CN111232921B - Method and device for preparing hydrogen and sulfur by decomposing hydrogen sulfide with assistance of flow battery - Google Patents
Method and device for preparing hydrogen and sulfur by decomposing hydrogen sulfide with assistance of flow battery Download PDFInfo
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- CN111232921B CN111232921B CN201811442172.9A CN201811442172A CN111232921B CN 111232921 B CN111232921 B CN 111232921B CN 201811442172 A CN201811442172 A CN 201811442172A CN 111232921 B CN111232921 B CN 111232921B
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0495—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by dissociation of hydrogen sulfide into the elements
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a method and a device for preparing hydrogen and sulfur by decomposing hydrogen sulfide assisted by a flow battery. Enabling chemical electrolyte containing an oxidation state to contact and react with hydrogen sulfide gas to obtain elemental sulfur and hydrogen ions, and reducing the chemical electrolyte containing the oxidation state; the mixture containing hydrogen ions and reduced chemical electrolyte is then returned to the anode chamber of the flow cell for circulation. The protons pass through the diaphragm of the flow battery to reach the cathode chamber, the protons reaching the cathode chamber and the reduced chemical electrolyte generate hydrogen under the action of the catalyst, meanwhile, the reduced chemical electrolyte is oxidized, and the oxidized chemical electrolyte flows back to the cathode chamber of the flow battery to realize circulation. The absorption rate of the hydrogen sulfide reaches 99.9 percent and the conversion rate reaches 98 percent. In another aspect of the invention, an apparatus for electrolyzing hydrogen sulfide is provided.
Description
Technical Field
The invention relates to a method and a device for preparing hydrogen and sulfur by decomposing hydrogen sulfide assisted by a flow battery, belonging to the field of harmful gas treatment.
Background
Hydrogen sulfide is a harmful gas widely found in industrial exhaust emissions, biogas, natural gas, and shale gas. Hydrogen sulfide not only causes great pollution to the environment but also seriously harms human health.
At present, the commonly used hydrogen sulfide treatment methods comprise an alkali liquor absorption method, a high-temperature cracking method, a plasma decomposition method, a high-temperature catalytic conversion method and the like, but secondary pollution, high energy consumption and low yield seriously restrict the development of the methods. Therefore, under mild reaction conditions, the invention of an effective green treatment method and device has important significance.
Disclosure of Invention
According to one aspect of the invention, a flow battery-assisted method for decomposition of hydrogen sulfide is provided, which can convert hydrogen sulfide into hydrogen gas and sulfur having high added values, thereby realizing harmless treatment of harmful hydrogen sulfide gas. The method has high treatment efficiency and remarkable effect.
The flow battery-assisted hydrogen sulfide conversion treatment method comprises the following steps:
when the flow battery is charged, the anode generates an oxidation-state chemical electrolyte, and the cathode generates a reduction-state chemical electrolyte.
Contacting the chemical electrolyte containing an oxidation state with hydrogen sulfide gas to obtain elemental sulfur and hydrogen ions, and reducing the chemical electrolyte containing the oxidation state; the mixture containing hydrogen ions and reduced chemical electrolyte is then returned to the anode chamber of the flow cell for circulation.
The protons pass through the diaphragm of the flow battery to reach the cathode chamber, the protons reaching the cathode chamber and the reduced chemical electrolyte generate hydrogen under the action of the catalyst, meanwhile, the reduced chemical electrolyte is oxidized, and the oxidized chemical electrolyte flows back to the cathode chamber of the flow battery to be circulated.
