CN103406019B - A kind of processing method of sulfur hexafluoride waste gas - Google Patents
A kind of processing method of sulfur hexafluoride waste gas Download PDFInfo
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- CN103406019B CN103406019B CN201310275806.7A CN201310275806A CN103406019B CN 103406019 B CN103406019 B CN 103406019B CN 201310275806 A CN201310275806 A CN 201310275806A CN 103406019 B CN103406019 B CN 103406019B
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- sulfur hexafluoride
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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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
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Abstract
The present invention relates to a kind of processing method of sulfur hexafluoride waste gas, first sulfur hexafluoride waste gas is introduced in the reacting furnace containing defluorinating agent, carry out sulfur hexafluoride cracking reaction, obtain reaction end gas and reaction tailings, wherein, defluorinating agent is the mixture of sodium fluoride, silica flour, metal oxide composition; Again the reaction end gas obtained is passed in water, carry out filtering and drying, obtain Powdered sulphur.The present invention selects to be mixed with solid-state defluorinating agent by sulfur hexafluoride in anhydrous conditions, react and sulfur hexafluoride is decomposed, sulfur hexafluoride resolution ratio is high, and does not produce the corrosive gas such as hydrogen fluoride, sulfur trioxide, to the corrosion-free effect of reactor, safety simple to operate, sulfur hexafluoride cracking reaction tail gas passes in water simultaneously, and the sulphur steam of generation meets water condensation, after simple filtration, drying, obtain Powdered sulphur, the Sulphur ressource in sulfur hexafluoride obtains sufficient recycling.
Description
Technical field
The present invention relates to a kind of processing method of sulfur hexafluoride waste gas, belong to field of environment protection.
Background technology
The greenhouse gases of anthropogenic discharge cause terrestrial climate increasingly to warm, and cause the extensive concern of people.In December, 1997, in the United Nations Framework Convention on Climate Change contracting party third session that the representative of 149 countries and regions is held in Japan, have passed the Kyoto Protocol of six kinds of main greenhouse gas discharge capacitys such as restriction carbon dioxide, methane, nitrous oxide, hydrofluorocarbons, perfluocarbon, sulfur hexafluoride.On February 16th, 2005, this protocol is formally effective.
Sulfur hexafluoride (SF
6) be the gas that a kind of colorless and odorless, chemical property are extremely stable, be widely used as the dielectric insulation medium in power plant, magnalium smelts antioxidant etc., the sulfur hexafluoride waste gas that these processes produce directly is discharged in air if not treated, can cause serious harm to ecological environment.
The existing processing method to sulfur hexafluoride waste gas, general employing high-temperature calcination and catalyzed hydrolytic methods.Wherein, high-temperature calcination requires calcining heat more than 1000 DEG C, and just can obtain higher SF when only reaching more than 1500 DEG C
6conversion ratio, energy consumption is very high.And existing catalyzed hydrolytic methods decomposes sulfur hexafluoride waste gas, carry out in the presence of water, by means of the effect of catalyst, sulfur hexafluoride and water reaction decomposes generate sulfur trioxide and hydrogen fluoride, sulfur trioxide, hydrogen fluoride are met water and are generated sulfuric acid, hydrofluoric acid respectively, have strong corrosiveness to reactor, operating process is complicated and dangerous.
