in water, cause having hydrogen to generate on negative electrode on negative electrode。
Described organic composite electrolyte comprises four kinds of function components: organic solvent, organic supporting electrolyte, proton conductive reinforcing agent and eelctro-catalyst。
Described organic solvent is the mixed solvent of a kind of or arbitrary proportion composition in Allyl carbonate, N-Methyl pyrrolidone, diethyl carbonate;Described organic supporting electrolyte is the mixed electrolyte of one or both arbitrary proportions combination in quaternary ammonium salt, choline chloride;Described proton conductive reinforcing agent is the mixture of a kind of or arbitrary proportion composition in trifluoromethyl ethanol, methanol and phenol;Described eelctro-catalyst is metal porphyrins, metal phthalocyanine compound, three carbonyl-2, one or more the arbitrary proportion mixture in 4 '-second bipyridine metal halide, glyoxaline ion liquid。
As the quaternary ammonium salt of supporting electrolyte organic in organic composite electrolyte, its chemical structural formula is:
R1、R2、R3、R4For C1-C5Hydrocarbon chain;X-For CF3SO3 -、ClO4 -、(CF3SO2)2N-、CF3COO-、H2PO4 -、HCO3 -、Cl-、HSO4 -、Br-
As the choline chloride of supporting electrolyte organic in organic composite electrolyte, its chemical structural formula is:
As the metal porphyrins of eelctro-catalyst in organic composite electrolyte, its chemical structural formula is:
M1For ferrum or cobalt element, R1、R2、R3、R4For hydrogen atom or C1-C5Hydrocarbon chain, or benzene substituent group;
As the metal phthalocyanine compound of eelctro-catalyst in organic composite electrolyte, its chemical structural formula is:
M2For ferrum, manganese or copper;
As three carbonyl-2 of eelctro-catalyst in organic composite electrolyte, 4 '-second bipyridine metal halide, its chemical structural formula is:
M3For manganese or rhenium element, X is Cl, Br or I, R1、R2For hydrogen atom or C1-C5Hydrocarbon chain;
As the glyoxaline ion liquid of eelctro-catalyst in organic composite electrolyte, its chemical structural formula is:
R1、R2For C1-C5Hydrocarbon chain;M, N are connected to hydrogen atom on hydrocarbon chain or functional group, and functional group is: CN, NH2Or OH;X-For (CF3SO2)2N-、CF3COO-、CF3SO3 -、HCO3 -、HSO4 -、H2PO4 -、Br-、Cl-
Supporting electrolyte in described anolyte is one or more the arbitrary proportion mixture in potassium bicarbonate, sodium bicarbonate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, dibastic sodium phosphate, potassium sulfate, sodium sulfate or sulphuric acid。
Described anode is yttrium oxide coating titanium anode, IrO2·Ta2O5Coating titanium anode, glass-carbon electrode or graphite electrode。
Described negative electrode is any one in Cu, Au, Ag, Zn electrode, or the alloy of above-mentioned metal。
By the multicell diaphragm electrolysis method that carbon dioxide electroreduction is carbon monoxide, it is as follows that it is embodied as step:
Step one, organic supporting electrolyte is dissolved in organic solvent, obtain the organic electrolyte of 0.1~3.0mol/L, organic electrolyte adds proton conductive reinforcing agent according to desired concn 0.1~0.4mol/L, it is that 0.01~0.2mol/L adds eelctro-catalyst according still further to desired concn, obtain organic composite electrolyte, carbon dioxide is dissolved in organic composite electrolyte, concentration is made to reach 0.09~0.21mol/L, gained solution is injected in diaphragm cell cathode chamber, is injected in diaphragm cell anode chamber by the aqueous solution that supporting electrolyte concentration is 0.1~2mol/L;
Step 2, connect electrolysis power, control decomposition voltage is 3.6~4.3V, under normal temperature and pressure conditions, carrying out cell reaction, at this moment there is electro-oxidation reaction in water on anode, generate hydrion and oxygen, the hydrion generated moves to negative electrode through perfluorinated sulfonic acid ion exchange membrane, participates in carbon dioxide electro-reduction reaction, generates carbon monoxide。Owing to carbon dioxide electro-reduction reaction itself has water to generate, cause that containing a certain amount of water in catholyte, electro-reduction reaction occurs water on negative electrode, generates hydrogen, therefore, by-product hydrogen on negative electrode。By negative electrode gas-phase reaction product collection in air accumulator, it is used for producing downstream product。