CN110124512A - A kind of processing method of sulfur hexafluoride exhaust gas - Google Patents
A kind of processing method of sulfur hexafluoride exhaust gas Download PDFInfo
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- CN110124512A CN110124512A CN201910515140.5A CN201910515140A CN110124512A CN 110124512 A CN110124512 A CN 110124512A CN 201910515140 A CN201910515140 A CN 201910515140A CN 110124512 A CN110124512 A CN 110124512A
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- molecular sieve
- sulfur hexafluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8659—Removing halogens or halogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/202—Alkali metals
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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 invention discloses a kind of processing methods of sulfur hexafluoride exhaust gas, comprising the following steps: 1) sulfur hexafluoride exhaust gas is passed through in the reaction column containing defluorinating agent, carries out sulfur hexafluoride cracking reaction, obtain reaction end gas；Wherein defluorinating agent is the mixture of modified mesoporous molecular sieve and silicon powder, and modified mesoporous molecular sieve is the mesopore molecular sieve that alkali metal fluoride and alkaline earth oxide are modified jointly；2) reaction end gas is successively passed through to harmless emission after A type molecular sieve, active carbon.The present invention makees catalyst SF with modified mesoporous molecular sieve6Decomposition, catalytic reaction temperature is low, reaction rate is fast, and sulfur hexafluoride resolution ratio is high, then carries out purified treatment to tail gas, realizes SF6Gas is continuous, efficient harmless treatment.
Description
Technical field
The present invention relates to a kind of processing methods of sulfur hexafluoride exhaust gas, belong to field of environment protection.
Background technique
Sulfur hexafluoride (SF6) because of its good insulation performance and arc extinction performance, it is widely used as electrically setting in recent years
Standby dielectric.Because of equipment deficiency or failure, leakage of sulfur hexafluoride gas will lead to, the sulfur hexafluoride gas being leaked in air
Know from experience the safety for endangering operation maintenance personnel, GB26860 " electric power safety working regulation power plant and substation's electric part " is just provided
The concentration of sulfur hexafluoride gas should not be greater than 1000ppm in air.And sulfur hexafluoride is strong greenhouse gases, greenhouse
Effect is 23000 times of carbon dioxide or more, and sulfur hexafluoride gas is such as directly discharged in atmosphere without processing in air, can be right
Ecological environment causes to seriously endanger.
The processing method of sulfur hexafluoride gas is mainly by majority is by the way of alkali cleaning, by gas in existing air
It is passed directly into cleaning solution, gas is dissolved in liquid using the characteristic that sulfur hexafluoride is dissolved in potassium hydroxide, is had reached
The purpose of recycling.109173613 A of Chinese invention patent CN discloses " sulfur hexafluoride waste gas recovering device ", mixed using hydrojet
Sulfur hexafluoride gas is dissolved in potassium hydroxide solution, achievees the purpose that recycling by the mode of conjunction.But this method to only provide recycling
Method does not provide processing method, and the recovery method is cumbersome, and complicated for operation, subsequent processing is also cumbersome.
Chinese invention patent CN103406019B discloses " a kind of processing method of sulfur hexafluoride exhaust gas ", first will be lithium
Sulphur exhaust gas is introduced into the reacting furnace containing defluorinating agent, carries out sulfur hexafluoride cracking reaction, obtains reaction end gas and reaction tailings,
In, defluorinating agent is the mixture of sodium fluoride, silicon powder, metal oxide composition；Obtained reaction end gas is passed through in water again, is carried out
Filtering and drying.But this method still has following defect: the first, the reactivity of defluorinating agent and sulfur hexafluoride resolution ratio and
Reaction speed needs the reaction time of 1 hour more slowly, is unfavorable for the real-time processing of gas；The second, required reaction temperature
Higher (750-850 DEG C), energy consumption is therefore higher, is not easy to field conduct.
207628186 U of Chinese utility model patent CN discloses " a kind of sulfur hexafluoride separator and the hexafluoro with it
Change sulphur separator ", sulfur hexafluoride and air are separated using fibrous material, isolated effect is not further illustrated,
Subsequent treatment process is also cumbersome.
Summary of the invention
To solve the technical problems existing in the prior art, the purpose of the invention is to provide a kind of sulfur hexafluoride exhaust gas
Processing method, catalyst SF is made with modified mesoporous molecular sieve6Decomposition, catalytic reaction temperature is low, reaction rate is fast,
Sulfur hexafluoride resolution ratio is high, then carries out purified treatment to tail gas, realizes SF6Gas is continuous, efficient harmless treatment.
