CN112725816B - Method and device for preparing hydrogen sulfide by sulfur dioxide electrocatalytic reduction in cooperation with membrane separation - Google Patents
Method and device for preparing hydrogen sulfide by sulfur dioxide electrocatalytic reduction in cooperation with membrane separation 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 70
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 38
- 239000012528 membrane Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000000926 separation method Methods 0.000 title claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 51
- 230000020477 pH reduction Effects 0.000 claims abstract description 39
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 26
- 238000005341 cation exchange Methods 0.000 claims abstract description 15
- 238000006722 reduction reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000005684 electric field Effects 0.000 claims abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000005273 aeration Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000013589 supplement Substances 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/16—Hydrogen sulfides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a method and a device for preparing hydrogen sulfide by sulfur dioxide electrocatalytic reduction in cooperation with membrane separation; the reaction chamber is divided into an anode chamber, an acidification chamber and a catalytic reduction reaction chamber by a cation exchange membrane and an anion exchange membrane, gas containing sulfur dioxide is introduced into the catalytic reduction reaction chamber, the gas containing sulfur dioxide is catalytically reduced at a cathode under the action of direct current voltage, a part of generated hydrogen sulfide gas is discharged from the upper part, and the rest S2‑Enters an acidification chamber and H under the drive of an electric field and the selection of an anion exchange membrane+Combining to generate hydrogen sulfide gas, and discharging the hydrogen sulfide gas from the upper part; h consumed in acidification Chamber+H produced by electrolysis of water in the anode compartment+Selectively migrating to the acidification chamber for replenishment; the invention has simple, green and economic process and H2The conversion and collection rate of S is high, the resource utilization of energy is realized, and the development requirement of green economy is met.
Description
Technical Field
The invention relates to a method and a device for preparing hydrogen sulfide by sulfur dioxide electrocatalysis reduction and membrane separation, belonging to the technical field of separation and purification of toxic polluted gas and environmental protection engineering.
Background
In recent years, the problems of sulfur dioxide emission and environmental pollution caused by the sulfur dioxide emission are still obvious, the average frequency of acid rain reduction in China is 10.8%, and the main anion is sulfate radical which accounts for 21.1% of the total equivalent of the ions. Acid rain not only seriously corrodes buildings and public transport facilities, but also destroys large-area forests and crops, so that the control standard of China is increasingly strict, and meanwhile, under the large background of reduction of ecological culture, the resource utilization of wastes becomes the main development direction of pollution control.
At present, the flue gas desulfurization technology widely adopts three types of traditional wet method, semi-dry method and dry method, the treatment system is complex, the occupied area of equipment is large, the investment and operation cost is high, the added value of products is low, the resource utilization of wastes is difficult to realize, and the process requirements at the present stage can not be met gradually. Application with publication number of CN 206138987U discloses a method for removing SO in flue gas by copper extraction tailings2And a resource recycling device, which utilizes the desulfurization active substance contained in the extracted copper tailings and SO contained in the aqueous solution2Contact of flue gases, SO2Absorbed and the smoke is purified; ammonium sulfide, ammonium hydrogen sulfide and lime milk are added step by step, so that iron ions, zinc ions, copper ions, ammonium ions and the like in the sulfur slurry are recycled. The method can achieve higher flue gas desulfurization efficiency, but the device is complicated and various, and a large amount of capital needs to be invested in early construction, SO that the economic cost is higher, and the method is not suitable for SO2Separate treatment of gas and production of medium and small enterprises.
The hydrogen sulfide is a chemical product widely applied, can be used for agricultural chemicals, polymer additives and vulcanizing agents, and is widely applied in the field of environmental pollution control. Application publication No. CN 108793084A discloses a method for producing hydrogen sulfide in a circulating catalytic bed reactor, which takes sulfur, metal sulfide and hydrogen as raw materials to produce hydrogen sulfide by contact reaction at the temperature of 150-300 ℃. The method takes the finished product substance as the raw material and needs external heating, and the production cost is higher. Therefore, sulfur dioxide is converted into hydrogen sulfide by a certain method, and the resource recycling of waste can be realized.