In order to enable carbon dioxide electro-reduction reaction to carry out continuously and stably, this utility model have employed catholyte circulating technology: is passed into by carbon dioxide in absorption column of gas, with organic composite electrolyte solution absorption carbon dioxide, when gas concentration lwevel reaches or close to time saturated, this organic composite electrolyte dissolved with great amount of carbon dioxide is injected the bottom of multicell diaphragm cell cathode chamber, meanwhile, the organic composite electrolyte being in multicell diaphragm cell cathode chamber top automatically flows out from cathode chamber, this organic composite electrolyte containing low concentration carbon dioxide is introduced again in absorption column of gas, for solution absorption carbon dioxide, gained contains saturated or close to saturated gas concentration lwevel organic composite electrolyte, it is injected again bottom multicell diaphragm cell cathode chamber, it is consequently formed catholyte circulation。Control the speed that organic composite electrolyte flows into, flows out multicell diaphragm cell cathode chamber, enable carbon dioxide electro-reduction reaction to carry out continuously and stably。
A kind of by multicell diaphragm electrolysis apparatus that carbon dioxide electroreduction is carbon monoxide:
Device includes absorption column of gas 1, negative electrode 2, anode 3, air accumulator 4, perfluorinated sulfonic acid ion exchange membrane 5, electrolyzer and catholyte liquid circulating device, electrolyzer is separated into multiple electrode chamber by perfluorinated sulfonic acid ion exchange membrane 5, constitute the multicell diaphragm cell of cathode chamber and anode chamber's interphase distribution, the bottom of cathode chamber and anode chamber is respectively equipped with negative electrode 2 and anode 3, top, anode chamber is provided with the entrance of water, the organic composite electrolyte dissolved with great amount of carbon dioxide flowed out in absorption column of gas 1 is flowed into the bottom of cathode chamber by the pipeline of catholyte liquid circulating device, the organic composite electrolyte dissolved with low concentration carbon dioxide on cathode chamber top returns to the top of absorption column of gas 1 by catholyte liquid circulating device, the side of absorption column of gas 1 is provided with carbon dioxide entrance, the top of cathode chamber is connected with air accumulator 4 by pipeline。
Compared with prior art, this utility model has techniques below advantage:
(1) the multicell diaphragm electrolysis apparatus that this utility model proposes, carbon dioxide electro-reduction reaction can carry out in organic composite electrolyte, and meanwhile, the electro-oxidation reaction of water can carry out in aqueous。Owing to carbon dioxide is nonpolar molecule, organic composite electrolyte has good dissolubility, therefore, electroreduction carbon dioxide in organic composite electrolyte, it is possible to improve the electric current density of carbon dioxide electro-reduction reaction;
(2) the multicell diaphragm electrolysis apparatus that this utility model proposes, its cathode chamber electrolyte is organic composite electrolyte, and this electrolyte comprises four kinds of function components: organic solvent, organic supporting electrolyte, proton conductive reinforcing agent and eelctro-catalyst。The organic solvent that this utility model adopts has very strong dissolved carbon dioxide ability, the supporting electrolyte adopted has significantly high electrochemical stability, the proton conductive reinforcing agent adopted can promote hydrion migration in organic electrolyte and ion exchange membrane, and the eelctro-catalyst adopted can reduce the overpotential of carbon dioxide electro-reduction reaction。Therefore, electroreduction carbon dioxide in above-mentioned organic composite electrolyte, it is possible to be effectively improved the electric current density of carbon dioxide electro-reduction reaction, reduces the overpotential of carbon dioxide electro-reduction reaction simultaneously;
(3) this utility model have employed catholyte circulating technology, it is possible to makes carbon dioxide electro-reduction reaction carry out when continuous-stable。Catholyte circulation is achieved in that in carbon dioxide absorption tower, with organic composite electrolyte solution absorption carbon dioxide, when gas concentration lwevel reaches or close to time saturated, organic composite electrolyte dissolved with great amount of carbon dioxide is injected bottom multicell diaphragm cell cathode chamber, meanwhile, the organic compound solution being in cathode chamber top constantly flows out from cathode chamber, this organic composite electrolyte containing low concentration carbon dioxide is introduced again in absorption column of gas, for solution absorption carbon dioxide, gained contains saturated or close to saturated gas concentration lwevel organic composite electrolyte and is injected again bottom multicell diaphragm cell cathode chamber, it is consequently formed catholyte circulation。By controlling the speed that organic composite electrolyte flows into, flows out multicell diaphragm cell cathode chamber, it is possible to make carbon dioxide electro-reduction reaction carry out when continuous-stable。
