CN102190573A - Method for preparing formic acid through electrochemical catalytic reduction of carbon dioxide - Google Patents
Method for preparing formic acid through electrochemical catalytic reduction of carbon dioxide Download PDFInfo
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- CN102190573A CN102190573A CN2011100783949A CN201110078394A CN102190573A CN 102190573 A CN102190573 A CN 102190573A CN 2011100783949 A CN2011100783949 A CN 2011100783949A CN 201110078394 A CN201110078394 A CN 201110078394A CN 102190573 A CN102190573 A CN 102190573A
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- formic acid
- carbon dioxide
- organic solvent
- ionic liquid
- dissolved
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 102
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 96
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 31
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 28
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 26
- 238000010531 catalytic reduction reaction Methods 0.000 title abstract description 3
- 239000002608 ionic liquid Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 11
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 9
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 43
- 235000011089 carbon dioxide Nutrition 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 19
- 238000006722 reduction reaction Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 8
- 238000010349 cathodic reaction Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 150000003222 pyridines Chemical class 0.000 claims description 5
- 150000003460 sulfonic acids Chemical class 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- -1 glyoxaline ion Chemical class 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 abstract description 8
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 229960004424 carbon dioxide Drugs 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- BEFWDPZVLOCGRP-UHFFFAOYSA-M 1-butylpyridin-1-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+]1=CC=CC=C1 BEFWDPZVLOCGRP-UHFFFAOYSA-M 0.000 description 1
- PXKPKGHXANCVMC-UHFFFAOYSA-N 3-butyl-1-methyl-1,2-dihydroimidazol-1-ium;trifluoromethanesulfonate Chemical compound OS(=O)(=O)C(F)(F)F.CCCCN1CN(C)C=C1 PXKPKGHXANCVMC-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- XOZOIUUTZXUTEF-UHFFFAOYSA-N FC(F)(F)S(=N)C(F)(F)F.C(CCC)N1CN(C=C1)C Chemical compound FC(F)(F)S(=N)C(F)(F)F.C(CCC)N1CN(C=C1)C XOZOIUUTZXUTEF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a method for preparing formic acid through electrochemical catalytic reduction of carbon dioxide, and belongs to the technical field of carbon dioxide recycling. In the method, a proton exchange membrane separates an electrolytic tank into a cathode chamber and an anode chamber, organic solvent/ionic liquid/water mixed solution in which a large amount of carbon dioxide is dissolved is injected into the cathode chamber, and aqueous solution containing supporting electrolyte is injected into the anode chamber; and after an electrolysis power supply is connected, the carbon dioxide undergoes electroreduction reaction on the cathode to form the formic acid. By the method, the organic solvent/ionic liquid/water mixed solution with the advantages of good conductivity, low viscosity, high capacity of dissolving the carbon dioxide, wide electrochemical window, and low use cost can be obtained, and when the carbon dioxide is electrically reduced in the mixed solution, the current density in the electroreduction reaction of the carbon dioxide can be improved and the electrocatalytic activity and long-time stability of a cathode material are improved.
Description
Technical field
This invention relates to the method that a kind of electrochemical catalysis reducing carbon dioxide prepares formic acid, belongs to carbonic acid gas application technology as the second resource field.
Background technology
Carbonic acid gas is the main component that causes the greenhouse gases effect, also is a kind of important resource simultaneously.Carbonic acid gas being converted into other industrial chemicals, reducing the fossil oil usage quantity, is the important technology approach that realizes carbon dioxide discharge-reduction, also is the realistic problem that carbonic acid gas maximum discharge industries such as thermoelectricity, iron and steel, cement press for solution.Research and develop the carbonic acid gas resource utilization energetically and transform new technology, can promote the fast development of carbonic acid gas recycling new industry.
Formic acid is a kind of important basic chemical industry raw material, is widely used in fields such as medicine, dyestuff, leather." carbonic acid gas electrochemical reduction progress " (Tao Yingchu, Wu Shaohui, open sunlight. " chemistry circular " 2001 (5): 272-277) in the literary composition, relating to a kind of is the method for formic acid with the carbonic acid gas catalytic reduction with electrochemical method in the aqueous solution, its reaction principle is: oxidizing reaction takes place in water on anode, generate hydrogen ion and oxygen, hydrogen ion is moved to negative electrode through mass transfer process, on negative electrode, participate in the reaction of carbonic acid gas electrical catalyze reduction, generate formic acid and side reaction product.