Optionally, the redox couple in the anode chamber chemical electrolyte of the flow battery is selected from I 3 - /I - 、Br 2 /Br - 、Fe 3+ /Fe 2+ 、VO 2 + /VO 2+ At least one of; the molar concentration of the redox couple is 1 x 10 -5 ～5mol/L。
Optionally, the redox couple in the cathode compartment chemical electrolyte of the flow cell is selected from H 6 [P 2 W 18 O 62 ]/Li 6 [P 2 W 18 O 62 ]、Cr 2+ /Cr 3+ 、V 2+ /V 3+ At least one of; the molar concentration of the redox couple is 1 x 10 -5 ～5mol/L。
Optionally, the electrolyte selected by the flow battery is hydrochloric acidAt least one of sulfuric acid, nitric acid and perchloric acid; the molar concentration of the acid liquor is 1 multiplied by 10 -3 ～10mol/L。
The chemical electrolyte in the oxidation state and the chemical electrolyte in the reduction state are formed correspondingly according to the state of the redox couple contained in the anode chemical electrolyte of the flow battery. With I 3 - /I - By way of example, a large number contain I - The chemical electrolyte of (A) is a reduced chemical electrolyte of (I) - After anodic oxidation, a large amount of a catalyst containing I is formed 3 - Is referred to as the chemical electrolyte in an oxidized state. And (3) forming a chemical electrolyte in an oxidation state and a chemical electrolyte in a reduction state corresponding to the states of the redox couple contained in the flow battery catholyte. At V 2+ /V 3+ By way of example, a large amount of V 3+ The chemical electrolyte of (2) is an oxidized chemical electrolyte, V 3+ After the anode reduction, a large amount of V is generated 2+ Is referred to as a reduced state chemical electrolyte.
Optionally, the selected membrane of the flow battery is one of a Nafion membrane, a porous ceramic membrane, a porous polyolefin membrane, and a sulfonated polyphenylsulfone membrane.
Optionally, the flow battery anode comprises an anode; the flow battery cathode comprises a cathode, and the voltage applied between the anode and the cathode is 0.1-5V.
Optionally, the voltage is a direct current voltage.
Optionally, the catalyst for catalyzing the cathodic redox couple hydrogen evolution reaction of the flow cell comprises NiP, feP, coP, WP, moWP, moS 2 、WS 2 And at least one of MoC, WC non-noble metal catalyst, pt/C and RuP noble metal catalyst.
The invention also provides a device required by the hydrogen sulfide cyclic conversion treatment, which comprises a flow battery device, an absorption tower device and a catalytic reactor device,
the oxidized state chemical electrolyte and the reduced state chemical electrolyte are generated in a flow battery device;
said absorption of hydrogen sulfide is carried out in said absorber means;
the hydrogen evolution reaction is carried out in a catalytic reactor unit;
the flow cell comprises an anode chamber and a cathode chamber; a liquid outlet of the anode chamber is connected with a liquid inlet pipeline of the absorption tower device; a liquid inlet of the anode chamber is connected with a liquid outlet pipeline of the absorption tower device; the liquid outlet of the cathode chamber is connected with the liquid inlet pipeline of the catalytic reactor device; and the liquid inlet of the cathode chamber is connected with the liquid outlet pipeline of the catalytic reactor device.
Optionally, the oxidized-state chemical electrolyte obtained in the flow battery anode is pumped to the absorption tower device to contact and react with hydrogen sulfide to obtain sulfur, hydrogen ions and reduced-state chemical electrolyte; wherein the sulfur is separated and recovered, and the hydrogen ions and the reduced chemical electrolyte are pumped to the anode chamber to complete the circulation. Optionally, hydrogen ions pass through the flow cell membrane to the cathode compartment, and the reduced-state chemical electrolyte containing hydrogen ions is pumped to the catalytic reactor device to produce hydrogen gas and an oxidized-state chemical electrolyte; wherein hydrogen is collected and the chemical electrolyte in an oxidized state is pumped to the cathode compartment of the flow cell to complete the cycle.
By adopting the device, the anode chemical electrolyte and the cathode chemical electrolyte are recycled in a closed circuit, and meanwhile, the hydrogen sulfide contained in the gas to be treated is recycled, so that the treatment efficiency is improved, and the strategy of changing the hydrogen sulfide into valuables is realized.
Optionally, multiple layers of sieve plates are arranged in the absorption tower device at intervals along the longitudinal direction of the absorption tower. Preferably, the sieve plate is a quartz sand sieve plate, and the diameter of the pore of the quartz sand sieve plate is 10-500 microns.
Optionally, multiple layers of sieve plates are arranged in the catalytic reactor device at intervals along the longitudinal direction of the catalytic reactor, the hydrogen evolution catalyst is fixed on the multiple layers of sieve plates, the sieve plates are porous ceramic sieve plates, and the pore diameters of the porous ceramic sieve plates are 10-500 microns.
Preferably, the device also comprises a voltage applying device, wherein the anode chamber of the flow battery comprises an anode; the cathode chamber of the flow battery comprises a cathode, and the voltage applying device is respectively connected with the cathode and the anode in a circuit mode.
