CN107815698B - A kind of method of the electrochemical decomposition hydrogen sulfide of mediator auxiliary - Google Patents
A kind of method of the electrochemical decomposition hydrogen sulfide of mediator auxiliary Download PDFInfo
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- CN107815698B CN107815698B CN201610818697.2A CN201610818697A CN107815698B CN 107815698 B CN107815698 B CN 107815698B CN 201610818697 A CN201610818697 A CN 201610818697A CN 107815698 B CN107815698 B CN 107815698B
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- hydrogen sulfide
- mediator
- hydrogen
- absorption tower
- elementary sulfur
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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
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
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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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
Abstract
A kind of method of the electrochemical decomposition hydrogen sulfide of mediator auxiliary, it is related to a kind of method and device of hydrogen sulfide conversion.Hydrogen sulfide conversion of the invention is carried out in two steps, and hydrogen sulfide is decomposed into elementary sulfur and hydrogen.The first step is completed in electrocatalysis device, and cathode electrocatalyst restores proton and generates hydrogen, while obtaining the mediator of oxidation state in anode.Second step carries out in absorption tower, and the mediator of oxidation state, which is pumped, to be transmitted to hydrogen sulfide absorption tower and react to obtain elementary sulfur and hydrogen ion with hydrogen sulfide, and elementary sulfur is separated and recovered, and the mediator of hydrogen ion and reduction-state is transmitted to electrocatalysis device by pump again and completes circulation.
Description
Technical field
The present invention relates to the method and devices of hydrogen sulfide conversion
Background technique
Hydrogen sulfide is largely present in coal bed gas as a kind of pernicious gas, in shale gas and natural gas, while a large amount of generating
During petroleum refining, natural gas processing and other chemical syntheses.It is industrial at present mainly to be solved using Crouse (Claus)
The problem of hydrogen sulfide.
H2S+3/2O2→SO2+H2O (1)
2H2S+SO2→2H2O+3/xSx (2)
Hydrogen sulfide partial oxidation can be generated water and sulphur by traditional claus process, recycle the sulphur in hydrogen sulfide, hydrogen is then
It is oxidized to water and generates waste.
Summary of the invention
The present invention is to provide a kind of electrochemistry of mediator auxiliary in order to which the resource for solving the problems, such as hydrogen sulfide is high-valued
The method and device of decomposing hydrogen sulfide not only solves problem of environmental pollution, but also keeps hydrogen sulfide high-valued, i.e., a kind of skill to turn waste into wealth
Art.
A kind of method of the electrochemical decomposition hydrogen sulfide of mediator auxiliary of the invention, it is related to a kind of hydrogen sulfide conversion
Method and device.Hydrogen sulfide conversion of the invention is carried out in two steps, and hydrogen sulfide is decomposed into elementary sulfur and hydrogen.The first step is in electricity
It is completed in catalytic unit, cathode electrocatalyst restores proton and produces hydrogen, while the mediator of oxidation state is obtained on anode.Second step exists
Carried out in absorption tower, the mediator of oxidation state pumped be transmitted to hydrogen sulfide absorption tower react to obtain with hydrogen sulfide elementary sulfur and hydrogen from
Son, elementary sulfur are separated and recovered, and the mediator of hydrogen ion and reduction-state is transmitted to electrocatalysis device by pump again and completes circulation.This hair
Bright cathod catalyst is high performance liberation of hydrogen catalyst, including noble metal is such as: Pt, Pt/C and non-precious metal catalyst such as CoP,
Ni2The phosphides such as P, FeP, MoP, MoS2、WS2、FeS2、NiS2, CoS2Sulfides FeSe2, CoSe2, NiSe2, MoSe2, WSe2
Equal selenides.Anode of the invention is base metal, such as Ti, Cu, Fe, carbon paper, graphite etc..Mediator of the invention is Ce3+/
Ce4+, I-/I3 -, Fe2+/Fe3+Deng.The present invention needs energy to be offered that can convert electric energy, solar energy, wind by traditional fossil energy
The renewable energy conversions electric energy such as energy, tide energy provides.
A kind of device of the electrochemical decomposition hydrogen sulfide of mediator auxiliary of the invention by one with film every reaction tank
It is formed with an absorption tower.
Detailed description of the invention
Fig. 1 is the device and reaction mechanism mechanism of reaction schematic diagram of specific embodiment one.
A in figure-/A+It is Ce for mediator3+/Ce4+, I-/I3 -, Fe2+/Fe3+One or more of Deng.
Specific embodiment
In order to further illustrate the present invention, following embodiment is enumerated.
Embodiment one:
It is followed successively by electrocatalytic reaction pond and hydrogen sulfide absorption tower from left to right (referring to Fig. 1).Electrocatalytic reaction pond inner cathode
It is separated between chamber and anode chamber with Nafion diaphragm, has diaphragm in hydrogen sulfide absorption tower.It is added in cathode chamber
The H of 0.5mol/L2SO4Aqueous solution.It is added in anode chamber and hydrogen sulfide absorption tower and contains FeCl3And H2SO4Respectively 1mol/
The aqueous solution of L and 0.5mol/L.The Ti piece of load MoP having a size of 2cm × 2cm is placed in cathode chamber, it will be having a size of 2cm
The C piece of × 2cm is placed in anode chamber as anode, and additional constant pressure source connects cathode and anode, ammeter series connection by conducting wire
Enter in circuit.This reaction constant pressure source applies 0.8V DC voltage, and the gas flow rate that hydrogen sulfide is passed through is 0.65ml/min, and purity is big
In 99.9%.After applying voltage, reaction system electric current is 80mA.A large amount of bubbles are generated on cathode, are collected using drainage.Anode
The color of solution is gradually deepened, and has pale yellow precipitate precipitation in hydrogen sulfide absorption tower.A whole set of reaction process is highly stable, react into
Stopping applied voltage input after row 10h, it is 33.5ml/h that hydrogen, which generates speed, the sediment in hydrogen sulfide absorption tower is collected,
It is centrifugated out elementary sulfur, weigh 0.53g after dry.Entire reaction process is passed through hydrogen sulfide 17.4mmol, obtains hydrogen
15mmol, elementary sulfur 14.5mmol, hydrogen sulfide conversion ratio are 86%.
