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SF6 GAS PROCESSING & RECOVERY

Sudhanshu Gupta
Qualitrol Company LLC

SF6 History
Sulfur Hexafluoride (SF6) discovered in 1900 by Henri Moissan In 1937 it was discovered that SF6 possessed a much higher dielectric strength than air Major supplier Allied Signal (Silver Bottle) began processing SF6 gas in 1948 Other major North American supplier is Air Products (Blue Bottle)

1) SF6 OVERVIEW

SF6 Characteristics
Sulfur Hexafluoride has a unique combination of physical and electrical properties:
- Colorless, odorless, and non-flammable gas - Chemical Inertness - Thermal Stability - Non-toxicity (in its un-altered state) - Excellent Heat Transfer, and cooling properties. - Non-flammability - High dielectric (Insulation)breakdown strength - Non-corrosive (in its un-altered state) - Ability to regenerate - SF6 is one of the heaviest known gases

SF6 Non-electrical Applications


Magnesium Casting Aluminum Degassing Leak Detection Particle Accelerators (Universities) Window Pane Insulation Nike-Air Shoes

Voltage levels of typical SF6 equipment

SF6 Electrical Applications


-Circuit Breakers Typically ~172kV-500kV
-Circuit Switches Typically ~7-35kV - SF6 Bus Duct ~172-800kV

-Puffer Breakers Typically ~72kV-800kV


-GIS (Gas Insulated Substation) Typically ~72kV-800kV

SF6 Characteristics
Not withstanding the excellent properties associated for use in high voltage switchgear, SF6 does have disadvantages

SF6 does breakdown under certain conditions, the products of which can be: A)Hazardous to human health. B)Detrimental to longevity of Switchgear Sulphur Hexafluoride is considered to be a fully fluorinated compound (FFC).

Origins of contamination in SF6


(when used in High Voltage apparatus applications)

1.Gas Handling. (Air and moisture contamination) 2.Leakage. (Air and moisture contamination) 3.Desorption from Surfaces, bulk materials and adsorbers.(Air and moisture contamination) 4.Mechanical generation of dust particles. 5. Decomposition by electrical discharges (Fragmented SF6 molecules created.) 6.Secondary reactions of electrical discharge decomposition products. (Fragmented SF6 molecules created.)

Contamination of SF6
(when used in High Voltage apparatus applications)

Contamination by decomposition products is normally very low and our main attention should normally be focussed on removing Humidity.
Typically the chemically active, corrosive and toxic products WF6, SF4, SOF4, SO2F2, SO2, HF remain below the 100ppmv level

The other main focus is on the reclamation of SF6 to minimise or eliminate release into the atmosphere.

Acceptable Moisture Levels


Transmission lines & bus duct can accept higher moisture levels Main concern is condensation of dew Switchgear requires lower levels due to potential for arcing. Due to moisture the main concern is formation of HF. Hydrofluoric Acid (HF) is a highly corrosive substance that attacks glass and porcelain More stringent requirements needed for GIS Manufacturers limits vary between 50 ppm and 1000ppm

Decomposition Products of SF6


(when used in High Voltage apparatus applications)

Reactive decomposition by-products are created when SF6 is exposed to: spark discharges, partial discharges, switching arcs, failure arcing

Decomposition Products of SF6


At very high temperatures, or in the presence of an electric arc, SF6 can be slowly decomposed Decomposition byproducts include lower fluorides of sulfur, which are hydrolysable, yielding SO2 and HF. Moisture will react with SF6 decomposition products in the presence of an electrical discharge to form a variety of compounds. Decomposition by-products can take the form of gas or powders Other types of contaminants can include moisture and air (from handling or leakage), dust and particles (mechanical
generation)

Detailed chemical analysis in section 3

SF6 Byproducts
SOF4 Thionyl tetrafluoride SOF2 Thionyl fluoride SO2 Sulfur Dioxide HF Hydrogen Fluoride

Many more complex compounds are formed in various concentrations

Good maintenance practices will include periodic SF6 gas analysis

Detailed chemical analysis in section 3

Decomposition Products of SF6


Low

Gas Categories
New

Degree of contamination
High

Gas In cylinders

Non Arced

Used Gas
Normally Arced

Heavily Arced

SF6 Greenhouse Gas??


Sulphur Hexafluoride is considered to be a fully fluorinated compound (FFC). Since FFC's have atmospheric lifetimes of up to 50,000 years, these potent greenhouse gases could contribute significantly and, essentially, permanently to global warming if emissions continue to grow.

For example, lets compare the global warming potential of CO2 and SF6. CO2 has a global warming potential of 1, whereas SF6 has a global warming potential of 24,900!!
The electric power industry uses roughly 80% of SF6 products

worldwide.
SF6 is an expensive asset.

It can be collected, purified and reused.