Disclosure of Invention
The invention aims to provide a method for preparing hydrogen sulfide by sulfur dioxide electrocatalytic reduction and membrane separation, namely, a reaction chamber is divided into an anode chamber, an acidification chamber and a catalytic reduction reaction chamber by a cation exchange membrane and an anion exchange membrane, a gas containing sulfur dioxide is introduced into the catalytic reduction reaction chamber, and the gas containing sulfur dioxide is catalytically reduced at a cathode under the action of direct current voltage to generate part of hydrogen sulfide gas from the upper partDischarging the remaining S2-Enters an acidification chamber and H under the drive of an electric field and the selection of an anion exchange membrane+Combining to generate hydrogen sulfide gas, and discharging the hydrogen sulfide gas from the upper part; h consumed in acidification Chamber+H produced by electrolysis of water in the anode compartment+Selectively migrate to the acidification chamber for replenishment.
The initial solutions in the anode chamber, the acidification chamber and the catalytic reduction reaction chamber are all dilute sulfuric acid with the mass concentration of 1-5%.
The flow velocity of the gas containing sulfur dioxide is 0.01-10 m3/h，SO2The concentration is 400-4000 mg/m3The oxygen content is 0-1%.
The catalyst is ferrous salt, is dissolved in dilute sulfuric acid in a catalytic reduction reaction chamber, and has the concentration of 0.01-0.2 mol/L.
The ion exchange membranes are all conventional membranes sold in the market, wherein the sulfuric acid concentration resistance of the anion exchange membranes is more than 40wt%, the anion selectivity is more than 98%, such as anion exchange membranes of model AMI-7001 and the like; cation exchange membranes cation selectivity >90%, such as model CMI-7000 cation exchange membranes.
The current density of the direct current power supply is 30-900 mA/m2Or the voltage is 0.1-20V.
Containing SO2Gas is introduced from the catalytic reduction reaction chamber, and SO is generated under the action of cathode catalytic reduction2Is absorbed and reduced into H2S and S2-S in solution2-Ions selectively enter the acidification chamber under the action of electric field drive and anion exchange membrane to react with H+Binding to form H2S; h consumed in acidification Chamber+H produced by electrolysis of water in the anode compartment+The water is transferred to an acidification chamber for supplement under the action of electric field drive and anion exchange membrane. The following reactions mainly occur in the process system:
a catalytic reduction reaction chamber:
SO2 + H2O ⇌H2SO3
H2SO3⇌ H++HSO3 -
2HSO3 - + 3H2O +4e- → HS2O3 - + 6OH- (φ - = 0.514 V)
H2S2O3 → S + SO2+H2O
S + 2H+ + 2e- → H2S↑ (φ - = 0.141 V)
an acidification chamber:
H+ + S2- → H2S↑
anode chamber:
2H2O – 4e- → O2(g)↑+ 4H+
H+ + HSO4 - → H2SO4
2H+ + SO4 2- → H2SO4
the external power supply is a direct current power supply, and the current density is 30-900 mA/m under the constant current condition2Or the voltage is 0.1-20V under the condition of constant voltage.
The invention also provides a device for implementing the method, which comprises a reaction chamber, an anode electrode, a cathode electrode and a power supply; the cation exchange membrane and the anion exchange membrane are arranged in the reaction chamber and divide the reaction chamber into an anode chamber, an acidification chamber and a catalytic reduction chamber from left to right; the anode and the cathode are respectively arranged at two ends in the reaction chamber and are respectively positioned in the anode chamber and the catalytic reduction chamber, the anode and the cathode are respectively connected with a power supply through leads, the air inlet pipe is arranged in the catalytic reduction chamber, the bottom of the cathode chamber is provided with an aeration sieve plate, the top of the reaction chamber is provided with an air outlet which is communicated with the catalytic reduction chamber and the acidification chamber, and the top of the anode chamber is provided with an air outlet.
