CN102500202A - Indirect electrolysis method for hydrogen sulfide - Google Patents
Indirect electrolysis method for hydrogen sulfide Download PDFInfo
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- CN102500202A CN102500202A CN2011103710085A CN201110371008A CN102500202A CN 102500202 A CN102500202 A CN 102500202A CN 2011103710085 A CN2011103710085 A CN 2011103710085A CN 201110371008 A CN201110371008 A CN 201110371008A CN 102500202 A CN102500202 A CN 102500202A
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- metal
- sulfide
- hydrogen
- elemental sulfur
- hydrogen sulfide
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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
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Abstract
The invention relates to an indirect electrolysis method for hydrogen sulfide, which comprises the following steps of: reacting the hydrogen sulfide with metal to generate hydrogen and metal sulfide or reacting the hydrogen sulfide with metal salt to generate acid and metal sulfide; decomposing the metal sulfide into metal elementary substance and elemental sulfur through a solid compound cathode molten salt electrolysis technology; and reacting the metal elementary substance with the hydrogen sulfide or the generated acid to obtain the hydrogen and the metal sulfide or the metal salt. The invention has the beneficial effects that in the method, the hydrogen sulfide can be electrolyzed into the hydrogen and elemental sulfur with high value added; the indirect electrolysis method has the advantages of high treatment efficiency, convenience in operation, low cost, no generated by-product or secondary pollutant and the like; and while industrial hydrogen sulfide waste gas is converted into the elemental sulfur, the hydrogen can also be made, the multiple purposes are achieved, therefore, the indirect electrolysis method has good industrial application prospect.
Description
Technical field
The present invention relates to a kind of indirect electric decomposition method of hydrogen sulfide, belong to environmental technology field.
Background technology
H
2S is the poisonous byproduct that produces in industries such as PETROLEUM PROCESSING, natural gas processing, biofermentations, and several hundred million tons output is arranged every year.If unordered discharging, healthy and ecological safety that will the serious harm people, how effectively handling hydrogen sulfide has become the research topic that people very pay close attention at present.The conventional method that purifies hydrogen sulfide has oxidizing process, absorption method, absorption process etc., and the new technology that still is in conceptual phase at present has bioanalysis, ozone oxidation method, electrochemical process and electron beam microwave decomposition method etc.Main in the market processing method is Claus method and Lo-cat method, is elemental sulfur all but these two kinds of method common features are products after the hydrogen sulfide treatment, and the hydrogen resource in the hydrogen sulfide is not used.In fact, the energy carrier that hydrogen was widely studied as present stage, its preparation is current research focus equally.If can directly convert hydrogen sulfide into hydrogen and elemental sulfur, then can farthest realize turning waste into wealth of hydrogen sulfide.In order to utilize the hydrogen in the hydrogen sulfide, the people such as Fujii of Japan propose in the aqueous solution to prepare through indirect electrolytic hydrogen sulfide the method for sulphur and hydrogen, but its complex process have the acid corrosion problem, and power consumption is higher.
Summary of the invention
To above-mentioned deficiency, technical problem to be solved by this invention provides the electrolytic method of the low hydrogen sulfide of a kind of energy consumption.
The inventor applies for a patent " a kind of metal sulfide M in early stage
1The metallurgical method of S " (number of patent application 200910063037.8).The present invention is on the basis of this solid metallic sulfide electrolysis tech invention; A kind of new solution of hydrogen sulfide treatment has been proposed: at first; Hydrogen sulfide is converted into metal sulfide, then the metal sulfide electrolysis is generated sulphur and metal, metal reacts with hydrogen sulfide more again accomplishes a circulation.
One of technical scheme provided by the invention is: the salt ML reaction with hydrogen sulfide and metal earlier generates metal sulfide M S and sour HL; Then this metal sulfide M S is decomposed into metal and elemental sulfur through the molten-salt electrolysis of solid metallic sulfide; Metal that is generated and HL reaction obtain the salt ML of hydrogen and this metal, and so circulation changes hydrogen sulfide into hydrogen and elemental sulfur, and described M comprises Sn, Cd; Described L comprises: Cl, SO
4, NO
3
Another kind of technical scheme provided by the invention is: earlier hydrogen sulfide and metal M reaction are generated metal sulfide M S and H
2Then through the molten-salt electrolysis of solid metallic sulfide this metal sulfide is decomposed into metal and elemental sulfur, so circulation changes hydrogen sulfide into hydrogen and elemental sulfur, and wherein, M comprises: Mn, Fe, Co, Ni, Zn, Ag, Cd, Sn.
Another kind of technical scheme provided by the invention is: hydrogen sulfide gas is absorbed with alkali earlier, and the reactant salt with metal generates metal sulfide M S again; Then through the molten-salt electrolysis of solid metallic sulfide this metal sulfide is decomposed into metal and elemental sulfur, wherein, M comprises: Mn, Fe, Co, Ni, Cu, Zn, Ag, Cd, Sn, Bi, Sb.