(4) the multicell diaphragm electrolysis apparatus that this utility model proposes is easily achieved industrial applications。Such as: can pass through to increase electrode chamber quantity, increase electrode chamber volume and the method expanding electrode area, improve the production capacity of multicell diaphragm electrolysis apparatus。
Accompanying drawing explanation
Fig. 1 is this utility model by the multicell diaphragm electrolysis apparatus schematic diagram that carbon dioxide electroreduction is carbon monoxide。
In figure: 1-absorption column of gas, 2-negative electrode, 3-anode, 4-air accumulator, 5-perfluorinated sulfonic acid ion exchange membrane。
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the utility model is described in further detail。
Embodiment 1
Multicell diaphragm electrolysis method by carbon dioxide electroreduction is carbon monoxide: divide the cell into multiple electrode chamber with perfluorinated sulfonic acid ion exchange membrane, constitute the multicell diaphragm cell of cathode chamber and anode chamber's interphase distribution, cathode chamber electrolyte is the organic composite electrolyte dissolved with carbon dioxide, anode chamber's electrolyte is the aqueous solution containing supporting electrolyte, negative electrode adopts has high selective metal electrode to electrolysis carbon dioxide carbon monoxide, anode is inert electrode, in cell reaction process, negative electrode there is carbon monoxide generate, simultaneously by-product hydrogen。
Described organic composite electrolyte comprises four kinds of function components: organic solvent, organic supporting electrolyte, proton conductive reinforcing agent and eelctro-catalyst。
Described organic solvent is Allyl carbonate;Described organic supporting electrolyte is tetrabutylammonium perchlorate's quaternary ammonium salt;Described proton conductive reinforcing agent is trifluoromethyl ethanol;Described eelctro-catalyst is iron content porphyrin compound。
The supporting electrolyte of described anolyte is sulphuric acid。
Described anode is IrO2·Ta2O5Coating titanium anode, negative electrode is Au。
Implement step as follows:
Step one, organic supporting electrolyte is dissolved in organic solvent, obtain the organic electrolyte of 3.0mol/L, in organic electrolyte according to desired concn be 0.1mol/L add proton conductive reinforcing agent, it is that 0.01mol/L adds eelctro-catalyst according still further to desired concn, obtain organic composite electrolyte, carbon dioxide is dissolved in organic composite electrolyte, concentration is made to reach 0.09mol/L, gained solution is injected in diaphragm cell cathode chamber, is injected in diaphragm cell anode chamber as anolyte by the aqueous solution that supporting electrolyte concentration is 0.1mol/L;
Step 2, connect electrolysis power, controls decomposition voltage is 4.3V, under normal temperature and pressure conditions, when cell reaction carry out 2 little constantly, record generation carbon monoxide electric current density be 430A/m2, the current efficiency generating carbon monoxide is 91%;Cell reaction carries out in process, catholyte is in recurrent state all the time, what flow out from absorption column of gas contains saturated or close to saturated gas concentration lwevel organic composite electrolyte, it is injected into bottom multicell diaphragm electrolysis apparatus cathode chamber, meanwhile, it is in the organic composite electrolyte on cathode chamber top, constantly flow out from cathode chamber, this organic composite electrolyte containing low concentration carbon dioxide is introduced again in absorption column of gas, for solution absorption carbon dioxide, gained contains saturated or close to saturated gas concentration lwevel organic composite electrolyte and is injected again bottom multicell diaphragm cell cathode chamber, it is consequently formed catholyte circulation。Control the speed that catholyte flows into, flows out multicell diaphragm cell cathode chamber, enable carbon dioxide electro-reduction reaction to carry out when continuous-stable。