The anode and the cathode are plate-shaped electrodes; the electrode material is a graphite electrode, such as a graphite plate, a graphite felt and the like, wherein the anode material can be a corrosion-resistant ruthenium-iridium coated electrode.
The advantages of the invention are as follows:
(1) the invention relates to a method for cooperating membrane separation through catalytic reductionWith SO2Preparation H2S gas with the conversion collection rate close to 100 percent, and SO is realized2Efficient purification and recycling;
(2) the reactions involved in the invention are driven electrically by H consumed in the process+The water is also electrolyzed in the anode chamber and is generated and supplemented, and the medicament is added in disorder;
(3) the method disclosed by the invention is carried out under the conditions of normal temperature and low voltage, the reaction condition is mild, the process is simple and convenient, and the operation is easy.
Drawings
FIG. 1 is a schematic diagram of the apparatus of the present invention;
in the figure: 1-a catalytic reduction chamber; 2-a cathode electrode; 3-aeration sieve plate; 4-an anion exchange membrane; 5, an air inlet pipe; 6-an acidification chamber; 7-a cation exchange membrane; 8-air outlet; 9-an anode chamber; 10-an anode electrode; 11-an exhaust port; 12 power supply.
Detailed Description
The invention is explained in more detail below with reference to the figures and examples, without limiting the scope of the invention.
Example 1: as shown in fig. 1, the device for preparing hydrogen sulfide by sulfur dioxide electrocatalytic reduction in cooperation with membrane separation comprises a reaction chamber, an anode electrode 10, a cathode electrode 2 and a power supply 11; the cation exchange membrane 7 and the anion exchange membrane 4 are arranged in the reaction chamber and divide the reaction chamber into an anode chamber 9, an acidification chamber 6 and a catalytic reduction chamber 1 from left to right; the anode electrode 10 and the cathode electrode 2 are respectively arranged at two ends in the reaction chamber and are respectively positioned in the anode chamber 9 and the catalytic reduction chamber 1, the anode electrode 10 and the cathode electrode 2 are respectively connected with a power supply through leads, the air inlet pipe 5 is arranged in the catalytic reduction chamber 1, the bottom of the cathode chamber is provided with an aeration sieve plate 3, the top of the reaction chamber is provided with an air outlet 8 which is communicated with the catalytic reduction chamber 1 and the acidification chamber 6, and the top of the anode chamber 9 is provided with an air outlet 11; the cathode electrode is a graphite electrode plate, and the anode electrode is a corrosion-resistant ruthenium-iridium coated electrode plate;
at room temperature, a reaction chamber is divided into an anode chamber, an acidification chamber and a catalytic reduction reaction chamber by a cation exchange membrane and an anion exchange membrane; the initial solutions of the anode chamber, the acidification chamber and the catalytic reduction reaction chamber are allDilute sulfuric acid with mass concentration of 1 percent, direct current voltage is applied to the reaction chamber, the gas containing sulfur dioxide is introduced into the catalytic reduction reaction chamber to be catalytically reduced, the generated hydrogen sulfide gas is partially discharged from the gas outlet 8, and the rest S2-Enters an acidification chamber and H under the drive of an electric field and the selection of an anion exchange membrane+Hydrogen sulfide gas is generated by combination and is discharged from a gas outlet 8; h consumed in acidification Chamber+H produced by electrolysis of water in the anode compartment+The water is transferred to an acidification chamber for supplement under the action of electric field drive and anion exchange membrane.
The method is used for treating sulfur dioxide gas, SO, in flue gas2The concentration is 2620mg/m3Gas flow rate of 0.8 m3H; at room temperature, at 0.02mol/L of FeSO4The solution is added into a catalytic reduction reaction chamber as a catalyst, and 0.1A/m is additionally added2The direct current constant current of (2); the anion exchange membrane is an AMI-7001 membrane, and the cation exchange membrane is a qianqiu I type cation membrane; no SO is detected at the outlet within 800h from the start of the treatment2Gas, by calculating H2The conversion of S was 99.8%.