In technique scheme; The molten-salt electrolysis of described solid metallic sulfide is meant; Fused salt with M1X is an electrolyte, and the metal sulfide and the metal collector of metal sulfide perhaps having been added the electronic conduction material are compound as solid state cathode, make anode with graphite; Under inert atmosphere, electrolysis temperature is controlled at 450-950
OC, press 0.6-3.0V with groove, the control electrolysis time make electrolysis electricity reach sulfide reduce fully required theoretical electric weight and more than, be metal and elemental sulfur with the metal sulfide electrochemical decomposition, wherein M1 contains Li, Na, K, Mg, Ca, Ba, a kind of among the Al and more than; X is F, and Cl is more than a kind of the reaching among the Br.
In the present invention, at first, hydrogen sulfide and metal reaction generate hydrogen and metal sulfide, perhaps the reaction of hydrogen sulfide metallizing thing are generated metal sulfide and acid; Then this metal sulfide is decomposed into metal and elemental sulfur through the molten-salt electrolysis of solid metallic sulfide; Metal that is generated and hydrogen sulfide perhaps obtain the compound of hydrogen and this metal with the acid reaction of last step generation.So circulation is converted into hydrogen sulfide the hydrogen and the elemental sulfur of high added value.For being not purpose with preparation hydrogen sometimes, the present invention proposes to use the alkali absorbing hydrogen sulphide earlier, and the reactant salt with metal obtains metal sulfide again, thereby the sulphur in the hydrogen sulfide is changed into the elemental sulfur of high added value through the electrolysis of solid metallic sulfide again.
Because the decomposition potential of metal sulfide is generally lower; Therefore; The indirect electric decomposition technique scheme of the processing hydrogen sulfide that the present invention proposes have the treatment effeciency height, easy and simple to handle, cost is low, do not produce advantages such as accessory substance or secondary pollution, when changing industrial hydrogen sulfide waste gas into elemental sulfur, can also make hydrogen; Serve multiple, thereby have favorable industrial application prospect.
The specific embodiment
Present invention is described will further to combine accompanying drawing and embodiment below.These are described is for further the present invention will be described, rather than limits the invention.
Embodiment 1: with acid (PH<2.12) butter of tin or stannous chloride solution absorption hydrogen sulfide waste gas, precipitation separation obtains SnS
2(or SnS) and HCl: again that this sulfide and conductive material is compound, 650
OCBe that anode carries out electrolysis with the graphite rod in sodium chloride and the potassium chloride fused salt mixt, negative electrode generates tin metal, and anode generates sulphur simple substance.With of the concentrated hydrochloric acid reaction of product tin metal, get the chloride and the hydrogen of tin with heat.
Embodiment 2: with dichloride cadmium solution absorption hydrogen sulfide waste gas, precipitation separation obtains CdS and HCl: again that this CdS and conductive material is compound, and 900
OCBe that anode carries out electrolysis with the graphite rod in the calcium chloride fused salt, negative electrode generates cadmium metal, and anode generates sulphur simple substance.With product cadmium metal and hydrochloric acid reaction, get dichloride cadmium and hydrogen.
Embodiment 3: hydrogen sulfide is reacted with metallic tin at 100-400 ℃, generate artificial gold and H
2Again through molten-salt electrolysis, 500
OCBe that anode carries out electrolysis with the graphite rod in lithium chloride and sodium chloride and the potassium chloride fused salt mixt, artificial gold is decomposed into metallic tin and elemental sulfur.
Embodiment 4: hydrogen sulfide waste gas is fed contain in the water of dissolved oxygen earlier, add silver-colored simple substance again, generate Ag
2S and H
2Again through molten-salt electrolysis, 600
OCBe that anode carries out electrolysis with the graphite rod in calcium chloride and sodium chloride and the potassium chloride fused salt mixt, silver sulfide is decomposed into argent and elemental sulfur.
Embodiment 5: hydrogen sulfide is reacted with cadmium vapor at 800 ℃, generate cadmium sulfide and H
2Again through molten-salt electrolysis, 600
OCBe that anode carries out electrolysis with the graphite rod in calcium chloride and sodium chloride and the potassium chloride fused salt mixt, cadmium sulfide is decomposed into cadmium metal and elemental sulfur.
Embodiment 6:Hydrogen sulfide at 600 ℃ of following and nickel reactants, is generated black nickel sulfide and H
2Again through molten-salt electrolysis, 800
OCBe that anode carries out electrolysis with the graphite rod in lithium fluoride and sodium fluoride and the potassium fluoride fused salt mixt, nickel sulfide is decomposed into metallic nickel and elemental sulfur.