As shown in Figure 1, by the multicell diaphragm electrolysis apparatus that carbon dioxide electroreduction is carbon monoxide, its composition includes absorption column of gas 1, negative electrode 2, anode 3, air accumulator 4, perfluorinated sulfonic acid ion exchange membrane 5, electrolyzer and catholyte liquid circulating device, multiple electrode chamber is divided the cell into perfluorinated sulfonic acid ion exchange membrane 5, constitute the multicell diaphragm cell of cathode chamber and anode chamber's interphase distribution, the bottom of cathode chamber and anode chamber is respectively equipped with negative electrode 2 and anode 3, top, anode chamber is provided with the entrance of water, the organic composite electrolyte dissolved with carbon dioxide flowed out in absorption column of gas 1 is flowed into the bottom of cathode chamber by the pipeline of catholyte liquid circulating device, cathode chamber top returns to the top of absorption column of gas 1 dissolved with the organic composite electrolyte of carbon dioxide by catholyte liquid circulating device, the side of absorption column of gas 1 is provided with carbon dioxide entrance, the top of cathode chamber is connected with air accumulator 4 by pipeline。
Embodiment 2
Multicell diaphragm electrolysis method by carbon dioxide electroreduction is carbon monoxide: divide the cell into multiple electrode chamber with perfluorinated sulfonic acid ion exchange membrane, constitute the multicell diaphragm cell of cathode chamber and anode chamber's interphase distribution, cathode chamber electrolyte is the organic composite electrolyte dissolved with carbon dioxide, anode chamber's electrolyte is the aqueous solution containing supporting electrolyte, electrolysis carbon dioxide is prepared carbon monoxide and is had high selective metal electrode by negative electrode employing, anode is inert electrode, in cell reaction process, negative electrode there is carbon monoxide generate, simultaneously by-product hydrogen。
Described organic composite electrolyte comprises four kinds of function components: organic solvent, organic supporting electrolyte, proton conductive reinforcing agent and eelctro-catalyst。
Described organic solvent is N-Methyl pyrrolidone;Described organic supporting electrolyte is choline chloride;Described proton conductive reinforcing agent is methanol;Described eelctro-catalyst is 1-butyl-3-Methylimidazole. trifluoromethyl sulfonic acid。
The supporting electrolyte of described anolyte is sodium sulfate。
Described anode is graphite electrode, and negative electrode is Ag。
Implement step as follows:
Step one, organic supporting electrolyte is dissolved in organic solvent, obtain the organic electrolyte of 0.1mol/L, in organic electrolyte according to desired concn be 0.4mol/L add proton conductive reinforcing agent, it is that 0.2mol/L adds eelctro-catalyst according still further to desired concn, obtain organic composite electrolyte, carbon dioxide is dissolved in organic composite electrolyte, concentration is made to reach 0.21mol/L, gained solution is injected in diaphragm cell cathode chamber, is injected in diaphragm cell anode chamber as anolyte by the aqueous solution that supporting electrolyte concentration is 2mol/L;
Step 2, connect electrolysis power, controls decomposition voltage is 3.6V, under normal temperature and pressure conditions, when cell reaction carry out 2 little constantly, record generation carbon monoxide electric current density be 410A/m2, the current efficiency generating carbon monoxide is 93%;Cell reaction carries out in process, catholyte is in recurrent state all the time, what flow out from absorption column of gas contains saturated or close to saturated gas concentration lwevel organic composite electrolyte, it is injected into bottom multicell diaphragm electrolysis apparatus cathode chamber, meanwhile, it is in the organic composite electrolyte on cathode chamber top, constantly flow out from cathode chamber, this organic composite electrolyte containing low concentration carbon dioxide is introduced again in absorption column of gas, for solution absorption carbon dioxide, gained contains saturated or close to saturated gas concentration lwevel organic composite electrolyte and is injected again bottom multicell diaphragm cell cathode chamber, it is consequently formed catholyte circulation。Control the speed that catholyte flows into, flows out multicell diaphragm cell cathode chamber, enable carbon dioxide electro-reduction reaction to carry out when continuous-stable。