But, but there is following problem in the technology that has electrical catalyze reduction carbonic acid gas system formic acid in the aqueous solution now: first and second carbonoxide is a non-polar molecule, solubleness is very little in the aqueous solution, has only 0.033mol/L under the standard state, causes cathodic reaction speed too slow; The second, electroreduction carbonic acid gas in the aqueous solution, in order to improve the electroconductibility of electrolytic solution, need in electrolytic solution, add inorganic supporting electrolyte, inevitably some inorganic impurities are brought in the electrolytic solution thus, some of them impurity is in cathode surface generation electrodeposit reaction, form the low surfactivity point of overpotential of hydrogen evolution, cause evolving hydrogen reaction to speed up, also cause electrode materials that the electro catalytic activity of carbonic acid gas electro-reduction reaction is reduced simultaneously.
Summary of the invention
The objective of the invention is to overcome the deficiency that above-mentioned carbonic acid gas electrical catalyze reduction technology exists, provide a kind of electrochemical catalysis reducing carbon dioxide to prepare the method for formic acid, in containing the organic solvent/ionic liquid solution of less water, carbonic acid gas efficiently is converted into formic acid with electrochemical catalysis reductive method.
Technical scheme of the present invention is achieved in that and adopts perfluorinated sulfonic acid type proton exchange membrane that electrolyzer is divided into cathode compartment and anolyte compartment, organic solvent/ionic liquid/water mixed solution that employing is dissolved with carbonic acid gas is a cathode compartment electrolytic solution, the aqueous solution that employing contains supporting electrolyte is anolyte compartment's electrolytic solution, adopting In, Pb, Zn or Sn electrode is negative electrode, adopts graphite, glass carbon or IrO
2Ta
2O
5Coated titanium electrode is an anode, adopts electrolytic reduction that carbonic acid gas is converted into formic acid.Detailed process is as follows:
Step 2 is connected electrolysis power at ambient temperature, and the control electrolysis voltage is that 3～4.2V, current density are 200～450A/m
2, carried out electrolytic reaction 1.5～3 hours (reaction times decides according to practical situation, makes the carbonic acid gas in the electrolytic solution be able to fully reduce get final product, and when electrolyte content was big in the electrolyzer, the time that needs was longer).Oxidizing reaction takes place in water on anode, generate hydrogen ion and oxygen, and hydrogen ion is moved to negative electrode through mass transfer process, with carbonic acid gas electro-reduction reaction takes place on negative electrode, and generation formic acid also is dissolved in the electrolytic solution;
Among the present invention, supporting electrolyte in anolyte compartment's aqueous solution is any in sodium bicarbonate, saleratus, potassium hydrogen phosphate, sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, sodium pyrosulfate, sal enixum or the sulfuric acid, and its concentration in the aqueous solution is that 0.1～2mol/L(determines according to actual needs).Organic solvent is a kind of in methyl-sulphoxide, acetonitrile, tetrahydrofuran (THF), methyl alcohol, ethanol or the propylene carbonate in the cathode compartment electrolytic solution, or any mixture of above-mentioned organic solvent, ionic liquid is glyoxaline ion liquid or pyridines ionic liquid, or above-mentioned ion liquid any mixture.
The structural formula of glyoxaline ion liquid is:
Wherein, R
1, R
2Be C
1-C
5Hydrocarbon chain; M, N are functional group or the hydrogen atom that is connected on the hydrocarbon chain, and functional group is :-NH
2,-CN or-OH; X
-Be CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-, HCO
3 -, H
2PO
4 -, HSO
4 -, Cl
-, Br
-, I
-
The ion liquid structural formula of pyridines is:
Wherein, R
1, R
2Be C
1-C
5Hydrocarbon chain; M, N are functional group or the hydrogen atom that is connected on the hydrocarbon chain, and functional group is :-NH
2,-CN or-OH; X
-Be CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-, HCO
3 -, H
2PO
4 -, HSO
4 -, Cl
-, Br
-, I
-
The main electrochemical reaction that the present invention relates to has:
Anodic reaction:
Cathodic reaction:
Total reaction:
The present invention compared with prior art has following beneficial effect:
(1) organic solvent such as methyl-sulphoxide, acetonitrile, tetrahydrofuran (THF), methyl alcohol, ethanol and imidazoles, pyridines ionic liquid have good dissolving absorptive character to carbonic acid gas, ionic liquid is dissolved in the mixing solutions that obtains in the organic solvent, has good conductivity, viscosity is little, the dissolved carbon dioxide ability is strong, electrochemical window is wide, use cost is low advantage;
(2) organic solvent/ionic liquid mixing solutions that will contain less water can make the current density of carbonic acid gas electro-reduction reaction reach 200～450A/m as cathode compartment electrolytic solution
2, the current efficiency that generates formic acid can reach 61～78%, and the electro catalytic activity of cathode material and permanent stability are improved.
