CN111663148B - Method for preventing elemental sulfur from adhering to electrode surface in process of electrocatalytic reduction of sulfur dioxide - Google Patents
Method for preventing elemental sulfur from adhering to electrode surface in process of electrocatalytic reduction of sulfur dioxide Download PDFInfo
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 98
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 238000011946 reduction process Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract description 4
- 238000006722 reduction reaction Methods 0.000 claims description 37
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 16
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 15
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 22
- 239000011133 lead Substances 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 235000010265 sodium sulphite Nutrition 0.000 description 11
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本发明公开了一种防止电催化还原二氧化硫过程中单质硫对电极表面黏附的方法。电催化还原过程采用三电极体系，三电极体系的阴阳极室采用质子膜隔开，阴极室内的电解液为添加了表面活性剂的二氧化硫吸收液，阳极室内的电解液为Na2SO4/H2SO4混合溶液，以铅等金属电极作为工作电极，Pt作为对电极，饱和甘汞电极作为参比电极，通过电催化还原后，从阴极室内的电解液中析出单质硫颗粒，该方法主要通过加入表面活性剂解决二氧化硫电催化还原过程中析出的单质硫在电极表面黏附的问题。该方法不但能高效电催化还原二氧化硫生成单质硫，且能够有效杜绝单质硫对电极表面的毒化，且流程短操作简单，无二次污染，有利于工业化应用。The invention discloses a method for preventing elemental sulfur from adhering to the surface of an electrode during electrocatalytic reduction of sulfur dioxide. The electrocatalytic reduction process adopts a three-electrode system. The cathode and anode chambers of the three-electrode system are separated by a proton membrane. The electrolyte in the cathode chamber is a sulfur dioxide absorption solution with surfactant added, and the electrolyte in the anode chamber is Na 2 SO 4 /H. 2 SO4 mixed solution, with lead and other metal electrodes as the working electrode, Pt as the counter electrode, and saturated calomel electrode as the reference electrode, after electrocatalytic reduction, elemental sulfur particles are precipitated from the electrolyte in the cathode chamber. The problem of the adhesion of elemental sulfur precipitated on the electrode surface during the electrocatalytic reduction of sulfur dioxide is solved by adding a surfactant. The method can not only electrocatalytically reduce sulfur dioxide to generate elemental sulfur, but also can effectively prevent the poisoning of the electrode surface by elemental sulfur. The process is short and simple to operate, and there is no secondary pollution, which is beneficial to industrial application.
Description
Technical Field
The invention relates to a method for synthesizing elemental sulfur by electrocatalytic reduction of sulfur dioxide, in particular to a method for preventing the elemental sulfur generated in the process of electrocatalytic reduction of sulfur dioxide from adhering to the surface of an electrode by using a surfactant, belonging to the technical field of recycling useful resources from nonferrous smelting flue gas.
Background
Based on the concepts of environmental protection and resource recycling, the current research on air pollution gradually focuses on the direction of how to utilize pollutants as resources. For the resource utilization of sulfur dioxide pollution gas, the sulfuric acid is prepared by oxidation or the sulfur is prepared by reduction. With the increase of the demand of sulfur in China, the technology of simply and effectively converting sulfur dioxide into elemental sulfur is continuously concerned and developed. Electrocatalytic reduction of sulfur dioxide generationElemental sulfur is a method with a good application prospect due to mild reaction conditions, low energy consumption and simple operation, but the problem of low catalytic reduction efficiency of an electro-reduction catalyst related in the prior art generally exists, and in the process of producing the elemental sulfur by reducing sulfur dioxide through a cathode, the effective area of an electrode is reduced due to easy adhesion of sulfur per se and an electrode material, and the electrolytic efficiency is greatly reduced after long-time continuous electrolysis, which is to realize the purpose of realizing high-concentration SO in colored smelting flue gas at present2The technical problem to be solved is urgently needed in the electrocatalytic reduction process.
Disclosure of Invention
Aiming at the defects that the existing method for converting sulfur dioxide into elemental sulfur through electrocatalysis has low catalytic efficiency, the elemental sulfur is adhered to the surface of an electrode to poison the electrode and the like, the invention aims to provide the method for preparing the elemental sulfur poisoning electroreduction catalyst, which has high electrocatalysis reduction efficiency on sulfur dioxide, can effectively prevent the elemental sulfur generated by reduction from being adhered to the poisoning electroreduction catalyst, can be implemented at normal temperature and normal pressure, is simple to operate, can greatly reduce energy consumption, and is favorable for popularization and application.