Chemical behavior under the influence of electrical discharges


High energy electrical discharges cause decomposition of SF6, dissociating into its atomic constituents SF6 S+6F The reaction is immediately reversible and the products recombine SF6 S+6F

Pure SF6 prior to electrical arc

Dissociated SF6 immediately after arc

Natural recombination

Origins of contamination in SF6


(when used in High Voltage apparatus applications)

1.Gas Handling. (Air and moisture contamination) 2.Leakage. (Air and moisture contamination) 3.Desorption from Surfaces, bulk materials and adsorbers.(Air and moisture contamination) 4.Mechanical generation of dust particles. 5. Decomposition by electrical discharges (Fragmented SF6 molecules created.) 6.Secondary reactions of electrical discharge decomposition products. (Fragmented SF6 molecules created.)

Partial discharges decompose SF6 into Fragments of SF4 and F which further react with O2 and H2O to form compounds:

Reactive decomposition by-products are created when SF6 is exposed to partial discharges:

SF5+OH SOF4 +HF SF5+O SOF4 +F SF4+O SOF2 +2F SF3+O+OH SO2F2 +HF HF Hydrogen Fluoride SO2 Sulphur Dioxide SOF4 Sulphur Tetrafluoride Oxide (Thionyl tetrafluoride) SOF2 Thionyl Fluoride (SF4 is readily Hydrolised to SOF2) SO2F2 Sulphural Fluoride

Higher molecular compounds are also formed


(However in practically insignificant Quantities)

S2F10 Disulphur Decafluoride S2OF10 Pentafluorsulphur Oxide S2O2F10 bis Pentafluor-sulphur peroxide S203F6
By products found in Breakers and disconnectors. Lesser quantities found in disconnectors they tend to operate rarely.

Spark discharges decompose SF6 into Fragments of SF4 and F which further react with O2 and H2O to form compounds:

Similar reactive decomposition by-products are created when SF6 is exposed to spark discharges:

SF5+OH SOF4 +HF SF5+O SOF4 +F SF4+O SOF2 +2F SF3+O+OH SO2F2 +HF HF Hydrogen Fluoride SO2 Sulphur Dioxide SOF4 Sulphur Tetrafluoride Oxide (Thionyl tetrafluoride) SOF2 Thionyl Fluoride (SF4 is readily Hydrolised to SOF2) SO2F2 Sulphural Fluoride

Higher molecular compounds are also formed


(However in practically insignificant Quantities)

S2F10 Disulphur Decafluoride S2OF10 Pentafluorsulphur Oxide S2O2F10 bis Pentafluor-sulphur peroxide S203F6
By products found in Breakers and disconnectors. Lesser quantities found in disconnectors they tend to operate rarely.

Powder decomposition by-products created when SF6 is exposed to Switching

arcs:

Some secondary reactions can take place with vaporized electrode metal, container walls, and other construction material. High current flow in these arcs leads to erosion of contact and insulation materials by the hot arc.

CU + SF6 W + 3SF6 CF2 + SF6

CUF2 +SF4 WF6 +3SF4 CF4 +SF4

Erosion of arcing contacts normally made from Copper/Tungsten.

Due to eroded PFTE(A CF2 Polymer)

Al +3F AlF3 3SOF2 +AlO3 2AlF3 + 3SO2

Erosion of arcing contacts normally made from Aluminium.

Other Powder By-products: WO3 (TungstenTrioxide/ Tungsten(VI) oxide / Tungstic anhydride ) WO2F2 (Tungsten dioxide difluoride) WOF4 (Tungsten oxide tetrafluoride) CUF2 Copper(II) fluoride WF6 Tungsten hexafluoride AlF3 (Aluminium trifluoride) Additional powder by products found in Breakers due to switching arcs occuring in load break switches and power circuit breakers.

Chemical behavior in the presence of water vapor. Attention should be focussed on Humidity removal filtration to remove major ppmv contaminants.

SF6 decomposition products combine with water to form secondary products SF6 + H2O 2 HF + SOF2 + 2 F

Hydrofluoric Acid (HF) is a highly corrosive substance that attacks glass and porcelain

Chemical Behavior in the presence of water vapor

Chemical Behavior in the presence of water vapor

Chemical Behavior in the presence of water vapor

H F
O S F F

The following two slides show us levels of contamination, what is critical and what really has no effects on SF6 performance.

Contaminant

Main Origin

Deteriorating effect on

Air CF4 Humidity

Handling Switching arcs Desorption from surfaces and polymers

Switching Gas insulation Surface insulation by liquid condensation

Maximum Tolerable impurity levels in equipment 3% vol

Impurity levels Practical Impurity for reclaimed SF6 detection level to be reused 2% vol < 1% vol < 25 ppmv

200ppmv at 2Mpa 120ppmv 1) compressed to liquification 800ppmv at 500 kPa 1) 4000 ppmv at 100 kPa 1) 100ppmv 100ppmv 320ppmv at 500 kPa 1) 1600 ppmv at 100 kPa 1) 50 ppmv total 7)

< 25 ppmv < 25 ppmv

SOF4 SF4 WF6 Arcing Partial Surface HF SO2 SOF2 SO2F2 discharges insulation Secondary Reactions Surface insulation CUF2 WO3 WO2F2 Contact erosion in Toxicity WOF4 A1F3 switchgear Internal arcing Carbon Polymer Surface Metal carbonisation insulation dust/particles Mechanical wear Gas Insulation Oil Pumps and lubrication Surface insulation