Embodiment two: with embodiment one the difference is that:
It is added in anode chamber and hydrogen sulfide absorption tower and contains KI and H2SO4The water of respectively 1mol/L and 0.5mol/L
Solution.Hydrogen sulfide conversion ratio is 82%.
Embodiment three: with embodiment one the difference is that:
(the NO containing Ce is added in anode chamber and hydrogen sulfide chamber3)3And H2SO4Respectively 1mol/L's and 0.5mol/L
Aqueous solution.Hydrogen sulfide conversion ratio is 56%.
Skilled addressee readily understands that in the item for the thought for not departing from material and method disclosed in description above
The present invention can be combined or be changed under part, it is believed that this change is included within the scope of the invention.Therefore, specifically above
The special embodiment of description is merely illustrative, and is not limited the scope of the invention, by accessory claim and its it is any and
Whole equivalent ways provide complete scope of the invention.
Claims (3)
1. a kind of method of the electrochemical decomposition hydrogen sulfide of mediator auxiliary, is completed in two steps, it is characterised in that:
The first step is completed in electrocatalysis device, and cathode electrocatalyst restores proton and generates hydrogen, while obtaining oxidation state in anode
Mediator；Second step carries out in absorption tower, and the mediator of oxidation state is pumped, and to be transmitted to hydrogen sulfide absorption tower anti-with hydrogen sulfide
Elementary sulfur and hydrogen ion should be obtained, elementary sulfur is separated and recovered, and the mediator of hydrogen ion and reduction-state is transmitted to electricity by pump again and urges
Completion circulation is set in makeup；The supporting electrolyte that cathode electrocatalyst restores proton is HNO3、H2SO4、HCl、HClO4One of or
Two or more, the molar concentration of supporting electrolyte is 0.01-5 M；Mediator is I-/I3 -, Fe2+/Fe3+,
Cathod catalyst is MoP in electrocatalysis device.
2. method according to claim 1, it is characterised in that: in electrocatalysis device, DC power supply is in anode and cathode
Between the voltage that applies be 0.6-10 V.
3. method according to claim 1, it is characterised in that: reaction process carries out in aqueous solution.
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| CN201610818697.2A CN107815698B (en) | 2016-09-12 | 2016-09-12 | A kind of method of the electrochemical decomposition hydrogen sulfide of mediator auxiliary |
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| CN107815698B true CN107815698B (en) | 2019-11-26 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110607531A (en) * | 2018-06-14 | 2019-12-24 | 中国科学院大连化学物理研究所 | Cyclic electrochemical conversion treatment method and device for gas containing hydrogen sulfide and carbon dioxide |
| CN111232921B (en) * | 2018-11-29 | 2023-04-07 | 中国科学院大连化学物理研究所 | Method and device for preparing hydrogen and sulfur by decomposing hydrogen sulfide with assistance of flow battery |
| CN110813282B (en) * | 2019-09-27 | 2022-09-09 | 南京宁智高新材料研究院有限公司 | Device and method for coupling application of single-site metal catalyst and electrolytic hydrogen sulfide system |
| CN112569754B (en) * | 2019-09-29 | 2022-07-01 | 中国科学技术大学苏州高等研究院 | Bioelectrochemical reaction device and gas purification method |
| CN114481157A (en) * | 2021-12-15 | 2022-05-13 | 中国科学院大连化学物理研究所 | Full-flow process method for preparing hydrogen and sulfur by electrochemically decomposing hydrogen sulfide with assistance of mediator |
| CN114752961A (en) * | 2022-05-24 | 2022-07-15 | 宁波锋成先进能源材料研究院有限公司 | Heterogeneous catalyst, preparation method thereof and application thereof in hydrogen evolution by water electrolysis |
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| CN105018958A (en) * | 2014-04-22 | 2015-11-04 | 中国科学院大连化学物理研究所 | Method for coupled decomposition of hydrogen sulfide through photocatalytic/electrocatalytic-chemical ring reaction |
| CN105603450A (en) * | 2014-11-13 | 2016-05-25 | 中国科学院大连化学物理研究所 | Method for preparing hydrogen and sulfur through photoelectrocatalysis-chemical ring reaction coupling decomposition of hydrogen sulfide |
| CN105648464A (en) * | 2014-11-13 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method for coupling decomposition of hydrogen sulfide through photoelectric catalysis and chemic ring reaction |
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| CN105018958A (en) * | 2014-04-22 | 2015-11-04 | 中国科学院大连化学物理研究所 | Method for coupled decomposition of hydrogen sulfide through photocatalytic/electrocatalytic-chemical ring reaction |
| CN105603450A (en) * | 2014-11-13 | 2016-05-25 | 中国科学院大连化学物理研究所 | Method for preparing hydrogen and sulfur through photoelectrocatalysis-chemical ring reaction coupling decomposition of hydrogen sulfide |
| CN105648464A (en) * | 2014-11-13 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method for coupling decomposition of hydrogen sulfide through photoelectric catalysis and chemic ring reaction |
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