In order to achieve the technical purpose, the invention provides a method for preventing elemental sulfur from adhering to the surface of an electrode in the process of electrocatalytic reduction of sulfur dioxide, wherein a three-electrode system is adopted in the electrocatalytic reduction process, a cathode chamber and an anode chamber of the three-electrode system are separated by adopting a proton membrane (DuPont N117), electrolyte in the cathode chamber is sulfur dioxide absorption liquid added with a surfactant, and electrolyte in an anode chamber is Na2SO4/H2SO4In the mixed solution, a metal electrode (lead, copper, titanium and the like) is used as a working electrode, Pt is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, and elemental sulfur particles are separated out from electrolyte in a cathode chamber after electrocatalytic reduction. The reduction voltage is controlled to be-0.6V to-1.2V.
In a preferred embodiment, the surfactant is at least one of isopropyl alcohol, sodium dodecyl benzene sulfonate and polyvinylpyrrolidone. By adopting the preferable surfactant, the adhesion of elemental sulfur generated by sulfur dioxide electrocatalysis reduction on the surface of an electrocatalysis reduction electrode can be reduced, so that the poisoning effect of the elemental sulfur on the electrode is obviously weakened.
In a preferable scheme, the addition concentration of the surfactant in the sulfur dioxide absorption liquid is 0.1-5 g/L.
In a preferred scheme, the sulfur dioxide absorption liquid is sulfur dioxide water absorption liquid or sulfur dioxide alkaline absorption liquid. The water absorption liquid of sulfur dioxide is mainly H2SO3Solutions, sulfur dioxide alkaline absorption solutions such as ammonia sulfite solution, potassium sulfite solution, sodium sulfite solution, etc., which are all suitable for the technical solution of the present invention.
Preferably, the metal electrode is a lead electrode, a copper electrode or a titanium electrode. The electrocatalytic reduction efficiency of sulfur dioxide can be obviously improved by selecting a proper metal electrode as an electrocatalytic reduction catalyst. Particularly, when a lead electrode is used as an electrocatalytic reduction catalyst, the electrocatalytic reduction efficiency of sulfur dioxide is far superior to that of a copper electrode and a titanium electrode.
Preferably, the pH value of the sulfur dioxide absorption liquid is controlled to be less than 2 in the electrocatalytic reduction process. The control of the acidic environment with a pH of less than 2 is beneficial to the implementation of the electrocatalytic reduction process of sulfur dioxide, which is difficult to implement if the pH is higher than 2, and the pH can be adjusted to less than 2 by means of inorganic acid.
Preferably, the temperature is controlled to be above room temperature during the electrocatalytic reduction process. The electrocatalytic reduction process of the sulfur dioxide can be smoothly carried out at room temperature.
In a preferable scheme, the reduction potential is controlled to be-0.6V to-1.2V (relative to a saturated calomel electrode) in the electrocatalytic reduction process. Elemental sulfur is difficult to obtain in the electrolytic process under the condition that the reduction potential is-0.6V-0V, and the hydrogen evolution reaction in the electrolytic process is serious under the condition that the reduction potential exceeds-1.2V, so that the Faraday efficiency for reducing the elemental sulfur is greatly reduced.
The invention adopts a path of generating elemental sulfur by electrocatalytic reduction of sulfur dioxide: first, sulfur dioxide forms thiosulfate (S) during the reaction2O3 2-)，S4O6 2-Is SO2And thiosulfate radical (eq.1),second, S4O6 2-Can pass through S2O3 2-(eq.3) and S is presumed to be formed by a combination of the two reaction paths2O3 2-Is S4O6 2-A precursor of (a); since thiosulfate and tetrathionate are easily converted into elemental sulfur at low pH, the reaction path in this system is presumed to be as shown in equations 4 and 5. S2O3 2-And S4O6 2-Is an intermediate product of the reaction, and the lead (copper, titanium and the like) electrode mainly acts on the formation process of the intermediate product to accelerate the transfer of electrons.