The people such as Park (Catal.Today, 2012,185,247-252) have studied AlPO
4/ γ-Al
2o
3catalyst sulfur hexafluoride hydrolysis, reaction gas composition 0.5%SF
6/ 8.5%O
2/ 12.5%H
2o/78.5%N
2(percentage by volume), during reaction temperature 750 DEG C, SF
6resolution ratio more than 90%, but creates severe corrosive gas HF and SO
3, and waste SF
6in Sulphur ressource.The people such as Kashiwagi (J.Colloid Interface Sci., 2009,332,136-144) have studied GdPO
4, YbPO
4, DyPO
4, ErPO
4, SmPO
4, PrPO
4, TbPO
4, NdPO
4, LaPO
4deng phosphate catalyst catalysis sulfur hexafluoride hydrolysis, reaction gas composition 1%SF
6/ 17.8%O
2/ 10%H
2o/71.2%N
2(percentage by volume), also creates severe corrosive gas HF and SO
3, and waste SF
6in Sulphur ressource.The people such as Timms (J.Chem.Soc., DaltonTrans., 1999,815 822), the people such as Lee (Environ.Sci.Technol., 2002,36,1367-1371), the people such as Xu Xiufeng (J.Nat.Gas Chem., 2011,20,543-546; J.Nat.Gas Chem., 2012,21,109-112) have studied the cracking reaction of carbon tetrafluoride on sodium fluoride-silica flour-calcium oxide mixture under anhydrous condition respectively, the simple substance carbon that carbon tetrafluoride cracking produces and other solid products mix, cannot be separated, waste the carbon resource in carbon tetrafluoride.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of processing method of sulfur hexafluoride waste gas, solves the deficiencies in the prior art, has processed sulfur hexafluoride waste gas, can also retain Sulphur ressource, and product environmentally safe.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of processing method of sulfur hexafluoride waste gas, comprises the following steps:
1) sulfur hexafluoride waste gas is introduced in the reacting furnace containing defluorinating agent, carry out sulfur hexafluoride cracking reaction, obtain reaction end gas and reaction tailings; Wherein, defluorinating agent is the mixture of sodium fluoride, silica flour, metal oxide composition;
2) reaction end gas that step 1) obtains is passed in water, carry out filtering and drying, obtain Powdered sulphur.
The invention has the beneficial effects as follows: the present invention selects to be mixed with solid-state defluorinating agent by sulfur hexafluoride in anhydrous conditions, react and sulfur hexafluoride is decomposed, sulfur hexafluoride resolution ratio is high, and do not produce the corrosive gas such as hydrogen fluoride, sulfur trioxide, to the corrosion-free effect of reactor, safety simple to operate, sulfur hexafluoride cracking reaction tail gas passes in water simultaneously, the sulphur steam generated meets water condensation, after simple filtration, drying, obtain Powdered sulphur, the Sulphur ressource in sulfur hexafluoride obtains sufficient recycling.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the temperature in described reacting furnace is 750 ~ 850 DEG C, and pressure is normal pressure, and the flow introducing sulfur hexafluoride waste gas to the reacting furnace containing defluorinating agent is 1 liter per hour of every gram of defluorinating agent.
The beneficial effect of above-mentioned further scheme is adopted to be that when using process of the present invention to contain the industrial waste gas of sulfur hexafluoride, required reaction temperature is starkly lower than high-temperature calcination, and energy consumption significantly reduces, thus reduces cost.
Further, described defluorinating agent by sodium fluoride, silica flour, metal oxide according to mol ratio 1:1:(0.5 ~ 3) mix.
Further, described defluorinating agent by sodium fluoride, silica flour, metal oxide according to mol ratio 1:1:(1 ~ 2) mix.
Further, described metal oxide is the mixing of one or more in aluminium oxide, lanthana, ceria, praseodymium oxide, yittrium oxide, magnesia, barium monoxide, if when wherein many oxide mixes, mix by identical molal quantity.
Further, described reaction tailings comprises metal fluoride, silica or silicate.
Adopt the beneficial effect of above-mentioned further scheme be adopt the object of above-mentioned metal oxide be raw material, product to human body and environment without harm, pollution-free.
Detailed description of the invention
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment one
Defluorinating agent is the mixture of sodium fluoride, silica flour, aluminium oxide, the mixture (1:1:1.5, mol ratio) of sodium fluoride, silica flour, aluminium oxide is loaded reaction tube, inserts reacting furnace, pass into reaction gas 1%SF
6/ 99%He(percentage by volume), the flow that reaction gas introduces reacting furnace is 1 liter per hour of every gram of defluorinating agent.Electrified regulation, 800 DEG C of synthesis under normal pressure 1 hour, SF
6decompose percentage 97.2%.Reaction end gas passes in water, and the sulphur steam of generation meets water condensation, filters, and dry, obtain Powdered sulphur, sulfur recovery rate is higher than 90%.