As shown in Figure 1, by the multicell diaphragm electrolysis apparatus that carbon dioxide electroreduction is carbon monoxide, its composition includes absorption column of gas 1, negative electrode 2, anode 3, air accumulator 4, perfluorinated sulfonic acid ion exchange membrane 5, electrolyzer and catholyte liquid circulating device, multiple electrode chamber is divided the cell into perfluorinated sulfonic acid ion exchange membrane 5, constitute the multicell diaphragm cell of cathode chamber and anode chamber's interphase distribution, the bottom of cathode chamber and anode chamber is respectively equipped with negative electrode 2 and anode 3, top, anode chamber is provided with the entrance of water, the organic composite electrolyte dissolved with carbon dioxide flowed out in absorption column of gas 1 is flowed into the bottom of cathode chamber by the pipeline of catholyte liquid circulating device, cathode chamber top returns to the top on absorption tower 1 dissolved with the organic composite electrolyte of carbon dioxide by catholyte liquid circulating device, the side of absorption column of gas 1 is provided with carbon dioxide entrance, the top of cathode chamber is connected with air accumulator 4 by pipeline。
Embodiment 3
Multicell diaphragm electrolysis method by carbon dioxide electroreduction is carbon monoxide: divide the cell into multiple electrode chamber with perfluorinated sulfonic acid ion exchange membrane, constitute the multicell diaphragm cell of cathode chamber and anode chamber's interphase distribution, cathode chamber electrolyte is the organic composite electrolyte dissolved with carbon dioxide, anode chamber's electrolyte is the aqueous solution containing supporting electrolyte, electrolysis carbon dioxide is prepared carbon monoxide and is had high selective metal electrode by negative electrode employing, anode is inert electrode, in cell reaction process, negative electrode there is carbon monoxide generate, simultaneously by-product hydrogen。
Described organic composite electrolyte comprises four kinds of function components: organic solvent, organic supporting electrolyte, proton conductive reinforcing agent and eelctro-catalyst。
Described organic solvent is diethyl carbonate;Described organic supporting electrolyte is tetrabutylammonium perchlorate's quaternary ammonium salt;Described proton conductive reinforcing agent is phenol;Described eelctro-catalyst is FePC。
The supporting electrolyte of described anolyte is potassium bicarbonate。
Described anode is glass-carbon electrode, and negative electrode is Cu/Zn alloy electrode。
Implement step as follows:
Step one, organic supporting electrolyte is dissolved in organic solvent, obtain the organic electrolyte of 0.2mol/L, in organic electrolyte according to desired concn be 0.4mol/L add proton conductive reinforcing agent, it is that 0.03mol/L adds eelctro-catalyst according still further to desired concn, obtain organic composite electrolyte, carbon dioxide is dissolved in organic composite electrolyte, concentration is made to reach 0.11mol/L, gained solution is injected in diaphragm cell cathode chamber, is injected in diaphragm cell anode chamber as anolyte by the aqueous solution that supporting electrolyte concentration is 0.3mol/L;
Step 2, connect electrolysis power, controls decomposition voltage is 4.3V, under normal temperature and pressure conditions, when cell reaction carry out 2 little constantly, record generation carbon monoxide electric current density be 430A/m2, the current efficiency generating carbon monoxide is 93%;Cell reaction carries out in process, catholyte is in recurrent state all the time, what flow out from absorption column of gas contains saturated or close to saturated gas concentration lwevel organic composite electrolyte, it is injected into bottom multicell diaphragm electrolysis apparatus cathode chamber, meanwhile, it is in the organic composite electrolyte on cathode chamber top, constantly flow out from cathode chamber, this organic composite electrolyte containing low concentration carbon dioxide is introduced again in absorption column of gas, for solution absorption carbon dioxide, gained contains saturated or close to saturated gas concentration lwevel organic composite electrolyte and is injected again bottom multicell diaphragm cell cathode chamber, it is consequently formed catholyte circulation。Control the speed that catholyte flows into, flows out multicell diaphragm cell cathode chamber, enable carbon dioxide electro-reduction reaction to carry out when continuous-stable。