<10ppmv total

Non Critical 4)

No value required
5)

Detection not practical


Detection not practical Detection not practical

Low 4)

No value required
5)

Low 4)

No value required
6)

Prepared for U.S. Environmental Protection AgencyOffice of Air and RadiationGlobal Programs Division1200 Pennsylvania Avenue, NWWashington, DC 20460 Prepared by :ICF Consulting 9300 Lee Highway Fairfax, VA 22031

Moisture in Gas Insulated Switchgear


Sources of moisture in sealed GIE
Surface adsorption (Major cause) Bulk absorption (Second Major cause) Leaks through cracks (Small affects but will accumulate) Permeation through seals (Small affects but will accumulate) Aluminum porosity (Small affects but will accumulate)

Adsorbed and Absorbed Moisture


Adsorbed moisture sticks to surfaces of aluminum conductors, enclosures, and epoxy spacers Absorbed moisture is water in molecular form that permeates into the organic solid such as the filled epoxy spacers Due to initial exposure prior to assembly Large mass of spacers hold large amount of moisture

Application of Desiccants
Desiccants can help to remove moisture from SF6 filled equipment. Desiccants should not be re-used due to absorption of arc by-products Recharging (heating) of the desiccant could release these harmful byproducts

SF6 Acceptable Moisture Levels in HV equipment


Transmission lines & bus duct can accept higher moisture levels Main concern is condensation of dew Switchgear requires lower levels due to potential for arcing. Main concern is formation of HF. Hydrofluoric Acid (HF) is a highly corrosive substance that attacks glass and porcelain More stringent requirements needed for GIS Manufacturers limits vary between 50 ppm and 1000ppm

SF6 Gas Processing - Mixed gas


COLD-WEATHER APPLICATION OF GAS MIXTURE (SF6/N2, SF6/CF4) CIRCUIT BREAKERS Typical in Canada, Russia, Nordic Countries. Very low temperatures stress a circuit breaker in a complex manner. Mixed-gas circuit breakers were developed for use at temperatures as low as -50oC. These breakers utilize a gas mixture of SF6 and CF4 or SF6 and N2 to prevent condensation of the SF6 gas. At low ambient temperatures, below -30oC or -40oC (depending on filling pressure), there is a risk of SF6 condensation, which can cause some reduction of breaking capacity. Mixed gas filling with SF6 and N2 deteriorates the thermal and dielectric breaking capacity. The deteriorated dielectric characteristics can be compensated for with a slightly higher operating pressure.

SF6 Gas Processing


The SF6 recovery units are designed to minimise the disadvantages of SF6 by means of the following:1)Greenhouse gas reduction through transfer of the SF6 from its current housing to onboard or external storage cylinders the gas does not need to be vented into the atmosphere. 2) By-product removal by use of suitably designed filters and scrubbers it is possible to remove hazardous contaminants from the SF6 gas. 3) Cost reduction by efficiently recycling the gas through the recovery unit it is possible to reuse the existing SF6 gas minimising the requirement of purchasing new gas.

2. SF6 PRODUCTS

SF6 Gas Recovery & Purification Products


Typical specification Water removal down to 10 PPM or less Particulate removal to less than 0.1 Equipment vacuum to below 1 Torr Recovery to better than 99.8%

SF6 Gas Recovery & Purification Products


Typical Features

Oil-less or oil-free compressors Onboard or external storage of liquefied SF6 Mobile, static or hand-cart Wide range of accessories Comprehensive test equipment option

SF6 Gas Recovery Products


Accessories and test equipment Systems can be supplied with hoses, power cables, inline hygrometer and weighing scales. Gauging can be digital or analogue.
Operating voltage can be 220V (50/60 Hz), 380V (50 Hz), 415V (50 Hz), 460V (60 Hz) or 575V (60 Hz)

Optional accessories include: Contamination detection Leak detectors Electronic moisture measurement External scrubbing systems for heavily contaminated gas

Interesting stuff
International standards - Purify Gas by filtering 50 ppmv-maximum tolerable impurity level for reuse which translates into a reading of 12 ppmv if the sum concentration of SO2and SOF2is measured (IEC 60480 and CIGRE TFB3.01.01/2004) (China National standard(GB12022-89)

For Sf6 we purify to virtually new parameters. A desiccant dryer complete with Molecular Sieve and Redragon Proprietary Media to remove moisture and lower fluorides of sulphur from arced SF6 gas. Stainless steel filter housing c/w filter cartridge good for 0.1 micron filtration at 98% efficiency. This filter is used at the dryer discharge side to remove any dust or particulate matter. Inlet Stainless Steel Filter housing complete with filter cartridge good for 0.1 micron filtration at 98% efficiency. This filter is used at the suction side of the vacuum compressor to prevent any contamination from getting into the pumping side of the system. Suitably designed filters and scrubbers remove and lower fluorides of sulphur from arced SF6 gas. Water removal down to 10ppm or less Particulate removal down to less than 0.1 Micron Vacuum to below 1 Torr Recovery better than 99.8%