4SO2+3H2O→2SO4 2-+S2O3 2-+6H+ (1)
2SO2+S2O3 2-+2H++2e→S4O6 2-+H2O (2)
2S2O3 2-→S4O6 2-+2e (3)
S4O6 2-+H+→S+SO2+H2O+SO4 2- (4)
S2O3 2-+H+→S+SO2+H2O+SO4 2- (5)
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) according to the technical scheme, the metal electrode (lead, copper, titanium and the like) has high activity on electrocatalytic reduction of sulfur dioxide or sulfite ions to generate elemental sulfur, so that sulfur resources in high-concentration sulfur dioxide gas in non-ferrous smelting flue gas can be effectively recovered and converted into elemental sulfur with high value, the problem of environmental pollution is solved, and economic value is also generated;
2) the technical scheme of the invention reduces the adhesion of elemental sulfur generated by electrocatalytic reduction of sulfur dioxide on the surface of the electrode by using the surfactant, so as to solve the technical problem that the elemental sulfur adheres on the surface of the electrode to poison the electrode.
3) The technical scheme of the invention can realize the conversion of the sulfur dioxide absorption liquid at room temperature and normal pressure, has mild reaction conditions and low energy consumption, and is beneficial to industrial application.
4) The technical scheme of the invention adopts an electrocatalytic reduction mode, and has the characteristic of high reaction efficiency.
Drawings
FIG. 1 shows a comparison of the effects of different surfactant additions on the i-t curve.
FIG. 2 is an SEM image of the surface of the electrode before and after the addition of the surfactant.
FIG. 3 is a comparison of the effect of adding different concentrations of surfactant on the i-t curve.
FIG. 4 shows the current density and hydrogen evolution potential of different electrodes at lower overpotentials.
Detailed Description
The following examples are intended to further illustrate the present invention, but not to limit the scope of the claims.
The sulfur dioxide absorption solution in the following examples was electrocatalytic reduced using a three-electrode system. The cathode chamber and the anode chamber of the three-electrode system are separated by a DuPont N117 proton membrane, the electrolyte in the cathode chamber is sulfur dioxide absorption liquid, and the electrolyte in the anode chamber is Na2SO4/H2SO4The solution was mixed, the metal sheet as the working electrode, Pt as the counter electrode and SCE as the reference electrode.
The following examples are not specifically illustrated, and the chemical reagents used are all conventional commercial products, and are analytical reagents.
Example 1
Analytically pure sodium sulfite, no surfactant.
50mL of water and sodium sulfite (0.08mol/L) in a certain ratio are uniformly mixed and taken out to a cathode chamber to be used as a catholyte, 50mL of anhydrous sodium sulfate aqueous solution is used as an anolyte, a lead sheet is used as a working electrode, Pt is used as a counter electrode, and SCE is used as a reference electrode. And carrying out electrochemical performance test. In the process, an electrolytic potential of-0.8V is selected, the electrolytic capacity is controlled to be the same (400C), the concentration of sulfite is 0.08mol/L, the pH value of a cathode and anode electrolytic chamber is adjusted to 0.5 by adopting sulfuric acid, the stirring speed is 1000rmp, and a current density-time curve (i-t curve) is tested. The slope of the i-t curve is 0.09.
Example 2
50mL of water, sodium sulfite (0.08mol/L) and 5% isopropanol solution (0.01mol/L) in a certain ratio are uniformly mixed and taken out to a cathode chamber to be used as catholyte, 50mL of anhydrous sodium sulfate aqueous solution is used as anolyte, a lead sheet is used as a working electrode, Pt is used as a counter electrode, and SCE is used as a reference electrode, and electrochemical performance test is carried out. In the process, an electrolytic potential of-0.8V is selected, the electrolytic capacity is controlled to be the same (400C), the concentration of sulfite is 0.08mol/L, the pH value of a cathode and anode electrolytic chamber is adjusted to 0.5 by adopting sulfuric acid, the stirring speed is 1000rmp, and a current density-time curve (i-t curve) is tested. The slope of the i-t curve can be reduced from 0.09 to 0.06.