In order to achieve the above technical purposes, the present invention adopts the following technical scheme:
A kind of processing method of sulfur hexafluoride exhaust gas, comprising the following steps:
1) sulfur hexafluoride exhaust gas is passed through in the reaction column containing defluorinating agent, carries out sulfur hexafluoride cracking reaction, obtained anti-
Answer tail gas；Wherein defluorinating agent is the mixture of modified mesoporous molecular sieve and silicon powder, and modified mesoporous molecular sieve is alkali metal fluoride
The mesopore molecular sieve being modified jointly with alkaline earth oxide；
2) reaction end gas is successively passed through to harmless emission after A type molecular sieve, active carbon.
Preferably, the sulfur hexafluoride exhaust gas first passes through membrane separation technique and is isolated and purified, membrane module PDMS,
PI, PMP, PPO or PT, membrane aperture are 2~20nm, and membrane flux is greater than 2500gh-1·m-2, separation factor is greater than 500, film surface
Product is 0.5~2m2, the membrane module of 1~3 grade of configuration, sulphur hexafluoride gas purity after purification is greater than 98wt%.
Preferably, the temperature in the reaction column is 450~550 DEG C, and pressure is normal pressure, and the flow velocity for flowing through reaction column is 1
~10mL/min, residence time are 5~50s.
Preferably, in the defluorinating agent, the mass ratio of modified mesoporous molecular sieve and silicon powder is 1:2~5, preferably 1:2~
3。
Preferably, the mesopore molecular sieve is plane hexagonal phase mesopore molecular sieve, and aperture is 4~10nm, specific surface area
Greater than 900m2/ g, silica alumina ratio (SiO2/Al2O3) it is greater than 300, relative crystallinity is greater than 90%, such as MCM-41, SBA-15 etc. are put down
Face hexagonal phase mesopore molecular sieve, modifying process are as follows:
1) modified water of the alkali metal fluoride of 0.5~2mol/L and the alkaline earth nitrate of 0.5~2mol/L is prepared
Solution, wherein alkali metal fluoride is selected from one or more of sodium fluoride, potassium fluoride, cesium fluoride, alkaline earth nitrate choosing
From one or more of magnesium nitrate, calcium nitrate, barium nitrate, strontium nitrate；
2) the ratio mixing by mesopore molecular sieve and modified aqueous solution in volume mass than 50~100mL/g again, obtains
Suspension stirs 24~48 hours under conditions of 40~70 DEG C, filters；
3) dry 12 at filtering obtained filter cake prior to 100~150 DEG C~for 24 hours, 2~5h is calcined at 400~600 DEG C
Up to modified mesoporous molecular sieve.
Preferably, the length of the reaction column is 1~5m, and reaction column interior diameter is 3~6mm.
The present invention is handled by the purification for gas of early period, greatly reduces the content of foreign gas in exhaust gas, especially
Reduce CO2To the negative interaction of catalyst.Mesopore molecular sieve aperture and SF6Gas molecule diameter is close, to SF6Gas has good
Good absorption property, SF6Gas is after entering modified mesopore molecular sieve, with the defluorinating agent for being attached to mesopore molecular sieve surface
Steam sulphur and other products (6NaF+3Si+12MgO+2SF are resolved into reaction6=3Mg2SiO4+6NaMgF3+ 2S), then flow out point
Son sieve, improves SF6The selectivity and efficiency of decomposition.In addition, the high-content Si in framework of molecular sieve also provides for defluorination reaction
Silicon source, the Al in skeleton2O3Also part alkaline earth oxide can be replaced to participate in reaction (12NaF+3Si+2Al2O3+2SF6=
3SiO2+4Na3AlF6+ 2S), collaboration promotes the defluorinate ability of defluorinating agent.
