CN105506665B - A kind of method of high-temperature electrolysis CO2 CNTs - Google Patents
A kind of method of high-temperature electrolysis CO2 CNTs Download PDFInfo
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002041 carbon nanotube Substances 0.000 title description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 23
- 238000005485 electric heating Methods 0.000 claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000010431 corundum Substances 0.000 claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 230000036647 reaction Effects 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 230000007246 mechanism Effects 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical group [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 2
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 2
- 229910001953 rubidium(I) oxide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000007784 solid electrolyte Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 7
- 238000004140 cleaning Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 229910001120 nichrome Inorganic materials 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- -1 Fr2O Chemical compound 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910007470 ZnO—Al2O3 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of high-temperature electrolysis CO2The method of CNT processed, high-temperature electrolysis CO therein2CNT system processed includes electrolysis cells and electric heating unit, electrolysis cells are made up of dc source, negative electrode, anode, electrolytic cell and electrolyte, electrolyte is the mixture of fused carbonate and molten oxide, the mol ratio of oxide and carbonate is (0,0.2] in section, electrolysis temperature is between 610~690 DEG C, and during using constant-current electrolysis, the current density of dc source is controlled in 20~500mA/cm2Between, during using constant-potential electrolysis, the voltage of dc source is controlled between 2.2V~3.2V.The step of system one generates CNT, and reaction is simple, and accessory substance is few, and selectivity is good, has cleaning, energy-conservation, efficient, safe and sustainable feature, is energy-saving and emission-reduction and CO2Recycling provides new approach.
Description
Technical field
The present invention relates to a kind of high-temperature electrolysis CO2The method of CNT processed, belongs to energy-saving and emission-reduction and CO2Recycling
Field.
Background technology
Since the industrial revolution, the excessive exploitation of fossil fuel (coal, oil, natural gas etc.) makes CO in air2Concentration
0.4 ‰ are alreadyd exceed till now as 0.27 ‰ increases at the beginning of last century.According to statistics, the whole world is every year because caused by combustion of fossil fuel
CO2Up to 6Gt, end 2013, fossil energy provides the 90% of total world energy demand amount, it means that CO from now on2Row
High-volume it will also be continuously increased.However, the final product as the process of substance combustion containing carbons, CO2And content is most in nature
Abundant C1 resources, therefore, explore CO2Chemical conversion with using technology either to environmental protection or utilization of resources
It is all significant.
At present, CO2Chemical conversion technology focuses primarily upon catalytic activation synthesis organic-fuel or industrial chemicals, such as CH4、CO+
H2, urea, methanol etc..Cong Yu etc. uses ultra-fine Cu-ZnO-ZrO2Catalyst is methanol by carbon dioxide conversion and high income reaches
73.4g(k·h)-1, higher than industrial CH3OH catalyst Cu-ZnO-Al2O3；Tomishige etc. is by appropriate 2,2- dimethoxys third
Alkane is mixed with CeO2-ZrO2In catalyst system, carbon dioxide is promoted to generate dimethyl carbonate with methanol using the catalyst system and catalyzing；
Choudhary etc. makes CO using NiO-CaO catalyst2To CH4Conversion ratio reach 99%, and CO and H2Selectivity reach
100%.Reaction is required to carry out under more exacting terms above, such as high temperature, high pressure, catalyst etc., it is therefore desirable to matches somebody with somebody
Standby special reactor, expensive, service life is relatively low.In its course of reaction, because catalyst performance is relatively low, under high temperature
Easily inactivation, and also easily caused danger in production process, therefore the money of carbon dioxide is realized using high-pressure catalytic hydrogenization method
Sourceization, which utilizes, still suffers from many challenges and difficulty.
The very harsh method for transformation more than, in recent years, safe and clean and easily operated electrochemistry, which is caught, to be turned
Change CO2Technology turns into CO2One of focus of recycling area research.Currently, to CO2The research of electrochemical reduction is main
Concentrate in aqueous solvent or non-aqueous organic solvent to CO2It is electrolysed, in addition, CO2As a kind of highly stable incombustible
Molecule, its thermodynamic stability is very superior, therefore, it is very difficult, it is necessary to greater energy consumption that electroreduction is directly carried out to it
(high decomposition voltage), while cell reaction is extremely complex, efficiency and selectivity are poor.Based on this, a kind of low cost, device are developed
Simply, efficient CO2The method and device of recycling, it is very must to obtain preferably economic, society and environmental benefit
Want.
