163

GUIDE FOR SF6 GAS MIXTURES

Working Group 23.02

Task Force 01

August 2000
 Draft 7 (SC23 Final)

GUIDE FOR SF6 GAS MIXTURES

(Application and handling in electrical power equipment).

CIGRE WG 23.02

TASK FORCE 01

March 2000
SUMMARY

The present applications of SF6 mixtures in electrical power equipment are determined by
the forces driving their use: technical – avoiding SF6 liquefaction in circuit breakers,
financial – reducing capital expenses on SF6, and environmental – reducing the quantity
of SF6 to reduce emissions of SF6 to the atmosphere. This guide addresses the issues of
using an SF6 mixture, where SF6 is diluted by one other gas, typically nitrogen or CF4,
added at a concentration in the range of 5 to 90%. The practical application of SF6
mixtures in electrical equipment requires an understanding of their performance, both
environmental and functional, as well as methods and equipment for handling gas
mixtures.

The environmental impact of SF6 as a greenhouse gas is reviewed as the first step in
comparing the environmental performance of an application using undiluted SF6 with the
same application using an SF6 mixture. The basis for the comparison is a method for an
environmental Life Cycle Assessment. The comparison illustrates that mixtures with
nitrogen reduce the environmental impact, whereas mixtures with CF4 have no advantage
over undiluted SF6.

The functional performance of SF6 mixtures in electrical equipment is evaluated with

respect to electrical insulation, circuit interruption, the consequences of fault arcing, and
leakage. As the dielectric strength of an SF6 mixture is always less than undiluted SF6,
the gas pressure must be increased to maintain the same insulation, although care must be
taken as the equipment may become more susceptible to defects. For mixtures with
nitrogen there is a synergy, an enhancement in the dielectric strength for the fraction of
SF6, which results in a net reduction in the quantity of SF6 even at the increased pressure.
For all other aspects, the functional performance is similar to undiluted SF6.

Handling SF6 mixtures entails both new and used mixtures of gases, and criteria for
safety, emissions, reuse, transport, and ultimately disposal. In most respects, the technical
definitions and criteria are the same as for undiluted SF6. The important new requirement
is to control the composition of the gas mixture, i.e. the concentration of SF6. Devices for
dynamic mixing of the gases while filling are preferable to diffusive mixing after filling.
Removal and storage of an SF6 mixture intended for reuse requires care to prevent partial
separation by liquefaction of the SF6. A gas mixture that will not be reused can be treated
to recover the SF6 by commercial methods, such as membrane separation and selective
sorption, as well as cryogenic condensation. If reclamation or separation is not feasible,
then disposal of an SF6 mixture by burning in an environmentally acceptable process may
be the only option.

1
1. INTRODUCTION

2. APPLICATIONS OF MIXTURES IN TRANSMISSION &

DISTRIBUTION
2.1 Past and present applications
2.2 Current trends

3. ENVIRONMENTAL PERFORMANCE OF SF6 MIXTURES

3.1 Greenhouse gases
3.2 Basics of environmental life cycle assessment
3.3 SF6 emissions from equipment with SF6-N2 mixtures
3.4 Summary

4. FUNCTIONAL PERFORMANCE
4.1 Insulation
4.2 Interruption in switchgear
4.3 Fault arcing
4.4 Gas deterioration
4.5 Leakage
4.6 Summary

5. HANDLING DEFINITIONS AND CRITERIA

5.1 Definition of technical terms
5.2 Environmental handling efficiency criterion
5.3 Reuse criteria
5.4 Transport criteria
5.5 Summary

6. HANDLING EQUIPMENT AND PROCESSES

6.1 Mixing and composition control
6.2. Gas quality checking and monitoring
6.3 Recoverers
6.4 Storage and transport containers
6.5 Reclaimers
6.6 SF6 separators
6.7 Final disposal
6.8 Commercial equipment and services
6.9 Summary

7. CONCLUSIONS

8. REFERENCES


2
1. INTRODUCTION

Due to an exceptional combination of physical and chemical properties, SF6

has become an indispensable insulation material for electric power
transmission and distribution equipment. Due to its functional superiority it
has replaced older insulation and switching technologies to a large extent. In
particular, high voltage transmission circuit breakers and gas insulated
substations (GIS) are almost entirely based on SF6 as a switching and
insulation medium. Equipment containing SF6 has been shown, in general,
to have a lower environmental impact over life when compared with
equipment not using this excellent gas.

SF6 has, however, been identified as a strong man-made greenhouse gas with
a high global warming potential and a long atmospheric lifetime of the order
of 3000 years [1]. Extensive research to find environmentally preferable
substitute gases for SF6 has been without success (e.g. [2]). It has also been
shown that it is difficult to substitute another gas for SF 6 without increasing
the total environmental impact of the equipment [3].

As SF6 cannot be substituted completely, attempts are being made to reduce

the quantity required to perform a given function. Three major lines are
being followed to attain this goal :-

1. Reducing the size of equipment by better design and quality control –

this automatically entails smaller SF6 quantities per function and
continues to be a major issue in equipment development.

2. Diluting SF6 with a “synergistic” admixture gas such that the SF6
controls the insulation performance of the mixture more than in
proportion to its concentration.