Compared with the prior art, beneficial effects of the present invention are as follows:
For the present invention using modified mesoporous molecular sieve as sulfur hexafluoride catalyst for cracking, specific surface is greater than 900m2/ g, alkali
Soil metal oxide and alkali metal fluoride are distributed in its duct and surface, and reactivity is higher, and reaction activity is lower,
Catalytic reaction temperature is down to 450 DEG C~550 DEG C, SF6The residence time that gas flows through reaction column is only 5~50s, outlet after processing
SF in air6Volume fraction is in 10ppm or less, it can be achieved that SF6Instant, the efficient process of exhaust gas.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
Defluorinating agent is the mixture (1:2, mass ratio) of modified mesoporous molecular sieve, silicon powder.Modified mesoporous molecular sieve be by
MCM-41 is made, and modification procedure is as follows: 1) preparing NaF concentration is 0.5mol/L and Mg (NO3)2Concentration is the modification of 1mol/L
Aqueous solution；2) the MCM-41 original powder after mould and modified aqueous solution will be gone to mix with the ratio of every gram of 50mL again, obtained suspension
It stirs 48 hours, filters under conditions of 70 DEG C；3) it filters obtained filter cake and is first put into baking oven, the dry 12h at 110 DEG C, then
It is put into Muffle furnace and calcines 3h, grind into powder, that is, modified mesopore molecular sieve at 400 DEG C.Concentration of sulfur hexafluoride is
The air of 2000ppm passes through the membrane separator equipped with PDMS membrane module with 600mL/min and is concentrated, and membrane pressure difference is 0.6MPa,
Membrane area is 0.5m2, the membrane flux of air is 2930gh-1·m-2, sulfur hexafluoride purity using 2 grades of membrane modules, after concentration
For 98.5wt%, it is passed through the reaction column that caliber 4mm long 5m is equipped with 350g defluorinating agent, it is 500 that electrified regulation, which controls reacting furnace temperature,
DEG C, gas flow rate 3mL/min, residence time about 25s, reaction end gas remove after being successively passed through A type molecular sieve and active carbon again
Steam sulphur and a small amount of SO in tail gas2Etc. poisonous and harmful substances, through measurement discharge air in SF6Volume fraction is 8.5ppm,
SF6 gas integrated resolution ratio is up to 99.6%.
Embodiment 2
Defluorinating agent is the mixture (1:3, mass ratio) of modified mesoporous molecular sieve, silicon powder.Modified mesoporous molecular sieve be by
SBA-15 is made, and modification procedure is as follows: 1) preparing KF concentration is 1mol/L and Ca (NO3)2Concentration is the modified water-soluble of 2mol/L
Liquid；2) the SBA-15 original powder after mould and modified aqueous solution will be gone to mix with the ratio of every gram of 100mL again, obtained suspension is 70
It stirs 48 hours, filters under conditions of DEG C；3) it filters obtained filter cake and is first put into baking oven, dry 12h, places at 110 DEG C
Muffle furnace calcines 5h, grind into powder, that is, modified mesopore molecular sieve at 500 DEG C.Concentration of sulfur hexafluoride is 1000ppm's
Air is concentrated by the membrane separator equipped with PMP membrane module, and membrane pressure difference is 0.5MPa, membrane area 0.6m2, air
Membrane flux is 2650gh-1·m-2, using 2 grades of membrane modules, the concentration of sulfur hexafluoride after concentration is 98.2wt%, is passed through caliber
6mm long 4m is equipped with the reaction column of 480g defluorinating agent, and it is 550 DEG C that electrified regulation, which controls reacting furnace temperature, gas flow rate 2mL/
Min, residence time about 35s, reaction end gas remove the steam sulphur in tail gas after being successively passed through A type molecular sieve and active carbon again and lack
The SO of amount2Etc. poisonous and harmful substances, through measurement discharge air in SF6Volume fraction is 5.6ppm, SF6 gas integrated resolution ratio
Reach 99.4%.
Claims (8)
1. a kind of processing method of sulfur hexafluoride exhaust gas, which comprises the following steps:
1) sulfur hexafluoride exhaust gas is passed through in the reaction column containing defluorinating agent, carries out sulfur hexafluoride cracking reaction, obtain reaction tail
Gas；Wherein defluorinating agent is the mixture of modified mesoporous molecular sieve and silicon powder, and modified mesoporous molecular sieve is alkali metal fluoride and alkali
The mesopore molecular sieve that soil metal oxide is modified jointly；
2) reaction end gas is successively passed through to harmless emission after A type molecular sieve, active carbon.
2. the processing method of sulfur hexafluoride exhaust gas according to claim 1, it is characterised in that: the sulfur hexafluoride exhaust gas is first
It is isolated and purified by membrane separation technique, membrane module PDMS, PI, PMP, PPO or PT, membrane aperture is 2~20nm, and film is logical
Amount is greater than 2500gh-1·m-2, for separation factor greater than 500, membrane area is 0.5~2m2, the membrane module of 1~3 grade of configuration, purifying
Sulphur hexafluoride gas purity afterwards is greater than 98wt%.