Example 3
50mL of water, sodium sulfite (0.08mol/L) and 0.3g/L of polyvinylpyrrolidone (PVP) in a certain ratio are uniformly mixed and taken out to a cathode chamber to be used as catholyte, 50mL of anhydrous sodium sulfate aqueous solution is used as anolyte, a lead sheet is used as a working electrode, Pt is used as a counter electrode, and SCE is used as a reference electrode, and electrochemical performance test is carried out. In the process, an electrolytic potential of-0.8V is selected, the electrolytic capacity is controlled to be the same (400C), the concentration of sulfite is 0.08mol/L, the pH value of a cathode and anode electrolytic chamber is adjusted to 0.5 by adopting sulfuric acid, the stirring speed is 1000rmp, and a current density-time curve (i-t curve) is tested. The slope of the i-t curve can be reduced from 0.09 to 0.05.
Example 4
Analytically pure sodium sulfite, and 0.01mol/L Sodium Dodecyl Benzene Sulfonate (SDBS) is selected as the surfactant.
50mL of water, sodium sulfite (0.08mol/L) and 0.01mol/L Sodium Dodecyl Benzene Sulfonate (SDBS) in a certain ratio are uniformly mixed and taken out to a cathode chamber to be used as catholyte, 50mL of anhydrous sodium sulfate aqueous solution is used as anolyte, a lead sheet is used as a working electrode, Pt is used as a counter electrode, and SCE is used as a reference electrode, so that the electrochemical performance test is carried out. In the process, an electrolytic potential of-0.8V is selected, the electrolytic capacity is controlled to be the same (400C), the concentration of sulfite is 0.08mol/L, the pH value of a cathode and anode electrolytic chamber is adjusted to 0.5 by adopting sulfuric acid, the stirring speed is 1000rmp, and a current density-time curve (i-t curve) is tested. The slope of the i-t curve can be reduced from 0.09 to 0.03.
Example 5
Analytically pure sodium sulfite, and four Sodium Dodecyl Benzene Sulfonate (SDBS) with different concentrations are selected as the surfactant.
50mL of water, sodium sulfite (0.08mol/L) and Sodium Dodecyl Benzene Sulfonate (SDBS) (0.01mol/L, 0.0075mol/L, 0.005mol/L and 0.0025mol/L) in a certain proportion are uniformly mixed and taken out to a cathode chamber to be used as a cathode electrolyte, 50mL of anhydrous sodium sulfate aqueous solution is used as an anode electrolyte, a lead sheet is used as a working electrode, Pt is used as a counter electrode, and SCE is used as a reference electrode, and electrochemical performance test is carried out. In the process, an electrolytic potential of-0.8V is selected, the electrolytic capacity is controlled to be the same (400C), the concentration of sulfite is 0.08mol/L, the pH value of a cathode and anode electrolytic chamber is adjusted to 0.5 by adopting sulfuric acid, the stirring speed is 1000rmp, and a current density-time curve (i-t curve) is tested. After linear fitting, the slopes are respectively 0.0056, 0.0053, 0.0055 and 0.0056, and the difference between the slopes is small, which shows that the influence of the concentrations of the SDBS on the current attenuation condition is not large in a certain time, that is, the SDBS with small concentration has a good inhibition effect on the adhesion of sulfur on the surface of the electrode, so in the subsequent experiments, the addition amount of the SDBS is controlled to be 0.0025 mol/L.
Example 6
Analytically pure sodium sulfite, the reduction voltage is-0.8V, the pH value is 0.25, and 0.01mol/L Sodium Dodecyl Benzene Sulfonate (SDBS) is selected as a surfactant.
50mL of water, sodium sulfite (0.08mol/L) and a surfactant (0.01mol/L sodium dodecyl benzene sulfonate) in a certain ratio are uniformly mixed and taken out to a cathode chamber to serve as catholyte, 50mL of an anhydrous sodium sulfate aqueous solution serves as anolyte, a lead sheet serves as a working electrode, Pt serves as a counter electrode, SCE serves as a reference electrode, sulfuric acid is used for adjusting the pH value of the cathode and anode electrolytic chamber to be 0.25, the electrodes are fixed, and a sealing cover is screwed down. Reducing voltage is minus 0.8V, water at normal temperature is circularly cooled, electrolysis is stopped after 30min, and elemental sulfur is generated. Electrolyzing to obtain milky white or milky yellow suspension. And transferring the suspension to a beaker, and carrying out constant-temperature water bath at 70-80 ℃. After a period of time, the small solid particles in the solution agglomerate and the solution becomes clear. And then, carrying out suction filtration on the solution to obtain a solid product, and drying the solid product at 60 ℃ to constant weight, wherein the Faraday efficiency is 83.5%.