The content of the invention
The invention provides a kind of simple system, energy-conservation, low cost, efficient CO2Resource utilization method, high-temperature electrolysis
CO2CNT system processed, the system can realize CO under the conditions of low decomposition voltage and relative low temperature2Recycling, system
The CNT that the other field obtained in nanometer technology, electronics, optics and material science and technology is all of great value, and be electrolysed anti-
Should be relatively easy, can step generation CNT, good reaction selectivity, accessory substance is few.
The purpose of the present invention is achieved by the following technical solution：
A kind of high-temperature electrolysis CO2CNT system processed, the system include electrolysis cells and electric heating unit, electric heating unit
Member is heated to electrolysis cells, and electrolysis cells are made up of dc source, negative electrode, anode, electrolytic cell and electrolyte, and its feature exists
In：The electrolyte is the mixture of fused carbonate and molten oxide, in mixture, the mol ratio of oxide and carbonate
(0,0.2] in section, electrolysis temperature is between 610~690 DEG C, using constant-current electrolysis or constant-potential electrolysis, using perseverance
During current electroanalysis, the current density of dc source is controlled in 20~500mA/cm2Between, during using constant-potential electrolysis, direct current
The voltage in source is controlled between 2.2V~3.2V；In electrolysis, CNT and CO are obtained in negative electrode, anode obtains O2, electrolyte
With CO2Reaction is regenerated.
Its cell reaction mechanism is：
Anode reaction：2O2--4e-=O2
Cathode reaction：CO3 2-+4e-=C+3O2-
CO3 2-+2e-=CO+2O2-
CO3 2-+3e-=1/2CO+1/2C+5/2O2-
CNT is wherein enriched with simple substance carbon caused by negative electrode.
Further, the dc source current density is preferably 100~400mA/cm2, electrolytic cell temperature is preferably
627~677 DEG C.
Further, carbonate Li2CO3、Na2CO3、K2CO3、Rb2CO3、Cs2CO3、Fr2CO3、MgCO3、CaCO3、
SrCO3、 BaCO3、ZnCO3One or both of more than mixture；Oxide is Li2O、Na2O、K2O、Rb2O、Cs2O、
Fr2O、 MgO、CaO、SrO、BaO、ZnO、SiO2、Al2O3、Fe2O3One or both of more than mixture.
Further, when electrolyte is solid-state, provides electrolyte by the electric heating unit and reach complete molten condition institute
The heat energy needed.
Further, the electric heating unit is born using ceramics or other high temperature modification electric heating covers by adjusting transformer
Carry to regulate and control heating-up temperature.
Further, the cathode material of the electrolysis cells is nickel, platinum, titanium, ruthenium, iridium, palladium, iron, tungsten, chromium, copper, gold, stone
Ink or the alloy of several formation in stainless steel, or above-mentioned material；The anode material of the electrolysis cells be nickel, platinum, titanium, ruthenium,
The alloy of several formation in iridium, palladium, iron, tungsten, chromium, copper, gold, graphite or stainless steel, or above-mentioned material.
Further, the electrolytic cell uses high-purity corundum body crucible, high purity nickel or other high temperature corrosion-resisting type reactors.