(3) ionic liquid has very high mobility of ions and specific conductivity, electroreduction carbonic acid gas in containing the organic solvent of less water/ionic liquid mixing solutions, need in electrolytic solution, not add inorganic supporting electrolyte, can avoid some inorganic impurity galvanic deposit at cathode surface thus, cause that the electrode materials catalytic activity reduces and liberation of hydrogen side reaction aggravation.
Description of drawings
Fig. 1 is an electrolyser construction principle schematic of the present invention.
Among the figure: 1-electrolysis power, 2-negative electrode, 3-cathode compartment electrolytic solution, 4-proton exchange membrane, 5-anolyte compartment electrolytic solution, 6-anode.
Embodiment
Below in conjunction with drawings and Examples, the technical scheme of this invention is described further, but technology contents of the present invention is not limited to described scope.
Embodiment 1: as shown in Figure 1, with perfluorinated sulfonic acid type proton exchange membrane electrolyzer is divided into cathode compartment and anolyte compartment, adopting the In electrode is negative electrode, and the employing Graphite Electrodes is an anode, by electro-reduction reaction, carbonic acid gas is converted into formic acid.Detailed process is as follows:
Step 2 is at room temperature connected electrolysis power, and the control electrolysis voltage is that 3.9V, current density are 280A/m
2, carried out electrolytic reaction 3 hours, oxidizing reaction takes place and generates hydrogen ion and oxygen in water on anode, hydrogen ion is moved to negative electrode through mass transfer process, with carbonic acid gas electro-reduction reaction takes place on negative electrode, generate formic acid and be dissolved in the electrolytic solution, the current efficiency that generates formic acid reaches 61%;
Embodiment 2: as shown in Figure 1, adopt perfluorinated sulfonic acid type proton exchange membrane that electrolyzer is divided into cathode compartment and anolyte compartment, adopting the Pb electrode is negative electrode, and the employing glass-carbon electrode is an anode, by electro-reduction reaction, carbonic acid gas is converted into formic acid.Detailed process is as follows:
Step 2 is at room temperature connected electrolysis power, and the control electrolysis voltage is that 3V, current density are 200A/m
2, carried out electrolytic reaction 2 hours, oxidizing reaction takes place and generates hydrogen ion and oxygen in water on anode, hydrogen ion is moved to negative electrode through mass transfer process, with carbonic acid gas electro-reduction reaction takes place on negative electrode, the formic acid of generation is dissolved in the electrolytic solution, and the current efficiency that generates formic acid reaches 69%;
Embodiment 3: as shown in Figure 1, adopt perfluorinated sulfonic acid type proton exchange membrane that electrolyzer is divided into cathode compartment and anolyte compartment, adopting the Sn electrode is negative electrode, adopts IrO
2Ta
2O
5Coated titanium electrode is an anode, by electro-reduction reaction, carbonic acid gas is converted into formic acid.Detailed process is as follows:
Step 2 is at room temperature connected electrolysis power, and the control electrolysis voltage is that 4.2V, current density are 450A/m
2, carried out electrolytic reaction 1.5 hours, oxidizing reaction takes place and generates hydrogen ion and oxygen in water on anode, hydrogen ion is moved to negative electrode through mass transfer process, with carbonic acid gas electro-reduction reaction takes place on negative electrode, the formic acid of generation is dissolved in the electrolytic solution, and the current efficiency that generates formic acid can reach 78%;
Claims (5)
1. an electrochemical catalysis reducing carbon dioxide prepares the method for formic acid, it is characterized in that: electrolyzer is divided into cathode compartment and anolyte compartment with perfluorinated sulfonic acid type proton exchange membrane, cathode compartment electrolytic solution is the mixing solutions of the organic solvent, ionic liquid and the water that are dissolved with carbonic acid gas, anolyte compartment's electrolytic solution is the aqueous solution that contains supporting electrolyte, adopt In or Pb, Zn, Sn electrode as negative electrode, adopt Graphite Electrodes or glass-carbon electrode, IrO
2Ta
2O
5Coated titanium electrode is formic acid with electrolytic method with the carbonic acid gas electroreduction as anode.