The invention relates to a method and a device for preparing hydrogen and sulfur by decomposing hydrogen sulfide with the assistance of a flow battery. In the present invention, the process for converting hydrogen sulfide into a high value-added product is carried out in three steps. The first step is completed in a flow cell, and an anode chamber and a cathode chamber of the flow cell are isolated by adopting a proton membrane; under the action of an external power supply, the chemical electrolyte in an oxidation state is obtained at the anode, and the chemical electrolyte in a reduction state is obtained at the cathode. And the second step is carried out in an absorption tower, the chemical electrolyte in an oxidation state is pumped to a hydrogen sulfide absorption tower to react with hydrogen sulfide to obtain sulfur and hydrogen ions, the sulfur is separated and recovered, and the hydrogen ions and the chemical electrolyte in a reduction state are pumped to the anode chamber of the flow cell to complete circulation. And the third step is carried out in a catalytic reactor, hydrogen ions and the chemical electrolyte in a reduction state are pumped to the catalytic reactor, hydrogen and the chemical electrolyte in an oxidation state are generated at room temperature under the action of a catalyst, and the chemical electrolyte in the oxidation state is pumped to a cathode chamber of the flow battery to complete circulation.
In the present invention, the "anode chamber of the flow cell" is meant to include the anode region of the flow cell device, the electrolyte contained in the anode region, and the anode inserted into the electrolyte. By "flow cell cathode compartment" is meant a cathode region comprising an electrolyzer, an electrolyte contained within the cathode region, and a cathode inserted into the electrolyte. "anodic chemical electrolyte" refers to an acidic solution containing a specific redox couple, and "cathodic chemical electrolyte" refers to an acidic solution containing a specific redox couple. The anodic and cathodic chemical electrolytes differ in the redox couple involved.
By the method, the hydrogen sulfide can be circularly converted into sulfur and hydrogen with additional values, the absorption rate of the hydrogen sulfide reaches 99.9%, and the conversion rate reaches 98%. In another aspect of the invention, an apparatus for electrolyzing hydrogen sulfide is provided.
The beneficial effects of the invention include but are not limited to:
(1) The invention provides a flow battery assisted hydrogen sulfide cyclic conversion treatment method, which comprises the steps of generating oxidation state chemical electrolyte at the anode of a flow battery, using the obtained oxidation state chemical electrolyte for oxidizing hydrogen sulfide to convert to form sulfur, generating reduction state chemical electrolyte at the cathode of the flow battery, and generating hydrogen gas by hydrogen ions and the reduction state chemical electrolyte under the action of a catalyst. The method has high oxidation rate of hydrogen sulfide, and the conversion rate of the hydrogen sulfide can reach 98%.
(2) The flow battery assisted hydrogen sulfide cyclic conversion treatment device provided by the invention comprises a flow battery, an absorption tower and a catalytic reactor which are circularly used in series, wherein the flow battery, the absorption tower and the catalytic reactor are connected through a gas circuit and a liquid circuit, so that the hydrogen sulfide-containing gas is synchronously recycled, and one set of device can convert the hydrogen sulfide into sulfur and hydrogen to recycle waste gas.
Drawings
FIG. 1 is a schematic diagram of the reaction process of the method for preparing hydrogen and sulfur by using hydrogen sulfide assisted by a flow battery according to a preferred embodiment of the invention;
FIG. 2 is a schematic diagram of a process for preparing hydrogen and sulfur from hydrogen sulfide by flow battery assistance according to a preferred embodiment of the invention.
List of parts and reference numerals:
| name of component | Reference numerals |
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100 |
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200 |
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300 |
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
The raw materials in the examples of the present invention were all purchased from commercial sources unless otherwise specified.
Example 1
Referring to fig. 1, the generation of a redox couple of an anode and a cathode in the present embodiment is performed in a flow battery; the absorption of hydrogen sulfide is carried out in a hydrogen sulfide absorption tower; the evolution of hydrogen is carried out in a catalytic reactor unit. The flow cell is provided with a cathode chamber and an anode chamber. The cathode chamber and the anode chamber are separated by a Nafion 117 diaphragm. 6 layers of quartz sand sieve plates are arranged in the hydrogen sulfide absorption tower at intervals along the longitudinal direction of the hydrogen sulfide absorption tower, and the pore diameters of the sieve plates are 20 microns. And 8 layers of stone porous ceramic sieve plates are arranged in the catalytic reactor at intervals along the longitudinal direction of the catalytic reactor, the pore diameters of the sieve plates are 10 microns, and the MoC hydrogen evolution catalyst is fixed on the porous ceramic sieve plates.