Based on above-mentioned high-temperature electrolysis CO2The high-temperature electrolysis CO of CNT system processed2The method of CNT processed, including
Following steps：
(1) electrolysis cells being made up of dc source, negative electrode, anode, electrolytic cell and electrolyte are built；
(2) solid electrolyte is heated by electric heating unit to form molten state electrolyte；
(3) control electrolytic cell temperature constant at 610~690 DEG C；
(4) CO is passed through into electrolytic cell by airway tube2, during using constant-current electrolysis, control the electric current of dc source close
Degree is in 20~500mA/cm2Between, during using constant-potential electrolysis, the voltage of dc source is controlled between 2.2V~3.2V；Instead
Answer certain time, the step of main reaction one generation primary product simple substance carbon, be enriched with CNT in simple substance carbon, overall reaction is：
CO2=C+O2；
CO2=1/2O2+CO；
CO2=3/4O2+1/2CO+1/2C；
Its cell reaction mechanism is：
Anode reaction：2O2--4e-=O2
Cathode reaction：CO3 2-+4e-=C+3O2-
CO3 2-+2e-=CO+2O2-
CO3 2-+3e-=1/2CO+1/2C+5/2O2-。
The advantageous effects of the present invention are as follows：
1st, cell reaction process, heat energy is converted electrical energy into by electric heating unit, electrolyte is heated, according to electrolyte
Difference regulation and control heating-up temperature；Electric energy is provided using dc source simultaneously, according to the species and heating-up temperature of electrolyte, needed for regulation and control
Decomposition voltage or electric current, by being electrolysed CO2, negative electrode obtains CNT and CO, and anode obtains O2, electric energy is realized to chemistry
Transformation of energy and storage, the CO that electrolyte solution absorption is fed in electrolytic process2, electrolyte is regenerated, it is achieved thereby that
By CO2Recycle and recycling.
2nd, CO of the present invention2The mechanism of electrolysis of high-temperature electrolysis CNT is：
Anode reaction：
[1]2O2--4e-=O2
Cathode reaction：
[2] formation of carbon：CO3 2-+4e-=C+3O2-
[3] formation of carbon monoxide：CO3 2-+2e-=CO+2O2-
[4] formation of carbon monoxide and carbon：CO3 2-+3e-=1/2CO+1/2C+5/2O2-
Adduction cathode and anode is reacted, and can obtain cell reaction：
[5]M2CO3=C (s)+O2+M2O；
[6]M2CO3=CO+M2O+1/2O2；
[7]M2CO3=1/2CO+1/2C+M2O+3/4O2；
CO2Absorbing reaction：
[8]：M2O+CO2=M2CO3
By cell reaction [5], [6], [7] and CO2Absorbing reaction [8] sum up, electrolysis cells overall reaction can be obtained：
[9]CO2=C+O2；
[10]CO2=1/2O2+CO；
[11]CO2=3/4O2+1/2CO+1/2C
Carbanion in fused carbonate electrolyte is by converting for solid-state carbon simple substance and CO (such as equations [2]
With equation [3] Suo Shi), while generate O2-.The negative oxygen ion discharged on the one hand can be with the CO in atmosphere2React and regenerate
Carbonate (equation [8]), so as to realize sustainable CO2Trapping and be electrochemically transformed, also can migrate to anode occur oxidation and
Oxygen (equation [1]) is generated, forms CO2-CO3 2--C+CO+O2The circulatory system, wherein being rich in simple substance carbon caused by negative electrode
CNT.
3rd, the system by control electric current density and electrolysis temperature or control voltage and electrolysis temperature come synthesizing carbon nanotubes,
Electrolysis temperature is 610~690 DEG C, using constant-current electrolysis or constant-potential electrolysis, during using constant-current electrolysis, dc source
Current density is controlled in 20~500mA/cm2Between, during using constant-potential electrolysis, the voltage control of dc source 2.2V~
Between 3.2V, 0.5-2h is electrolysed, contains a large amount of CNTs in the simple substance carbon of negative electrode generation.
4th, compared with prior art, the system has the characteristics of following prominent：First, current density substantially reduces, electric current
Density is only 20~500mA/cm2, decomposition voltage is only 2.2V~3.2V；Second：Using a variety of carbonate and metal oxide
Mixture while system fusing point is reduced, adds capturing ability of the electrolyte to carbon dioxide, makes electricity as electrolyte
The renewal speed of solution matter greatly improves；3rd：Cheap iron wire and nichrome wire can be selected in electrode material, significantly reduces
Production cost.
5th, step generation CNT of the invention, reaction is simple, and accessory substance is few, and selectivity is good.Simultaneously using electric energy and
Electrochemical effect, build CO2Conversion CNT system processed, constitute perfect energy conversion and stocking system, have cleaning,
Efficiently, safe and sustainable feature, it is energy-saving and emission-reduction and CO2Recycling provides new approach.