Embodiment two
Defluorinating agent is the mixture of sodium fluoride, silica flour, lanthana, the mixture (1:1:2, mol ratio) of sodium fluoride, silica flour, lanthana is loaded reaction tube, inserts reacting furnace.Pass into reaction gas 1%SF
6/ 99%He(percentage by volume), the flow that reaction gas introduces reacting furnace is 1 liter per hour of every gram of defluorinating agent.Electrified regulation, 750 DEG C of synthesis under normal pressure 1 hour, SF
6decompose percentage 93.2%.Reaction end gas passes in water, and the sulphur steam of generation meets water condensation, filters, and dry, obtain Powdered sulphur, sulfur recovery rate is higher than 90%.
Embodiment three
Defluorinating agent is the mixture of sodium fluoride, silica flour, ceria, the mixture (1:1:1, mol ratio) of sodium fluoride, silica flour, ceria is loaded reaction tube, inserts reacting furnace.Pass into reaction gas 1%SF
6/ 99%He(percentage by volume), the flow that reaction gas introduces reacting furnace is 1 liter per hour of every gram of defluorinating agent.Electrified regulation, 850 DEG C of synthesis under normal pressure 1 hour, SF
6decompose percentage 98.2%.Reaction end gas passes in water, and the sulphur steam of generation meets water condensation, filters, and dry, obtain Powdered sulphur, sulfur recovery rate is higher than 90%.
Embodiment four
Defluorinating agent is the mixture of sodium fluoride, silica flour, praseodymium oxide, the mixture (1:1:0.5, mol ratio) of sodium fluoride, silica flour, praseodymium oxide is loaded reaction tube, inserts reacting furnace.Pass into reaction gas 1%SF
6/ 99%He(percentage by volume), the flow that reaction gas introduces reacting furnace is 1 liter per hour of every gram of defluorinating agent.Electrified regulation, 750 DEG C of synthesis under normal pressure 1 hour, SF
6decompose percentage 97.1%.Reaction end gas passes in water, and the sulphur steam of generation meets water condensation, filters, and dry, obtain Powdered sulphur, sulfur recovery rate is higher than 90%.
Embodiment five
Defluorinating agent is the mixture of sodium fluoride, silica flour, yittrium oxide, the mixture (1:1:3, mol ratio) of sodium fluoride, silica flour, yittrium oxide is loaded reaction tube, inserts reacting furnace.Pass into reaction gas 1%SF
6/ 99%He(percentage by volume), the flow that reaction gas introduces reacting furnace is 1 liter per hour of every gram of defluorinating agent.Electrified regulation, 800 DEG C of synthesis under normal pressure 1 hour, SF
6decompose percentage 93.8%.Reaction end gas passes in water, and the sulphur steam of generation meets water condensation, filters, and dry, obtain Powdered sulphur, sulfur recovery rate is higher than 90%.
Embodiment six
Defluorinating agent is sodium fluoride, silica flour, magnesian mixture, sodium fluoride, silica flour, magnesian mixture (1:1:1, mol ratio) is loaded reaction tube, inserts reacting furnace.Pass into reaction gas 1%SF
6/ 99%He(percentage by volume), the flow that reaction gas introduces reacting furnace is 1 liter per hour of every gram of defluorinating agent.Electrified regulation, 850 DEG C of synthesis under normal pressure 1 hour, SF
6decompose percentage 95.2%.Reaction end gas passes in water, and the sulphur steam of generation meets water condensation, filters, and dry, obtain Powdered sulphur, sulfur recovery rate is higher than 90%.