A3 mol/L NaI hydrochloric acid solution containing 1.5mol/L was added to the anode chamber as an anode chemical electrolyte. The cathode chamber is charged with VCl containing 1mol/L 3 Hydrochloric acid solution (3 mol/L) is used as the cathode chemical electrolyte. The cathode and the anode are both graphite electrodes, and the graphite electrodes are respectively inserted into the cathode chemical electrolyte and the anode chemical electrolyte. The cathode and anode have a square shape with a longitudinal cross-sectional dimension of 5cm × 5 cm.
The external constant voltage source is respectively connected with the cathode and the anode through leads. And the ammeter is connected in series into the circuit. In this example, the reactive constant voltage source applies a DC voltage of 1.4V. After the voltage was applied, a reaction system current of 120mA was observed.
After the reaction starts, the color of the anodic chemical electrolyte gradually deepens, and the color of the cathodic chemical electrolyte gradually lightens. After reacting for 15h, the anode chamber obtains the chemical electrolyte in an oxidation state, the chemical electrolyte in the oxidation state is introduced into a hydrogen sulfide absorption tower,1.5mol/L NaI hydrochloric acid solution (3 mol/L) is pumped into the anode chamber to continue the reaction. And (3) obtaining a reduced chemical electrolyte from the cathode chamber, introducing the reduced chemical electrolyte into a catalytic reactor, precipitating a large amount of hydrogen under the catalytic action of MoC at room temperature, collecting and measuring. The cathode chamber was pumped with 1.0mol/L VCl 3 The hydrochloric acid solution (3 mol/L) solution continues the reaction.
Mixing hydrogen sulfide gas (N) 2 :H 2 20% of S =80% and V/V) is slowly introduced into the hydrogen sulfide absorption tower, and the gas flow rate is 8ml/min. As the reaction proceeds, a yellowish precipitate is precipitated in the hydrogen sulfide absorption tower. The color of the absorption liquid is lightened, and the liquid flowing out of the liquid outlet of the hydrogen sulfide absorption tower is led into the anode chamber to be used as anode chemical electrolyte for recycling. The liquid at the cathode was slowly flowed into the catalytic reactor at a flow rate of 5ml/min, and immediately, the separation of bubbles was observed and collected. The solution color of the catalytic reactor is changed to be dark, and the liquid flowing out of the liquid outlet of the catalytic reactor is led into the cathode chamber to be used as cathode chemical electrolyte for recycling.
In the whole process, the hydrogen generation rate is 5.8L/h. And collecting the sediment in the hydrogen sulfide absorption tower, centrifugally separating out sulfur, drying, and weighing 120g. 3.88mol of hydrogen sulfide is introduced in the whole reaction process, and 3.80mol of hydrogen and 3.75mol of sulfur elementary substance are obtained. The absorption rate of the hydrogen sulfide reaches 99.95%, and the conversion rate of the hydrogen sulfide is 97%.
Example 2
The difference from the embodiment 1 is that:
the diaphragm of the flow battery is a sulfonated polyphenylsulfone membrane, and 1.0mol/L FeCl is added in an anode chamber 2 Hydrochloric acid solution (3 mol/L) was the anode chemical electrolyte. The diameter of the holes of the sieve plate of the absorption tower is 50 microns, and the diameter of the holes of the sieve plate of the catalytic reactor is 75 microns. The catalyst of the catalytic reactor is MoS 2 . The absorption rate of the hydrogen sulfide reaches 99.97%, and the conversion rate of the hydrogen sulfide is 95%.
Example 3
The difference from the embodiment 1 is that:
the diaphragm of the flow battery is a porous polyolefin film, and 1.0mol/L FeCl is added into an anode chamber 2 Hydrochloric acid solution (3 mol/L) is used as anode chemistryAnd (3) an electrolyte. In the cathode chamber, at 0.5mol/L Li 6 [P 2 W 18 O 62 ]Hydrochloric acid solution (3 mol/L) is the cathode chemical electrolyte. The diameter of the sieve plate pore of the absorption tower is 100 microns, and the diameter of the sieve plate pore of the catalytic reactor is 75 microns. The catalyst of the catalytic reactor was Pt/C. The absorption rate of the hydrogen sulfide reaches 99.93%, and the conversion rate of the hydrogen sulfide is 98%.