Example 7
Comparison of electrocatalytic properties and electrocatalytic selectivity properties of different electrodes. Mainly comparing the current density and hydrogen evolution potential of different electrodes at lower overpotentials. In the electrolysis experiment, lead, titanium and copper are respectively used as cathodes, and the electrolyte in a cathode chamber is 0.08mol/L Na2SO3And 0.5mol/L H2SO4The mixed solution is 0.08mol/L Na electrolyte in an anode chamber2SO4And 0.5mol/L H2SO4The solution was mixed, the pH of the two electrolysis chambers was adjusted to 0.5, and the solution was subjected to linear voltammetry, the results of which are shown in fig. 4. The initial potentials of lead and titanium electrolysis are not obviously different and are about-0.4V (relative to SCE), and the reduction peak current in a Pb electrode system is obviously enhanced compared with that of titanium and glassy carbon electrodes at a more negative potential, so that Pb has better catalytic performance. Cu shows a smaller initial reduction potential, but at low potentials the hydrogen evolution reaction of Cu is equally vigorous and SO2The catalytic reduction reaction potential window on the surface of the copper electrode is narrow (-0.5 to-0.75V vs. SCE), the hydrogen evolution potential of the Pb electrode is obviously higher than that of Ti, Cu and the like, and SO is added2The reduction potential window is wider, and the inhibition of the hydrogen evolution reaction and the SO are favorably realized by controlling the potential2The reduction efficiency is improved, and the reduction efficiency is better SO2The catalytic cathode material is electro-reduced.
Claims (5)
1. A method for preventing elemental sulfur from adhering to the surface of an electrode in the process of electrocatalytic reduction of sulfur dioxide is characterized by comprising the following steps: the electrocatalytic reduction process adopts a three-electrode system, a cathode chamber and an anode chamber of the three-electrode system are separated by adopting a proton membrane, the electrolyte in the cathode chamber is sulfur dioxide absorption liquid added with a surfactant, and the electrolyte in the anode chamber is Na2SO4/H2SO4The mixed solution is prepared by taking a metal electrode as a working electrode, Pt as a counter electrode and a saturated calomel electrode as a reference electrode, and separating out elemental sulfur particles from electrolyte in a cathode chamber after electrocatalytic reduction;
the surfactant is at least one of isopropanol, sodium dodecyl benzene sulfonate and polyvinylpyrrolidone;
the addition concentration of the surfactant in the sulfur dioxide absorption liquid is 0.1-5 g/L;
the pH of the electrolyte in the cathode chamber is adjusted to <2 during the electro-catalytic reduction process.
2. The method of claim 1, wherein the step of preventing elemental sulfur from adhering to the surface of the electrode during the electrocatalytic reduction of sulfur dioxide comprises: the sulfur dioxide absorption liquid is sulfur dioxide water absorption liquid or sulfur dioxide alkaline absorption liquid.
3. The method of claim 1, wherein the step of preventing elemental sulfur from adhering to the surface of the electrode during the electrocatalytic reduction of sulfur dioxide comprises: the metal electrode is a lead electrode, a copper electrode or a titanium electrode.
4. The method of claim 1, wherein the step of preventing elemental sulfur from adhering to the surface of the electrode during the electrocatalytic reduction of sulfur dioxide comprises: the temperature is controlled to be above room temperature in the electrocatalytic reduction process.