Brief description of the drawings
Fig. 1 present system schematic diagrames
In figure：1 anode；2 electric heating covers；3 electrolyte；4 electrolytic cells；5 negative electrodes；6 airway tubes；7 dc sources；8 wires；9
Anodic product O2；10 reaction raw materials CO2；11 negative electrode accessory substance CO
Embodiment
Embodiment 1
Respectively by 22g Li2CO3、61g Na2CO3With 17g K2CO3Grind well mixed, shifted in mortar
Enter in corundum crucible；It is respectively 50cm by surface area2Nichrome wire and iron wire as anode and negative electrode；Make that temperature is constant to be
610 (± 2) DEG C, constant current density 20mA/cm2.After reaction 1 hour, received in simple substance carbon caused by negative electrode containing a large amount of carbon
Mitron.
Embodiment 2
Respectively by 61g Li2CO3、22g Na2CO3、17g K2CO3And 2.15g Na2It is equal that O grinds mixing in mortar
It is even, it is transferred in corundum crucible；It is respectively 10cm by surface area2Nichrome wire and iron wire as anode and negative electrode；
It is 620 (± 2) DEG C to make temperature constant, constant current density 150mA/cm2.After reaction 1 hour, in simple substance carbon caused by negative electrode
Contain a large amount of CNTs.
Embodiment 3
Respectively by 20g MgCO3、42g SrCO3、30g BaCO3And 3.17g K2It is equal that O grinds mixing in mortar
It is even, it is transferred in corundum crucible；It is respectively 5cm by surface area2Nichrome wire and iron wire as anode and negative electrode；Make
It is 630 (± 2) DEG C that temperature is constant, constant current density 350mA/cm2.After reaction 0.8 hour, in simple substance carbon caused by negative electrode
Contain a large amount of CNTs.
Embodiment 4
Respectively by 61g Li2CO3、22g Na2CO3、17g K2CO3And 2.7g Li2It is equal that O grinds mixing in mortar
It is even, it is transferred in corundum crucible；It is respectively 5cm by surface area2Nichrome wire and iron wire as anode and negative electrode；Make
It is 640 (± 2) DEG C that temperature is constant, constant current density 450mA/cm2.After reaction 0.8 hour, in simple substance carbon caused by negative electrode
Contain a large amount of CNTs.
Embodiment 5
Respectively by 46.5g Li2CO3、16.5g Na2CO3、12.75g K2CO3And 8.15g Na2O grounds travels in mortar
It is broken well mixed, it is transferred in corundum crucible；It is respectively 5cm by surface area2Nichrome wire and iron wire as anode
And negative electrode；It is 650 (± 2) DEG C to make temperature constant, and constant electric current is 500mA/cm2.It is single caused by negative electrode after reaction 0.8 hour
Contain a large amount of CNTs in matter carbon.
Embodiment 6
Respectively by 31g Li2CO3、11g Na2CO3、8.5g K2CO3And 6.5g K2It is equal that O grinds mixing in mortar
It is even, it is transferred in corundum crucible；It is respectively 5cm by surface area2Nichrome wire and iron wire as anode and negative electrode；Make
Constant temperature is 660 (± 2) DEG C, and voltage constant is 2.2~2.5V.After reaction 0.5 hour, contain in simple substance carbon caused by negative electrode
A large amount of CNTs.
Embodiment 7
Respectively by 20g MgCO3、42g SrCO3、30g BaCO3And 1.1g Li2It is equal that O grinds mixing in mortar
It is even, it is transferred in corundum crucible；It is respectively 5cm by surface area2Nichrome wire and iron wire as anode and negative electrode；Make
Constant temperature is 670 (± 2) DEG C, and voltage constant is 2.5~3.2V.After reaction 0.5 hour, contain in simple substance carbon caused by negative electrode
A large amount of CNTs.
Embodiment 8
Respectively by 20g MgCO3、42g SrCO3、30g BaCO3And 2g Li2O ground in mortar it is well mixed,
It is transferred in corundum crucible；It is respectively 5cm by surface area2Nichrome wire and iron wire as anode and negative electrode；Make temperature
It is 680 (± 2) DEG C to spend constant, and voltage constant is 2.2~3.2V.After reaction 0.5 hour, containing big in simple substance carbon caused by negative electrode
Measure CNT.
Embodiment 9
Respectively by 31g Li2CO3、11g Na2CO3、8.5g K2CO3And 2.8g Li2It is equal that O grinds mixing in mortar
It is even, it is transferred in corundum crucible；It is respectively 5cm by surface area2Nichrome wire and iron wire as anode and negative electrode；Make
Constant temperature is 690 (± 2) DEG C, and voltage constant is 2.5~3.2V.After reaction 0.5 hour, contain in simple substance carbon caused by negative electrode
A large amount of CNTs.