As shown in Figure 1, by the multicell diaphragm electrolysis apparatus that carbon dioxide electroreduction is carbon monoxide, its composition includes absorption column of gas 1, negative electrode 2, anode 3, air accumulator 4, perfluorinated sulfonic acid ion exchange membrane 5, electrolyzer and catholyte liquid circulating device, multiple electrode chamber is divided the cell into perfluorinated sulfonic acid ion exchange membrane 5, constitute the multicell diaphragm cell of cathode chamber and anode chamber's interphase distribution, the bottom of cathode chamber and anode chamber is respectively equipped with negative electrode 2 and anode 3, top, anode chamber is provided with the entrance of water, the organic composite electrolyte dissolved with carbon dioxide flowed out in absorption column of gas 1 is flowed into the bottom of cathode chamber by the pipeline of catholyte liquid circulating device, cathode chamber top returns to the top of absorption column of gas 1 dissolved with the organic composite electrolyte of carbon dioxide by catholyte liquid circulating device, the side on absorption tower 1 is provided with carbon dioxide entrance, the top of cathode chamber is connected with air accumulator 4 by pipeline。
Embodiment 4
Multicell diaphragm electrolysis method by carbon dioxide electroreduction is carbon monoxide: divide the cell into multiple electrode chamber with perfluorinated sulfonic acid ion exchange membrane, constitute the multicell diaphragm cell of cathode chamber and anode chamber's interphase distribution, cathode chamber electrolyte is the organic composite electrolyte dissolved with carbon dioxide, anode chamber's electrolyte is the aqueous solution containing supporting electrolyte, negative electrode adopts has high selective metal electrode to electrolysis carbon dioxide carbon monoxide, anode is inert electrode, in cell reaction process, negative electrode there is carbon monoxide generate, simultaneously by-product hydrogen。
Described organic composite electrolyte comprises four kinds of function components: organic solvent, organic supporting electrolyte, proton conductive reinforcing agent and eelctro-catalyst。
Described organic solvent is mass ratio is diethyl carbonate and the N-Methyl pyrrolidone mixture of 1:1;Described organic supporting electrolyte is mass ratio is tetrabutylammonium perchlorate's quaternary ammonium salt and the choline chloride mixture of 1:1;Described proton conductive reinforcing agent is mass ratio is the trifluoromethyl ethanol of 1:1:1, methanol and phenol mixture;Described eelctro-catalyst is CuPc and three carbonyl-2 of mass ratio 1:1,4 '-second bipyridine manganese chloride mixture。
Described supporting electrolyte is mass ratio is the potassium dihydrogen phosphate of 1:1:1, sodium dihydrogen phosphate and potassium hydrogen phosphate mixture。
Described anode is yttrium oxide coating titanium anode, and negative electrode is Cu electrode。
Implement step as follows:
Step one, organic supporting electrolyte is dissolved in organic solvent, obtain the organic electrolyte of 2.8mol/L, in organic electrolyte according to desired concn be 0.3mol/L add proton conductive reinforcing agent, it is that 0.2mol/L adds eelctro-catalyst according still further to desired concn, obtain organic composite electrolyte, carbon dioxide is dissolved in organic composite electrolyte, concentration is made to reach 0.21mol/L, gained solution is injected in diaphragm cell cathode chamber, is injected in diaphragm cell anode chamber as anolyte by the aqueous solution that supporting electrolyte concentration is 2mol/L;
Step 2, connect electrolysis power, controls decomposition voltage is 4.0V, under normal temperature and pressure conditions, when cell reaction carry out 2 little constantly, record generation carbon monoxide electric current density be 493A/m2, the current efficiency generating carbon monoxide is 94%;Cell reaction carries out in process, catholyte is in recurrent state all the time, what flow out from absorption column of gas contains saturated or close to saturated gas concentration lwevel organic composite electrolyte, it is injected into bottom multicell diaphragm electrolysis apparatus cathode chamber, meanwhile, it is in the organic composite electrolyte on cathode chamber top, constantly flow out from cathode chamber, this organic composite electrolyte containing low concentration carbon dioxide is introduced again in absorption column of gas, for solution absorption carbon dioxide, gained contains saturated or close to saturated gas concentration lwevel organic composite electrolyte and is injected again the bottom of multicell diaphragm cell cathode chamber, it is consequently formed catholyte circulation。Control the speed that catholyte flows into, flows out multicell diaphragm cell cathode chamber, enable carbon dioxide electro-reduction reaction to carry out when continuous-stable。