Embodiment 7: hydrogen sulfide is reacted with cobalt powder at 400 ℃, generate cobaltosic sulfide and H
2, perhaps then generate cobalt sulfide 700 ℃ of reactions; Again through molten-salt electrolysis, 600
OCBe that anode carries out electrolysis with the graphite rod in lithium chloride and sodium chloride and the potassium chloride fused salt mixt, this cobalt sulfide is decomposed into metallic cobalt and elemental sulfur.
Embodiment 8: hydrogen sulfide 600 ℃ of following and manganese or iron or zinc reactions, is generated metal sulfide and H
2Again through molten-salt electrolysis, 700
OCBe that anode carries out electrolysis with the graphite rod in lithium fluoride and sodium chloride and the potassium chloride fused salt mixt, different metal sulfide is decomposed into respective metal and elemental sulfur.
Embodiment 9: elder generation with absorptions such as alkali such as NaOH or potassium hydroxide, obtains vulcanized sodium or potassium sulfide, again with acid stannous chloride solution (PH with hydrogen sulfide<2.12) reaction, precipitation separation obtains artificial gold; Again through molten-salt electrolysis, 550
OCBe that anode carries out electrolysis with the graphite rod in lithium chloride and the potassium chloride fused salt mixt, artificial gold is decomposed into metallic tin and elemental sulfur.
Embodiment 10: elder generation with absorptions such as alkali such as NaOH or potassium hydroxide, obtains vulcanized sodium or potassium sulfide, again with acid BiCl with hydrogen sulfide
3(or Sb Cl
3) solution reaction, precipitation separation obtains burgundy Bi
2S
3(perhaps Sb
2S
3); Again through molten-salt electrolysis, 650
OCBe that anode carries out electrolysis with the graphite rod in lithium chloride and the potassium chloride fused salt mixt, this sulfide is decomposed into metal Bi (or Sb) and elemental sulfur.
Embodiment 11: elder generation with absorptions such as alkali such as NaOH or potassium hydroxide, obtains vulcanized sodium or potassium sulfide, again with CuCl with hydrogen sulfide
2(perhaps CdCl
2﹑ MnCl
2﹑ FeCl
2﹑ NiCl
2﹑ ZnCl
2, CoCl
2, AgNO
3) solution reaction, precipitation separation obtains black copper sulfide (perhaps Liuization Ge ﹑ Liuization Meng ﹑ sulfuration Ya Tie ﹑ Liuization Nie ﹑ zinc sulphide, cobalt sulfide), through molten-salt electrolysis this sulfide is decomposed into metal and elemental sulfur again.
Claims (3)
1. the indirect electric decomposition method of a hydrogen sulfide is characterized in that, the salt ML reaction with hydrogen sulfide and metal earlier generates metal sulfide M S and sour HL; Then this metal sulfide M S is decomposed into metal and elemental sulfur through the molten-salt electrolysis of solid metallic sulfide; Metal that is generated and HL reaction obtain the salt ML of hydrogen and this metal, and so circulation changes hydrogen sulfide into hydrogen and elemental sulfur, and described M comprises Sn, Cd; Described L comprises: Cl, SO
4, NO
3The molten-salt electrolysis of described solid metallic sulfide is meant; Fused salt with M1X is an electrolyte, and the metal sulfide and the metal collector of metal sulfide perhaps having been added the electronic conduction material are compound as solid state cathode, make anode with graphite; Under inert atmosphere, electrolysis temperature is controlled at 450-950
OC, be metal and elemental sulfur with the metal sulfide electrochemical decomposition, wherein M1 contains Li, Na, K, Mg, Ca, Ba is more than a kind of the reaching among the Al; X is F, and Cl is more than a kind of the reaching among the Br.
2. an indirect electric decomposition method of handling hydrogen sulfide is characterized in that, earlier hydrogen sulfide and metal M reaction is generated metal sulfide M S and H
2Then through the molten-salt electrolysis of solid metallic sulfide this metal sulfide is decomposed into metal and elemental sulfur, so circulation changes hydrogen sulfide into hydrogen and elemental sulfur, and wherein, M comprises: Mn, Fe, Co, Ni, Zn, Ag, Cd, Sn; The molten-salt electrolysis of described solid metallic sulfide is meant; Fused salt with M1X is an electrolyte, and the metal sulfide and the metal collector of metal sulfide perhaps having been added the electronic conduction material are compound as solid state cathode, make anode with graphite; Under inert atmosphere, electrolysis temperature is controlled at 450-950
OC, be metal and elemental sulfur with the metal sulfide electrochemical decomposition, wherein M1 contains Li, Na, K, Mg, Ca, Ba is more than a kind of the reaching among the Al; X is F, and Cl is more than a kind of the reaching among the Br.