Embodiment seven
Defluorinating agent is sodium fluoride, silica flour, barytic mixture, sodium fluoride, silica flour, barytic mixture (1:1:2, mol ratio) is loaded reaction tube, inserts reacting furnace.Pass into reaction gas 1%SF
6/ 99%He(percentage by volume), the flow that reaction gas introduces reacting furnace is 1 liter per hour of every gram of defluorinating agent.Electrified regulation, 800 DEG C of synthesis under normal pressure 1 hour, SF
6decompose percentage 91.7%.Reaction end gas passes in water, and the sulphur steam of generation meets water condensation, filters, and dry, obtain Powdered sulphur, sulfur recovery rate is higher than 90%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. a processing method for sulfur hexafluoride waste gas, is characterized in that, comprises the following steps:
1) sulfur hexafluoride waste gas is introduced in the reacting furnace containing defluorinating agent, carry out sulfur hexafluoride cracking reaction, obtain reaction end gas and reaction tailings; Wherein, defluorinating agent is the mixture of sodium fluoride, silica flour, metal oxide composition;
2) reaction end gas that step 1) obtains is passed in water, carry out filtering and drying, obtain Powdered sulphur.
2. the processing method of sulfur hexafluoride waste gas according to claim 1, it is characterized in that, temperature in described reacting furnace is 750 ~ 850 DEG C, and pressure is normal pressure, and the flow introducing sulfur hexafluoride waste gas to the reacting furnace containing defluorinating agent is 1 liter per hour of every gram of defluorinating agent.
3. the processing method of sulfur hexafluoride waste gas according to claim 1, is characterized in that, described defluorinating agent by sodium fluoride, silica flour, metal oxide according to mol ratio 1:1:(0.5 ~ 3) mix.
4. the processing method of sulfur hexafluoride waste gas according to claim 1, is characterized in that, described defluorinating agent by sodium fluoride, silica flour, metal oxide according to mol ratio 1:1:(1 ~ 2) mix.
5. the processing method of sulfur hexafluoride waste gas according to claim 1, it is characterized in that, described metal oxide is the mixing of one or more in aluminium oxide, lanthana, ceria, praseodymium oxide, yittrium oxide, magnesia, barium monoxide, if wherein during many oxide mixing, mix by identical molal quantity.
6. the processing method of sulfur hexafluoride waste gas according to any one of claim 1 to 5, it is characterized in that, described reaction tailings comprises metal fluoride, silica or silicate.
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| CN103406019B true CN103406019B (en) | 2015-11-04 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028083B (en) * | 2014-07-01 | 2015-12-02 | 福建省邵武市永晶化工有限公司 | A kind of fluorinated tail gas treating apparatus and method |
| CN109045955A (en) * | 2018-09-12 | 2018-12-21 | 烟台大学 | A kind of efficient defluorinating agent and its application in sulfur hexafluoride exhaust-gas treatment |
| CN110124512B (en) * | 2019-06-14 | 2021-09-14 | 国网湖南省电力有限公司 | Method for treating sulfur hexafluoride waste gas |
| CN111186819B (en) * | 2019-12-20 | 2022-03-22 | 河南平高电气股份有限公司 | Sulfur hexafluoride gas purification system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254333A (en) * | 2008-04-09 | 2008-09-03 | 徐秀峰 | Defluorination agent for carbon tetrafluoride anhydrous scission reaction and method of use thereof |
| CN101406795A (en) * | 2008-10-31 | 2009-04-15 | 烟台大学 | Aluminum oxide-base defluorination agent for nitrogen trifluoride anhydrous decomposition reaction and method of use thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254333A (en) * | 2008-04-09 | 2008-09-03 | 徐秀峰 | Defluorination agent for carbon tetrafluoride anhydrous scission reaction and method of use thereof |
| CN101406795A (en) * | 2008-10-31 | 2009-04-15 | 烟台大学 | Aluminum oxide-base defluorination agent for nitrogen trifluoride anhydrous decomposition reaction and method of use thereof |
Non-Patent Citations (2)
| Title |
|---|
| CF4 decomposition over solid ternary mixture NaF-Si-MO;Yanfei Pan等;《Journal of Natural Gas Chemistry》;20120331;第109-112页 * |
| CF4 decomposition without water over a solid ternary mixture consisting of NaF,silicon and one metal oxide;Xiufeng Xu等;《Journal of Natural Gas Chemistry》;20110930;第543-546页 * |
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