As shown in Figure 1, by the multicell diaphragm electrolysis apparatus that carbon dioxide electroreduction is carbon monoxide, its composition includes absorption column of gas 1, negative electrode 2, anode 3, air accumulator 4, perfluorinated sulfonic acid ion exchange membrane 5, electrolyzer and catholyte liquid circulating device, multiple electrode chamber is divided the cell into perfluorinated sulfonic acid ion exchange membrane 5, constitute the multicell diaphragm cell of cathode chamber and anode chamber's interphase distribution, the bottom of cathode chamber and anode chamber is respectively equipped with negative electrode 2 and anode 3, top, anode chamber is provided with the entrance of water, the organic composite electrolyte dissolved with carbon dioxide flowed out in absorption tower 1 is flowed into the bottom of cathode chamber by the pipeline of catholyte liquid circulating device, cathode chamber top returns to the top of absorption column of gas 1 dissolved with the organic composite electrolyte of carbon dioxide by catholyte liquid circulating device, the side on absorption tower 1 is provided with carbon dioxide entrance, the top of cathode chamber is connected with air accumulator 4 by pipeline。
Above in association with accompanying drawing, detailed description of the invention of the present utility model is explained in detail, but this utility model is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art possess, it is also possible to make various change under the premise without departing from this utility model objective。

Claims (1)

1. one kind by multicell diaphragm electrolysis apparatus that carbon dioxide electroreduction is carbon monoxide, it is characterized in that: device includes absorption column of gas (1), negative electrode (2), anode (3), air accumulator (4), perfluorinated sulfonic acid ion exchange membrane (5), electrolyzer and catholyte liquid circulating device, perfluorinated sulfonic acid ion exchange membrane (5) is adopted to divide the cell into multiple electrode chamber, constitute the multicell diaphragm cell of cathode chamber and anode chamber's interphase distribution, the bottom of cathode chamber and anode chamber is respectively equipped with negative electrode (2) and anode (3), top, anode chamber is provided with the entrance of water, the organic composite electrolyte dissolved with carbon dioxide flowed out in absorption column of gas (1) is flowed into the bottom of cathode chamber by the pipeline of catholyte liquid circulating device, cathode chamber top returns to the top of absorption column of gas (1) dissolved with the organic composite electrolyte of carbon dioxide by catholyte liquid circulating device, the side of absorption column of gas (1) is provided with carbon dioxide entrance, the top of cathode chamber is connected with air accumulator (4) by pipeline。
CN201520909237.1U 2015-11-16 2015-11-16 Multi -chambered diaphragm electrolysis device that is carbon dioxide electroreduction carbon monoxide Withdrawn - After Issue CN205329170U (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN107841762A (en) * 2016-09-19 2018-03-27 中国科学院大连化学物理研究所 A kind of Carbon dioxide electrochemical reduction elctro-catalyst and its preparation and application
CN110344071A (en) * 2019-08-14 2019-10-18 碳能科技(北京)有限公司 Electroreduction CO2Device and method
EP3626861A1 (en) * 2018-09-18 2020-03-25 Covestro Deutschland AG Electrolytic cell, electrolyzer and method for the reduction of co2

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105297067B (en) * 2015-11-16 2018-02-09 昆明理工大学 A kind of multicell diaphragm electrolysis method and apparatus by carbon dioxide electroreduction for carbon monoxide
CN107841762A (en) * 2016-09-19 2018-03-27 中国科学院大连化学物理研究所 A kind of Carbon dioxide electrochemical reduction elctro-catalyst and its preparation and application
EP3626861A1 (en) * 2018-09-18 2020-03-25 Covestro Deutschland AG Electrolytic cell, electrolyzer and method for the reduction of co2
WO2020057998A1 (en) * 2018-09-18 2020-03-26 Covestro Deutschland Ag Electrolysis cell, electrolyzer and method for reducing co2
CN110344071A (en) * 2019-08-14 2019-10-18 碳能科技(北京)有限公司 Electroreduction CO2Device and method

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