3. a method of handling hydrogen sulfide is characterized in that, hydrogen sulfide gas is absorbed with alkali earlier, and the reactant salt with metal generates metal sulfide M S again; Then through the molten-salt electrolysis of solid metallic sulfide this metal sulfide is decomposed into metal and elemental sulfur, wherein, M comprises: Mn, Fe, Co, Ni, Cu, Zn, Ag, Cd, Sn, Bi, Sb; The molten-salt electrolysis of described solid metallic sulfide is meant; Fused salt with M1X is an electrolyte, and the metal sulfide and the metal collector of metal sulfide perhaps having been added the electronic conduction material are compound as solid state cathode, make anode with graphite; Under inert atmosphere, electrolysis temperature is controlled at 450-950
OC, be metal and elemental sulfur with the metal sulfide electrochemical decomposition, wherein M1 contains Li, Na, K, Mg, Ca, Ba is more than a kind of the reaching among the Al; X is F, and Cl is more than a kind of the reaching among the Br.
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|---|---|---|---|
| CN2011103710085A CN102500202A (en) | 2011-11-21 | 2011-11-21 | Indirect electrolysis method for hydrogen sulfide |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070893A (en) * | 2015-07-07 | 2015-11-18 | 大连理工大学 | Porous carbon/sulfur cathode material of lithium-sulfur battery and preparation method for cathode material |
| CN108342743A (en) * | 2017-01-23 | 2018-07-31 | 中国石油化工股份有限公司 | It is electrolysed the method and device of hydrogen sulfide preparing high purity hydrogen and sulphur |
| CN108677218A (en) * | 2018-04-26 | 2018-10-19 | 西安建筑科技大学 | A kind of method that molten-salt electrolysis prepares metallic zinc |
| CN109280941A (en) * | 2018-11-16 | 2019-01-29 | 北京科技大学 | A kind of method of ferrotianium grandidierite carbon vulcanization-electrolytic preparation Titanium |
| CN111729485A (en) * | 2020-06-10 | 2020-10-02 | 武汉钢铁有限公司 | High-concentration hydrogen sulfide waste gas treating agent, treating device and method |
| CN111996541A (en) * | 2019-05-27 | 2020-11-27 | 中国石油天然气股份有限公司 | Indirect hydrogen sulfide electrolysis method and device for improving hydrogen yield |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1241648A (en) * | 1999-07-29 | 2000-01-19 | 石油大学(北京) | Preparation of zinc sulfide and hydrogen from hydrogen sulfide |
| CN101597776A (en) * | 2009-07-07 | 2009-12-09 | 武汉大学 | A kind of metal sulfide M 1The metallurgical method of S |
-
2011
- 2011-11-21 CN CN2011103710085A patent/CN102500202A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1241648A (en) * | 1999-07-29 | 2000-01-19 | 石油大学(北京) | Preparation of zinc sulfide and hydrogen from hydrogen sulfide |
| CN101597776A (en) * | 2009-07-07 | 2009-12-09 | 武汉大学 | A kind of metal sulfide M 1The metallurgical method of S |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070893A (en) * | 2015-07-07 | 2015-11-18 | 大连理工大学 | Porous carbon/sulfur cathode material of lithium-sulfur battery and preparation method for cathode material |
| CN108342743A (en) * | 2017-01-23 | 2018-07-31 | 中国石油化工股份有限公司 | It is electrolysed the method and device of hydrogen sulfide preparing high purity hydrogen and sulphur |
| CN108342743B (en) * | 2017-01-23 | 2020-09-08 | 中国石油化工股份有限公司 | Method and device for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide |
| CN108677218A (en) * | 2018-04-26 | 2018-10-19 | 西安建筑科技大学 | A kind of method that molten-salt electrolysis prepares metallic zinc |
| CN109280941A (en) * | 2018-11-16 | 2019-01-29 | 北京科技大学 | A kind of method of ferrotianium grandidierite carbon vulcanization-electrolytic preparation Titanium |
| CN109280941B (en) * | 2018-11-16 | 2020-02-28 | 北京科技大学 | Method for preparing metallic titanium by titanic iron composite ore, carbon sulfurization and electrolysis |
| CN111996541A (en) * | 2019-05-27 | 2020-11-27 | 中国石油天然气股份有限公司 | Indirect hydrogen sulfide electrolysis method and device for improving hydrogen yield |
| CN111996541B (en) * | 2019-05-27 | 2022-01-04 | 中国石油天然气股份有限公司 | Indirect hydrogen sulfide electrolysis method and device for improving hydrogen yield |
| CN111729485A (en) * | 2020-06-10 | 2020-10-02 | 武汉钢铁有限公司 | High-concentration hydrogen sulfide waste gas treating agent, treating device and method |
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Application publication date: 20120620 |