CN101250711B - Electrochemical reduction method and apparatus for carbonic anhydride in ionic liquid - Google Patents
Electrochemical reduction method and apparatus for carbonic anhydride in ionic liquid Download PDFInfo
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- CN101250711B CN101250711B CN2008100582257A CN200810058225A CN101250711B CN 101250711 B CN101250711 B CN 101250711B CN 2008100582257 A CN2008100582257 A CN 2008100582257A CN 200810058225 A CN200810058225 A CN 200810058225A CN 101250711 B CN101250711 B CN 101250711B
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- ionic liquid
- electrochemical
- anode
- reaction
- carbon dioxide
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 10
- 235000011089 carbon dioxide Nutrition 0.000 title claims description 21
- 229960004424 carbon dioxide Drugs 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- -1 hydrogen ions Chemical class 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000003487 electrochemical reaction Methods 0.000 claims description 9
- 238000009792 diffusion process Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000007086 side reaction Methods 0.000 claims description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 9
- 238000006722 reduction reaction Methods 0.000 abstract description 9
- 239000001569 carbon dioxide Substances 0.000 abstract description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000002848 electrochemical method Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 230000002860 competitive effect Effects 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000010517 secondary reaction Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Abstract
The invention relates to an electrochemical reducing method of carbon dioxide in ionic liquid and an electrochemical reducing device. The method comprises following steps: injecting ionic liquid in a cathode chamber in the electrochemical reducing device, inputting the carbon dioxide, inputting hydrogen on the inner side of an anode bipolar plate, oxidizing the hydrogen on an anode, generating hydrogen ions, enabling H+ to traverse through proton exchange membrane to reach a cathode, transmitting electrons to the cathode through an external circuit, enabling the carbon dioxide and the H+ to generate electrochemical reduction reaction on the cathode, generating organic compound such as carbinol and the like, and obtaining the carbinol, water and other secondary reaction products through distilling the organic compound which is generated. The ionic liquid of the invention has very high electrical conductivity and ion mobility, the ionic liquid is suitable to be used as a media system ofelectrochemical reaction, simultaneously, the ionic liquid has the advantages of low volatility and small toxicity, competitive reaction of the H+ is inhibited, since the solubility of the carbon dioxide in the ionic liquid is very high, the efficiency of the electrochemical reduction reaction of the carbon dioxide is also comparatively high, and the electrochemical method of the invention utilizes CO2 to generate the organic compounds such as the carbinol and the like (by products are aminic acid, formaldehyde and the like), which realizes the resource utilization of the CO2.
Description
Technical field
The present invention relates to electrochemical reduction method and the device of carbonic acid gas in ionic liquid.
Background technology
Carbonic acid gas being converted into organic compound such as methyl alcohol with electrochemical method is an important channel of realizing the carbonic acid gas resource utilization, and the electrochemical Reduction of Carbon Dioxide reaction can be carried out in the aqueous solution, also can carry out [1] in non-aqueous system.In the aqueous solution, the subject matter that the electro-reduction reaction of carbonic acid gas runs into has: 1. the current efficiency of carbonic acid gas generation electro-reduction reaction is low; 2. carbonic acid gas solubleness in the aqueous solution is low excessively.In non-aqueous solvent, the subject matter that the electrochemical Reduction of Carbon Dioxide reaction runs into: 1. Chang Yong three kinds of organic solvents (acetonitrile, dimethyl formamide and methyl-sulphoxide) have volatility and toxic side effect; 2. water has very big influence to the electrochemical properties of above-mentioned three kinds of organic solvents, needs through refinement treatment before solvent uses, and must remove the moisture in desolvating, but carbonic acid gas has water to generate in the process that electrochemical reducting reaction takes place.For above-mentioned reasons, it is very necessary to explore new electrolyte system.
Reference:
[1] Zhang Li, Luo Yiwen, button east, Xiao Liping, Lu Jiaxing, CO
2Electroreduction behavior on copper electrode. SCI, 2007 (28) 1660-1662.
Summary of the invention
The purpose of this invention is to provide a kind of method, make carbonic acid gas that electrochemical reducting reaction take place in ionic liquid, and generate organic compound (by product is formic acid, formaldehyde etc.) such as methyl alcohol, realize the carbonic acid gas resource utilization.
The ion liquid structural formula that the present invention selects for use is:
R
1, R
2: H, C
1-C
5Alkyl
The method and apparatus of electrochemical reaction:
To separate with proton exchange membrane (perfluoro sulfonic acid membrane Nafion) between the cathode compartment of electrochemical reaction appts and the anolyte compartment, inject above-mentioned ionic liquid in the cathode compartment, be close to wire netting on the proton exchange membrane as negative electrode; The Pt/C catalyzer is arranged on the anode, and catalyst layer is made up of diffusion layer (carbon paper or carbon cloth) and Catalytic Layer (Pt/C catalyzer) two portions, is distributed with tiny groove on the bipolar plates, has collected current and guarantees H
2The effect of supply.Hydrogen is oxidized on anode, generates hydrogen ion, H
+Pass proton exchange membrane and arrive negative electrode, electronics is transferred to negative electrode by external circuit.Carbonic acid gas and H
+Electrochemical reducting reaction takes place on negative electrode, generates methyl alcohol and other side reaction products.The structure of electrochemical reaction appts can be expressed as:
H
2(g), Pt|Nafion| metallic cathode, CO
2, CH
3OH
The electrode reaction equation is:
Anode: 3H
2→ 6H
++ 6e
Negative electrode: CO
2+ 6H
++ 6e → CH
3OH+H
2O
Advantage that the present invention is compared with prior art had or positively effect:
1, above-mentioned ionic liquid has very high specific conductivity and mobility of ions, is suitable as the medium system of electrochemical reaction, and above-mentioned ionic liquid has the low and little advantage of toxicity of volatility simultaneously.