Example 4
The difference from the example 1 is that:
the anode chemical electrolyte has a composition of 1 × 10 -5 mol/L FeCl 2 Hydrochloric acid solution (1X 10) -3 mol/L). In the cathode chamber, 1 × 10 -5 mol/L Li 6 [P 2 W 18 O 62 ]Hydrochloric acid solution (1X 10) -3 mol/L) is a cathode chemical electrolyte. The voltage applied between the anode and the cathode was 0.1V. The diameter of the sieve plate pore of the absorption tower is 10 microns, and the diameter of the sieve plate pore of the catalytic reactor is 10 microns.
Example 5
The difference from the example 1 is that:
the component of the anode chemical electrolyte is 5mol/L FeCl 2 Hydrochloric acid solution (10 mol/L). In the cathode chamber, at 5mol/L Li 6 [P 2 W 18 O 62 ]Hydrochloric acid solution (10 mol/L) is cathode chemical electrolyte. The voltage applied between the anode and cathode was 5V. The aperture of the sieve plate of the absorption tower is 500 microns, and the aperture of the sieve plate of the catalytic reactor is 500 microns.
EXAMPLE 6 Cyclic electrochemical conversion treatment device for Hydrogen sulfide-containing gas
Referring to fig. 2, the apparatus includes: a flow cell device 100, an absorption tower device 200 and a catalytic reaction device 300; flow cell apparatus 100 includes an anode chamber that produces a chemical electrolyte containing an oxidized state and a cathode chamber that produces a chemical electrolyte in a reduced state; the anode chamber of the flow cell is connected with a liquid inlet pipeline of the absorption tower device 200. The chemical electrolyte containing the oxidized form is pumped into an absorber apparatus. The oxidized chemical electrolyte passes through the absorption device 200 from top to bottom, and reacts with the gas to be treated in the absorption device 200. The elemental sulfur formed after the hydrogen sulfide in the gas is oxidized is collected and recovered by the sieve plate in the absorption device 200. The bottom of the absorber 200 is provided with an air inlet and the top is provided with an air outlet. The gas to be treated enters the absorption device 200 from the gas inlet and moves upward through the multi-layer sieve plate, and then leaves from the gas outlet. After the reacted anode chemical electrolyte leaves from a liquid outlet at the bottom of the absorption device 200, the redox couple contained in the anode chemical electrolyte is in a reduced state and enters the electrochemical anode chamber through a pump to be recycled as the electrolyte. The catholyte solution containing hydrogen ions is pumped into the catalytic reactor unit. The reduced chemical electrolyte passes through the catalytic reactor device 300 from top to bottom, and the cathode reaction solution reacts with hydrogen ions to generate hydrogen under the action of the catalyst fixed on the sieve plate of the catalytic reactor 300. The hydrogen gas flows out of the catalytic reactor through the gas outlet. The reacted catholyte solution exits at the bottom outlet of the catalytic reactor 300, and the oxidized catholyte solution contained therein is pumped into the electrochemical cathode chamber for recycling as an electrolyte solution. The yield of waste gas and waste liquid in the whole treatment process is low, the effective conversion of hydrogen sulfide gas can be realized only by using the flow cell device 100, the absorption tower device 200 and the catalytic reactor 300 together, the equipment is simple, and the cost is low. Meanwhile, the treatment efficiency is higher.
The parameters used and the hydrogen sulfide conversion for examples 1 to 3 are listed in Table 1.
TABLE 1
TABLE 1 Hydrogen sulfide gas mixture (N) with a flow rate of treatment gas of 8ml/min in examples 1 to 3 2 :
H 2 S =80%:20%, V/V) results
Wherein a, the hydrogen sulfide conversion rate is as follows:
from the above examples 1 to 3, it can be seen that the method and the apparatus provided by the present invention can realize the conversion of hydrogen sulfide into sulfur and hydrogen with high added values, thereby realizing the recycling of harmful gases.
The above description is only for the purpose of illustrating the present invention and is not intended to limit the present invention in any way, and the present invention is not limited to the above description, but rather should be construed as being limited to the scope of the present invention.