Example 2: the device of the embodiment is the same as that of the embodiment 1, and a reaction chamber is divided into an anode chamber, an acidification chamber and a catalytic reduction reaction chamber by utilizing a cation exchange membrane and an anion exchange membrane at room temperature; the initial solution of the anode chamber, the acidification chamber and the catalytic reduction reaction chamber is dilute sulfuric acid with the mass concentration of 2%, direct current voltage is applied to the reaction chamber, gas containing sulfur dioxide is introduced into the catalytic reduction reaction chamber, the gas is catalytically reduced in the cathode chamber, part of generated hydrogen sulfide gas is discharged from an upper gas outlet, and the rest S2-Enters an acidification chamber and H under the drive of an electric field and the selection of an anion exchange membrane+Combining to generate hydrogen sulfide gas, and discharging the hydrogen sulfide gas from the gas outlet; h consumed in acidification Chamber+H produced by electrolysis of water in the anode compartment+The water is transferred to an acidification chamber for supplement under the action of electric field drive and anion exchange membrane.
Treating sulfur dioxide gas in flue gas by the above method, wherein SO2The concentration is 3580mg/m and the gas flow rate is 1.2 m3H is used as the reference value. At room temperature, at 0.1mol/L of FeSO4Solutions ofAs a catalyst; the anode electrode is a graphite plate, the cathode electrode is a graphite felt, and a constant voltage direct current of 2.5V is additionally applied; the anion exchange membrane is a qianqiu I type anion membrane; the type of the cation exchange membrane is a thousand autumn I type cation membrane;
no SO was detected at the outlet within 1500h from the start of the treatment2Gas, by calculating H2The conversion of S was 99.9%.
Example 3: the device of the embodiment is the same as that of the embodiment 1, and a reaction chamber is divided into an anode chamber, an acidification chamber and a catalytic reduction reaction chamber by utilizing a cation exchange membrane and an anion exchange membrane at room temperature; the initial solution of the anode chamber, the acidification chamber and the catalytic reduction reaction chamber is dilute sulfuric acid with the mass concentration of 5%, direct current voltage is applied to the reaction chamber, gas containing sulfur dioxide is introduced into the catalytic reduction reaction chamber, the gas is catalytically reduced in the cathode chamber, part of generated hydrogen sulfide gas is discharged from an upper gas outlet, and the rest S2-Enters an acidification chamber and H under the drive of an electric field and the selection of an anion exchange membrane+Combining to generate hydrogen sulfide gas, and discharging the hydrogen sulfide gas from the gas outlet; h consumed in acidification Chamber+H produced by electrolysis of water in the anode compartment+The water is transferred to an acidification chamber for supplement under the action of electric field drive and anion exchange membrane.
Treating sulfur dioxide gas in flue gas at room temperature by the above method, wherein SO2The concentration is 2094mg/m and the gas flow velocity is 5m3H; at 0.2mol/L of FeSO4The solution is used as a catalyst, the cathode and the anode are both graphite plates, and 0.2A/m is additionally added2The direct current constant current of (2); the anion exchange membrane is AMI-7001 membrane; the cation exchange membrane is a CMI-7000 membrane;
no SO was detected at the outlet within 100h from the start of the treatment2Gas, by calculating H2The conversion of S was close to 99.7%.
Claims (6)
1. A method for preparing hydrogen sulfide by sulfur dioxide electrocatalysis reduction and membrane separation is characterized in that: the reaction chamber is divided into an anode chamber, an acidification chamber and a catalytic reduction reaction chamber by a cation exchange membrane and an anion exchange membrane, and gas containing sulfur dioxide is introduced into the catalystIn the reduction reaction chamber, under the action of DC voltage, the gas containing sulfur dioxide is catalytically reduced at the cathode to produce partial hydrogen sulfide gas, and the rest S is discharged2-Enters an acidification chamber and H under the drive of an electric field and the selection of an anion exchange membrane+Combining to generate hydrogen sulfide gas, and discharging the hydrogen sulfide gas from the upper part; h consumed in acidification Chamber+H produced by electrolysis of water in the anode compartment+Selectively migrate to the acidification chamber for replenishment.