2, H
+Competing reaction be suppressed, and since the solubleness of carbonic acid gas in above-mentioned ionic liquid very high, the electro-reduction reaction efficient of carbonic acid gas is also higher.
Electrochemical method of the present invention utilizes CO
2Generate organic compound (by product is formic acid, formaldehyde etc.) such as methyl alcohol, realized CO
2Resource utilization.
Description of drawings
Fig. 1 is a carbonic acid gas electrochemical reaction appts synoptic diagram of the present invention.
Among the figure, 1-ionic liquid, 2-wire netting negative electrode, 3-proton exchange membrane, 4-Catalytic Layer, 5-diffusion layer, 6-bipolar plates.
Embodiment
As shown in Figure 1, will separate with proton exchange membrane (perfluoro sulfonic acid membrane Nafion) between the cathode compartment of electrochemical reaction appts and the anolyte compartment, inject above-mentioned ionic liquid in the cathode compartment, its structural formula is:
R
1, R
2: H, C
1-C
5Alkyl
Feed carbonic acid gas in the cathode compartment, be close to wire netting on the proton exchange membrane as negative electrode; The Pt/C catalyzer is arranged on the anode, catalyst layer is made up of diffusion layer (carbon paper or carbon cloth) and Catalytic Layer (Pt/C catalyzer) two portions, the effect of diffusion layer is to support Catalytic Layer, for electrochemical reaction provides gas passage, be distributed with tiny groove on the anode bipolar plate (material is carbon, stainless steel or titanium).
In the anolyte compartment of electrochemical reaction appts, feed hydrogen, the oxidized generation of hydrogen H
+, H
+Pass proton exchange membrane and arrive negative electrode, carbonic acid gas and H
+Electrochemical reducting reaction takes place on negative electrode, generate organic compound such as methyl alcohol, the mixture of generation obtains methyl alcohol, water and other side reaction products through rectifying.
Claims (2)
1. the method for electrochemical reducting reaction takes place in a carbonic acid gas in ionic liquid, it is characterized in that injecting ionic liquid in the cathode compartment in electrochemical reaction appts, and feeds carbonic acid gas, at the inboard hydrogen that feeds of anode bipolar plate, hydrogen is oxidized on anode, generates hydrogen ion, H
+Pass proton exchange membrane and arrive negative electrode, electronics is then transferred to negative electrode by external circuit, carbonic acid gas and H
+Electrochemical reducting reaction takes place on negative electrode, generate organic compound such as methyl alcohol, the organic compound of generation obtains methyl alcohol, water and other side reaction products through rectifying, and ion liquid structural formula is:
R
1, R
2: H, C
1-C
5Alkyl
The Pt/C catalyzer is arranged on the anode, and catalyzer is made up of diffusion layer and Catalytic Layer two portions, and diffusion layer is carbon paper or carbon cloth, and Catalytic Layer is the Pt/C catalyzer.
2. the electrochemical reducting reaction method used device of the described carbonic acid gas of claim 1 in ionic liquid, it is characterized in that: separate with proton exchange membrane between cathode compartment and the anolyte compartment, be close to wire netting on the proton exchange membrane as negative electrode, the Pt/C catalyzer is arranged on the anode, catalyst layer is made up of diffusion layer and Catalytic Layer two portions, and anode bipolar plate is close to diffusion layer.
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| CN2008100582257A CN101250711B (en) | 2008-03-27 | 2008-03-27 | Electrochemical reduction method and apparatus for carbonic anhydride in ionic liquid |
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|---|---|---|---|
| CN2008100582257A CN101250711B (en) | 2008-03-27 | 2008-03-27 | Electrochemical reduction method and apparatus for carbonic anhydride in ionic liquid |
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| CN101250711B true CN101250711B (en) | 2010-11-10 |
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| US9957624B2 (en) | 2010-03-26 | 2018-05-01 | Dioxide Materials, Inc. | Electrochemical devices comprising novel catalyst mixtures |
| US10023967B2 (en) | 2010-03-26 | 2018-07-17 | Dioxide Materials, Inc. | Electrochemical devices employing novel catalyst mixtures |
| US10173169B2 (en) | 2010-03-26 | 2019-01-08 | Dioxide Materials, Inc | Devices for electrocatalytic conversion of carbon dioxide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9957624B2 (en) | 2010-03-26 | 2018-05-01 | Dioxide Materials, Inc. | Electrochemical devices comprising novel catalyst mixtures |
| US10023967B2 (en) | 2010-03-26 | 2018-07-17 | Dioxide Materials, Inc. | Electrochemical devices employing novel catalyst mixtures |
| US10173169B2 (en) | 2010-03-26 | 2019-01-08 | Dioxide Materials, Inc | Devices for electrocatalytic conversion of carbon dioxide |
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