2. electrochemical catalysis reducing carbon dioxide according to claim 1 prepares the method for formic acid, it is characterized in that: concrete preparation process is as follows:
1.1 ionic liquid is dissolved in the aqueous organic solvent, obtain the mixing solutions of organic solvent, ionic liquid and water, carbonic acid gas is dissolved in this mixing solutions, the mixing solutions that will be dissolved with carbonic acid gas then is injected in the cathode compartment as electrolytic solution, simultaneously, in the anolyte compartment, inject the aqueous solution that contains supporting electrolyte;
Carry out electrolytic reaction 1.2 connect electrolysis power, make water that oxidizing reaction take place on anode, generate hydrogen ion and oxygen, hydrogen ion is moved to negative electrode through mass transfer process, with carbonic acid gas electro-reduction reaction takes place on negative electrode, generates formic acid;
Draw from cathode compartment 1.3 will be dissolved with the electrolytic solution of formic acid, the formic acid volatilization is overflowed, obtain the formic acid product with the distillatory method; The electrolytic solution that separates behind the formic acid is used to dissolve absorbing carbon dioxide once more, the electrolytic solution that is dissolved with carbonic acid gas of gained heavily is injected in the cathode compartment, form circulation of elecrolyte; The main by product hydrogen of reaction product of anode oxygen and cathodic reaction can be collected in anolyte compartment and cathode compartment top respectively.
3. the method for preparing formic acid according to claim 1,2 described electrochemical catalysis reducing carbon dioxides, it is characterized in that: the supporting electrolyte in anolyte compartment's aqueous solution is any in sodium bicarbonate, saleratus, potassium hydrogen phosphate, sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, sodium pyrosulfate, sal enixum or the sulfuric acid, and its concentration in water is 0.1-2mol/L; Organic solvent in the cathode compartment is a kind of in methyl-sulphoxide, acetonitrile, tetrahydrofuran (THF), methyl alcohol, ethanol or the propylene carbonate, or any mixture of above-mentioned organic solvent, and the water ratio of organic solvent is 5%～15%; Ionic liquid is imidazoles or pyridines ionic liquid, or above-mentioned ion liquid any mixture, and ionic liquid and organic solvent blended liquid/agent volume ratio are 1:1～6.
4. prepare the method for formic acid according to the described a kind of electrochemical catalysis reducing carbon dioxide of claim 3, it is characterized in that: the structural formula of glyoxaline ion liquid is:
Wherein, R
1, R
2Be C
1-C
5Hydrocarbon chain; M, N are functional group or the hydrogen atom that is connected on the hydrocarbon chain, and functional group is :-NH2 ,-CN or-OH; X
-Be CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-, HCO
3 -, H
2PO
4 -, HSO
4 -, Cl
-, Br
-, I
-
The ion liquid structural formula of pyridines is:
Wherein, R
1, R
2Be C
1-C
5Hydrocarbon chain; M, N are functional group or the hydrogen atom that is connected on the hydrocarbon chain, and functional group is :-NH2 ,-CN or-OH; X
-Be CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-, HCO
3 -, H
2PO
4 -, HSO
4 -, Cl
-, Br
-, I
-
5. the method for preparing formic acid according to claim 1,2 described electrochemical catalysis reducing carbon dioxides, it is characterized in that: with the mixing solutions dissolving absorbing carbon dioxide of organic solvent, ionic liquid and water, gas concentration lwevel reaches 0.05～0.69mol/L, and the liquid aspiration is received process and carried out in absorption column of gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100783949A CN102190573B (en) | 2011-03-30 | 2011-03-30 | Method for preparing formic acid through electrochemical catalytic reduction of carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100783949A CN102190573B (en) | 2011-03-30 | 2011-03-30 | Method for preparing formic acid through electrochemical catalytic reduction of carbon dioxide |
Publications (2)
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