2. The method for preparing hydrogen sulfide by sulfur dioxide electrocatalytic reduction cooperated with membrane separation as claimed in claim 1, wherein: the initial solutions in the anode chamber, the acidification chamber and the catalytic reduction reaction chamber are dilute sulfuric acid with the mass concentration of 1-5%.
3. The method for preparing hydrogen sulfide by sulfur dioxide electrocatalytic reduction cooperated with membrane separation as claimed in claim 1, wherein: the flow rate of the gas containing sulfur dioxide is 0.01-10 m3/h，SO2The concentration is 400-4000 mg/m3The oxygen content is 0-1%.
4. The method for preparing hydrogen sulfide by sulfur dioxide electrocatalytic reduction cooperated with membrane separation as claimed in claim 1, wherein: the catalyst is ferrous salt, is dissolved in dilute sulfuric acid in a catalytic reduction reaction chamber, and has the concentration of 0.01-0.2 mol/L.
5. The method for preparing hydrogen sulfide by sulfur dioxide electrocatalytic reduction cooperated with membrane separation as claimed in claim 1, wherein: the current density of the DC power supply is 30-900 mA/m2Or the voltage is 0.1-20V.
6. The device for completing the method for preparing hydrogen sulfide by the electrocatalytic reduction of sulfur dioxide and the membrane separation as set forth in any one of claims 1 to 5, is characterized in that: comprises a reaction chamber, an anode electrode (10), a cathode electrode (2) and a power supply (12); the cation exchange membrane (7) and the anion exchange membrane (4) are arranged in the reaction chamber and divide the reaction chamber into an anode chamber (9), an acidification chamber (6) and a catalytic reduction chamber (1) from left to right; anode electrode (10), cathode electrode (2) set up respectively in reaction chamber both ends department and lie in anode chamber (9) and catalytic reduction room (1) respectively, anode electrode (10), cathode electrode (2) are connected with the power respectively through the wire, intake pipe (5) set up in catalytic reduction room (1), the cathode chamber bottom is equipped with aeration sieve board (3), reaction chamber top is opened there is gas outlet (8) and its and catalytic reduction room (1) and acidizing chamber (6) intercommunication, anode chamber (9) top is equipped with gas vent (11).
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|---|---|---|---|---|
| US4519881A (en) * | 1984-06-25 | 1985-05-28 | Standard Oil Company (Indiana) | Regeneration of alkaline treating agents |
| CN104718156A (en) * | 2012-09-19 | 2015-06-17 | 液体光有限公司 | Electrochemical co-production of chemicals with sulfur-based reactant feeds to anode |
| CN206138987U (en) * | 2016-08-25 | 2017-05-03 | 昆明理工大学 | Carry in copper tailings desorption flue gas device of SO2 and resourceization |
| WO2019222602A1 (en) * | 2018-05-18 | 2019-11-21 | California Institute Of Technology | Process to convert reduced sulfur species and water into hydrogen and sulfuric acid |
-
2020
- 2020-12-25 CN CN202011563602.XA patent/CN112725816B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4519881A (en) * | 1984-06-25 | 1985-05-28 | Standard Oil Company (Indiana) | Regeneration of alkaline treating agents |
| CN104718156A (en) * | 2012-09-19 | 2015-06-17 | 液体光有限公司 | Electrochemical co-production of chemicals with sulfur-based reactant feeds to anode |
| CN206138987U (en) * | 2016-08-25 | 2017-05-03 | 昆明理工大学 | Carry in copper tailings desorption flue gas device of SO2 and resourceization |
| WO2019222602A1 (en) * | 2018-05-18 | 2019-11-21 | California Institute Of Technology | Process to convert reduced sulfur species and water into hydrogen and sulfuric acid |
Non-Patent Citations (1)
| Title |
|---|
| Efficient purification of hydrogen sulfide by synergistic effects of electrochemical and liquid phase catalysis;Junyan Li et al.;《Separation and Purification Technology》;20190220;第218卷;43-50 * |
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| CN112725816A (en) | 2021-04-30 |
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