5. The method of claim 1, wherein the step of preventing elemental sulfur from adhering to the surface of the electrode during the electrocatalytic reduction of sulfur dioxide comprises: the reduction potential is controlled to be minus 0.6V to minus 1.2V in the electrocatalytic reduction process, and the electrochemical reduction process is relative to a saturated calomel electrode.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762590A (en) * | 2004-10-21 | 2006-04-26 | 北京大学 | A transition metal-γ-Fe2O3 nanomaterial and its preparation method and application |
| CN102509803A (en) * | 2011-11-04 | 2012-06-20 | 中山大学 | Preparation method of carbon-coated sulfur anode material of lithium sulfur secondary battery |
| EP2704239A1 (en) * | 2012-08-29 | 2014-03-05 | SolviCore GmbH & Co KG | Colloidal dispersions comprising precious metal particles and acidic ionomer components and methods of their manufacture and use |
| CN106075438A (en) * | 2016-06-17 | 2016-11-09 | 上海理工大学 | A kind of ultra-small MoS2 nanosheet and its preparation method and application |
| CN107720707A (en) * | 2017-11-06 | 2018-02-23 | 中南大学 | A kind of method of sulfur dioxide absorbing liquid Photocatalysis disproportionation recovery elemental sulfur |
| KR20180036868A (en) * | 2016-09-30 | 2018-04-10 | 전자부품연구원 | Porous carbon cathode and lithium-sulfur dioxide secondary battery containing the same |
| CN109395712A (en) * | 2018-12-07 | 2019-03-01 | 昆明冶金研究院 | A kind of aluminum-based catalyst agent carrier and preparation method thereof |
| CN109434130A (en) * | 2018-12-07 | 2019-03-08 | 五邑大学 | Preparation method of spherical nano silver powder |
| CN109819979A (en) * | 2019-03-15 | 2019-05-31 | 尚蒙科技无锡有限公司 | Nano silver copper bimetallic colloid/liquid of high anti-microbial property and preparation method thereof |
-
2020
- 2020-06-11 CN CN202010528603.4A patent/CN111663148B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762590A (en) * | 2004-10-21 | 2006-04-26 | 北京大学 | A transition metal-γ-Fe2O3 nanomaterial and its preparation method and application |
| CN102509803A (en) * | 2011-11-04 | 2012-06-20 | 中山大学 | Preparation method of carbon-coated sulfur anode material of lithium sulfur secondary battery |
| EP2704239A1 (en) * | 2012-08-29 | 2014-03-05 | SolviCore GmbH & Co KG | Colloidal dispersions comprising precious metal particles and acidic ionomer components and methods of their manufacture and use |
| CN106075438A (en) * | 2016-06-17 | 2016-11-09 | 上海理工大学 | A kind of ultra-small MoS2 nanosheet and its preparation method and application |
| KR20180036868A (en) * | 2016-09-30 | 2018-04-10 | 전자부품연구원 | Porous carbon cathode and lithium-sulfur dioxide secondary battery containing the same |
| CN107720707A (en) * | 2017-11-06 | 2018-02-23 | 中南大学 | A kind of method of sulfur dioxide absorbing liquid Photocatalysis disproportionation recovery elemental sulfur |
| CN109395712A (en) * | 2018-12-07 | 2019-03-01 | 昆明冶金研究院 | A kind of aluminum-based catalyst agent carrier and preparation method thereof |
| CN109434130A (en) * | 2018-12-07 | 2019-03-08 | 五邑大学 | Preparation method of spherical nano silver powder |
| CN109819979A (en) * | 2019-03-15 | 2019-05-31 | 尚蒙科技无锡有限公司 | Nano silver copper bimetallic colloid/liquid of high anti-microbial property and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| "Cathode depassivation using ultrasound for the production of colloidal sulphur by reduction of sulphur dioxide";Fornes, J. P.等;《ELECTROCHIMICA ACTA》;20160920;第186-193页 * |
| "Electrochemical conversion of sulfur dioxide with a rotating cylinder electrode working as anode or cathode";Fornes, JP等;《JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY》;20160131;第219-225页 * |
| "Production of colloidal sulphur from reduction of sulphur dioxide by contact deposition with 304 stainless steel";Fornes, J. P.等;《ELECTROCHIMICA ACTA》;20190201;第484-489页 * |
| "二氧化硫膜电解制备硫磺机理与应用研究";张正阳 等;《有色金属(冶炼部分)》;20200430;第2页左栏第1小节、第3页右栏最后一段，图3，第6页左栏第1段、第2页右栏最后一段，图1 * |
| "二氧化硫还原回收单质硫技术研究及进展 ";杨本涛 等;《硫酸工业》;20191231;第11-17页 * |
| "电化学方法处理二氧化硫研究进展";张正阳 等;《有色金属(冶炼部分)》;20200331;第1-7页 * |
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