3. the processing method of sulfur hexafluoride exhaust gas according to claim 1, it is characterised in that: the temperature in the reaction column
It is 450~550 DEG C, pressure is normal pressure, and the flow velocity for flowing through reaction column is 1~10mL/min, and the residence time is 5~50s.
4. the processing method of sulfur hexafluoride exhaust gas according to claim 1, it is characterised in that: modified in the defluorinating agent
The mass ratio of mesopore molecular sieve and silicon powder is 1:2~5.
5. the processing method of sulfur hexafluoride exhaust gas according to claim 4, it is characterised in that: modified in the defluorinating agent
The mass ratio of mesopore molecular sieve and silicon powder is 1:2~3.
6. the processing method of sulfur hexafluoride exhaust gas according to claim 1, it is characterised in that: the mesopore molecular sieve is
Plane hexagonal phase mesopore molecular sieve, aperture are 4~10nm, and specific surface area is greater than 900m2/ g, silica alumina ratio are greater than 300, opposite crystallization
Degree is greater than 90%.
7. the processing method of sulfur hexafluoride exhaust gas according to claim 6, it is characterised in that: the mesopore molecular sieve its
Modifying process is as follows:
1) modified aqueous solution of the alkali metal fluoride of 0.5~2mol/L and the alkaline earth nitrate of 0.5~2mol/L is prepared,
Wherein alkali metal fluoride is selected from one or more of sodium fluoride, potassium fluoride, cesium fluoride, and alkaline earth nitrate is selected from nitric acid
One or more of magnesium, calcium nitrate, barium nitrate, strontium nitrate；
2) the ratio mixing by mesopore molecular sieve and modified aqueous solution in volume mass than 50~100mL/g again, obtained suspension
Liquid stirs 24~48 hours under conditions of 40~70 DEG C, filters；
3) dry 12 at filtering obtained filter cake prior to 100~150 DEG C~for 24 hours, calcine 2~5h at 400~600 DEG C to obtain the final product
Modified mesoporous molecular sieve.
8. the processing method of sulfur hexafluoride exhaust gas according to claim 1, it is characterised in that: the length of the reaction column is
1~5m, reaction column internal diameter are 3~6mm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114797462A (en) * | 2022-05-25 | 2022-07-29 | 武汉大学 | Sulfur hexafluoride thermal catalysis circulation degradation device with hydrogen added |
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| CN101450273A (en) * | 2007-11-28 | 2009-06-10 | 财团法人工业技术研究院 | Treatment method of fluorochemical gas |
| CN102351154A (en) * | 2011-07-28 | 2012-02-15 | 天津市泰亨气体有限公司 | Method for recovering sulfur hexafluoride through membrane separation and selective adsorption |
| KR20120077322A (en) * | 2010-12-30 | 2012-07-10 | 한국과학기술연구원 | Apparatus and method for recovery of sulfur hexafluoride |
| CN103406019A (en) * | 2013-07-02 | 2013-11-27 | 烟台大学 | Treatment method of sulfur hexafluoride exhaust gas |
| CN104108685A (en) * | 2014-07-24 | 2014-10-22 | 四川众力氟业有限责任公司 | Recovery processing and reusing technology of sulfur hexafluoride for power grid |
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2019
- 2019-06-14 CN CN201910515140.5A patent/CN110124512B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450273A (en) * | 2007-11-28 | 2009-06-10 | 财团法人工业技术研究院 | Treatment method of fluorochemical gas |
| KR20120077322A (en) * | 2010-12-30 | 2012-07-10 | 한국과학기술연구원 | Apparatus and method for recovery of sulfur hexafluoride |
| CN102351154A (en) * | 2011-07-28 | 2012-02-15 | 天津市泰亨气体有限公司 | Method for recovering sulfur hexafluoride through membrane separation and selective adsorption |
| CN103406019A (en) * | 2013-07-02 | 2013-11-27 | 烟台大学 | Treatment method of sulfur hexafluoride exhaust gas |
| CN104108685A (en) * | 2014-07-24 | 2014-10-22 | 四川众力氟业有限责任公司 | Recovery processing and reusing technology of sulfur hexafluoride for power grid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114797462A (en) * | 2022-05-25 | 2022-07-29 | 武汉大学 | Sulfur hexafluoride thermal catalysis circulation degradation device with hydrogen added |
| CN114797462B (en) * | 2022-05-25 | 2024-02-23 | 武汉大学 | Sulfur hexafluoride thermal catalytic cycle degradation device added with hydrogen |
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