Claims (7)
- A kind of 1. high-temperature electrolysis CO2The method of CNT processed, high-temperature electrolysis CO therein2CNT system processed includes electrolysis Unit and electric heating unit, electric heating unit heat to electrolysis cells, and electrolysis cells are by dc source, negative electrode, anode, electricity Xie Chi and electrolyte composition, it is characterised in that：The electrolyte is the mixture of fused carbonate and molten oxide, mixture In, the mol ratio of oxide and carbonate (0,0.2] in section, electrolysis temperature is between 610~690 DEG C, using constant current Electrolysis or constant-potential electrolysis, during using constant-current electrolysis, the current density of dc source is controlled in 20~500mA/cm2It Between, during using constant-potential electrolysis, the voltage of dc source is controlled between 2.2V~3.2V；In electrolysis, obtain carbon in negative electrode and receive Mitron and CO, anode obtain O2, electrolyte and CO2Reaction is regenerated；Above-mentioned high-temperature electrolysis CO2The high-temperature electrolysis CO of CNT system processed2The method of CNT processed, comprises the following steps：(1) electrolysis cells being made up of dc source, negative electrode, anode, electrolytic cell and electrolyte are built；(2) solid electrolyte is heated by electric heating unit to form molten state electrolyte；(3) control electrolytic cell temperature constant at 610~690 DEG C；(4) CO is passed through into electrolytic cell by airway tube2, during using constant-current electrolysis, control the current density of dc source to exist 20~500mA/cm2Between, during using constant-potential electrolysis, the voltage of dc source is controlled between 2.2V~3.2V；Reaction Certain time, the step of main reaction one generate primary product simple substance carbon, are enriched with CNT in simple substance carbon, overall reaction is：CO2=C+O2；CO2=1/2O2+CO；CO2=3/4O2+1/2CO+1/2C；Its cell reaction mechanism is：Anode reaction：2O2--4e-=O2Cathode reaction：CO3 2-+4e-=C+3O2-CO3 2-+2e-=CO+2O2-CO3 2-+3e-=1/2CO+1/2C+5/2O2-。
- 2. high-temperature electrolysis CO according to claim 12The method of CNT processed, it is characterised in that the dc source electricity Current density is 100~400mA/cm2, electrolytic cell temperature is 627~677 DEG C.
- 3. high-temperature electrolysis CO according to claim 12The method of CNT processed, it is characterised in that electrolyte is solid-state When, provide the heat energy required for electrolyte reaches complete molten condition as the electric heating unit.
- 4. high-temperature electrolysis CO according to claim 12The method of CNT processed, it is characterised in that the electric heating unit Using ceramics or other high temperature modification electric heating covers, regulate and control heating-up temperature by adjusting transformer load.
- 5. high-temperature electrolysis CO according to claim 12The method of CNT processed, it is characterised in that carbonate is Li2CO3、Na2CO3、K2CO3、Rb2CO3、Cs2CO3、Fr2CO3、MgCO3、CaCO3、SrCO3、BaCO3、ZnCO3In one kind or two The mixture of the kind above；Oxide is Li2O、Na2O、K2O、Rb2O、Cs2O、Fr2O、MgO、CaO、SrO、BaO、ZnO、SiO2、 Al2O3、Fe2O3One or both of more than mixture.
- 6. high-temperature electrolysis CO according to claim 12The method of CNT processed, it is characterised in that the electrolysis cells Cathode material is several shapes in nickel, platinum, titanium, ruthenium, iridium, palladium, iron, tungsten, chromium, copper, gold, graphite or stainless steel, or above-mentioned material Into alloy；The anode material of the electrolysis cells is nickel, platinum, titanium, ruthenium, iridium, palladium, iron, tungsten, chromium, copper, gold, graphite or stainless The alloy of several formation in steel, or above-mentioned material.
- 7. high-temperature electrolysis CO according to claim 12The method of CNT processed, it is characterised in that the electrolytic cell uses High-purity corundum body crucible, high purity nickel or other high temperature corrosion-resisting type reactors.
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