Claims (8)
1. A flow battery assisted method for producing hydrogen and sulfur by decomposing hydrogen sulfide, which is characterized by comprising the following steps:
under the condition of charging of the flow battery, an anode generates an oxidation-state chemical electrolyte, and a cathode generates a reduction-state chemical electrolyte;
enabling the anode chemical electrolyte containing an oxidation state to contact and react with hydrogen sulfide gas in an absorption tower to obtain elemental sulfur and hydrogen ions, and reducing the anode chemical electrolyte containing the oxidation state; then returning the mixture containing hydrogen ions and reduced anode chemical electrolyte to the flow cell anode chamber to regenerate the oxidized state anode chemical electrolyte; the anode chemical electrolyte circulates between the absorption tower and the anode chamber;
the proton passes through a diaphragm of the flow cell to reach a cathode chamber, the proton and the cathodic chemical electrolyte containing a reduction state in a catalytic reactor generate hydrogen under the action of a catalyst, meanwhile, the cathodic chemical electrolyte containing the reduction state is oxidized, the oxidized cathodic chemical electrolyte flows back to the cathode chamber of the flow cell to generate the cathodic chemical electrolyte containing the reduction state, and the cathodic chemical electrolyte circulates between an absorption tower and the catalytic reactor;
the device used in the method comprises a flow battery device, an absorption tower device and a catalytic reactor device;
the production of the anodic and cathodic chemical electrolytes is performed in a flow battery device;
said absorption of hydrogen sulfide is carried out in said absorber means;
the hydrogen evolution reaction is carried out in a catalytic reactor unit;
the flow cell comprises an anode chamber and a cathode chamber; the liquid outlet of the anode chamber is connected with the liquid inlet pipeline of the absorption tower device; a liquid inlet of the anode chamber is connected with a liquid outlet pipeline of the absorption tower device; the liquid outlet of the cathode chamber is connected with the liquid inlet pipeline of the catalytic reactor device; and the liquid inlet of the cathode chamber is connected with the liquid outlet pipeline of the catalytic reactor device.
2. The method of claim 1, wherein the redox couple in the chemical electrolyte of the anode chamber of the selected flow cell is selected from I 3 - /I - 、Br 2 /Br - 、Fe 3+ /Fe 2+ 、VO 2 + /VO 2+ At least one of (a);
the molar concentration of the redox couple is 1 x 10 -5 ~5mol/L。
3. The method of claim 1, wherein the redox couple in the chemical electrolyte of the cathode compartment of the selected flow cell is selected from H 6 [P 2 W 18 O 62 ]/Li 6 [P 2 W 18 O 62 ]、Cr 2+ /Cr 3+ 、V 2+ /V 3+ At least one of;
the molar concentration of the redox couple is 1 × 10 -5 ~5mol/L。
4. The method of claim 1, wherein the catalyst that catalyzes the cathodic redox couple hydrogen evolution reaction of a flow battery comprises NiP, feP, coP, WP, moWP, moS 2 、WS 2 MoC and WC as non-noble metal catalysts,and at least one of Pt/C and RuP noble metal catalysts.
5. The method of claim 1, 2, 3 or 4, wherein the electrolyte selected by the flow battery is at least one of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid;
the molar concentration of the redox couple is 1 x 10 -3 ~10mol/L。
6. The method of claim 1, wherein the selected separator membrane of the flow battery is one of a Nafion membrane, a porous ceramic separator membrane, a porous polyolefin membrane, and a sulfonated polyphenylsulfone membrane.
7. The method of claim 1, wherein the charging voltage of the flow battery is 0.1-5V.
8. The method according to claim 1, wherein a plurality of layers of screen plates are arranged in the absorption tower device at intervals along the longitudinal direction of the absorption tower device; the sieve plate is a quartz sand sieve plate, and the diameter of the pore of the quartz sand sieve plate is 10-500 microns; the catalytic reactor device is internally provided with a plurality of layers of sieve plates at intervals along the longitudinal direction of the catalytic reactor, the hydrogen evolution catalyst is fixed on the plurality of layers of sieve plates, the sieve plates are porous ceramic sieve plates, and the pore diameters of the porous ceramic sieve plates are 10-500 microns.
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| CN107815698B (en) * | 2016-09-12 | 2019-11-26 | 中国科学院大连化学物理研究所 | A kind of method of the electrochemical decomposition hydrogen sulfide of mediator auxiliary |
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