3. Improving the performance of SF6 by admixture of additives that

enhance corona stabilized breakdown levels or arc interruption
performance.

There are two further motivations for using SF6 diluted in a gas mixture: to
reduce the cost of the gas required for equipment, and to prevent liquefaction
in equipment in cold climates. For the latter case, the partial pressure of the
SF6 is reduced to below its vapour pressure for the lowest ambient
temperature expected in a mixture with a non-condensing gas.

This document reviews the main aspects of SF6 mixtures for use in electric
power equipment, namely,
3
- the past, present and possibly future applications of SF6 mixtures in
electric power transmission and distribution equipment,

- the environmental advantages of SF6 mixtures,

- the functional performance of SF6 mixtures as insulating and switching

media,

- the environmentally acceptable procedures for handling and recycling of

SF6 mixtures,

- the equipment for handling and recycling SF6 mixtures.

In this document, the only applications considered are those in which only
one admixture gas is purposely added at a significant concentration, typically
in the range 5 to 90%. The following issues are not treated :-

- mixtures of SF6 with contaminants that have already been treated in the
CIGRE Recycling Guide [4]),

- SF6 added to other gases in the range up to a few per cent,

- low concentration additives to SF6 to enhance corona stabilised

breakdown levels,

- mixtures that have only been studied in basic research laboratory

experiments and have not reached practical testing in equipment.

The only admixture gases that are considered in detail are nitrogen and CF 4,
both of which are already in practical use.

2. APLICATIONS OF MIXTURES IN TRANMSISSION &

DISTRIBUTION

2.1 Past and present applications

The driving forces to use SF6 mixtures in electrical power equipment are as
follows:-

- to avoid SF6 liquefaction at low ambient temperatures by reducing the

partial pressure of SF6
4
- to save on the cost of SF6 and

- to reduce the quantity of SF6 per function for environmental reasons.

In the past the only driving force for using SF6 mixtures has been the need to
reduce its partial pressure at low ambient temperatures to avoid SF6
liquefaction. As admixture gases, both nitrogen and CF4 are in use; each has
a sufficiently low boiling point so as not to liquefy down to the lowest
ambient temperatures and up to the highest filling pressures of interest
(typically -50 oC and 500 kPa). Whereas nitrogen is environmentally neutral,
CF4 may be considered objectionable as it is also a strong greenhouse gas.
However, it should be noted that CF4 is a major by-product of various
industrial processes such as aluminium smelting and fluorochemistry from
which it is emitted at a rate of more than 10 000 tons/y [5]. The emission
from cold climate circuit breakers by leakage and handling is estimated to be
at least three orders of magnitude lower, hence insignificant.

Fig. 2.1 shows the SF6 liquefaction temperature as a function of SF6

concentration in a mixture for 4 total pressures. Note that for an SF 6
concentration of less than 35%, there is no liquefaction down to -40 oC up to
the highest pressure shown.

5
Fig.2.1: SF6 liquefaction temperature Tliq as a function of SF6 concentration
 in a mixture for 4 total pressures 100, 400, 600, and 800 kPa. Calculated
from the SF6 vapour pressure curve.

2.2 Current trends

Current development trends are driven mainly by concerns for the

environment and by efforts to reduce cost, particularly for large installations
such as gas insulated lines (GIL) or large-scale gas insulated substations. Of
particular interest for insulation are SF6-nitrogen mixtures with low SF6
concentrations (5 to 20 % typically) in which the insulation performance is
controlled by the SF6 component in greater proportion than its concentration.
This effect, known as synergism, is due to an optimal match of the molecular
properties of SF6 and nitrogen [6]. Such “diluted” SF6 mixtures have
received high attention in research and are now being used in several
prototype GIL [7][8].

3. ENVIRONMENTAL PERFORMANCE OF SF6 MIXTURES

3.1 Greenhouse gases

SF6 is a strong greenhouse gas with a long atmospheric lifetime. However,

the quantity in which it is produced is rather small so that its present
contribution to global warming is negligible [9]. Nevertheless, in view of the
long atmospheric lifetime of the gas, its emission has to be minimised to
avoid atmospheric accumulation in the long-term future. For this reason, the
SF6 contained in electric power equipment must not be deliberately released
and has to be systematically reused and recycled.

Procedures, equipment and standards for handling, reuse and recycling of

undiluted SF6 in electric power equipment are fully developed [4] [10] and
are being implemented by the electric industry. Furthermore, the
manufacturers of SF6 insulated power equipment are continually reducing the
quantity of SF6 required per function, the manufacturers of SF6 handling
equipment are improving the performance of their devices, and the chemical
industry has developed processes for environmentally acceptable final
destruction of SF6.

One of the drivers for mixing SF6 with other gases is to reduce the
environmental impact of the mixture by reducing the quantity of SF6 in use.
Clearly, the best choices for admixture gases are ones that have less impact
on the environment than SF6. One measure of the impact of a gas is its
6
global warming potential (GWP), a parameter that combines the greenhouse
effect of a gas on a molecular basis with its atmospheric lifetime. SF6 has
the largest GWP of all gases analysed to date, and CF4 also has a large
GWP. On the other hand, nitrogen is a major component of the atmosphere
and has no global warming potential. Therefore, there is practically no
environmental advantage to replacing SF6 with CF4, but there is an
advantage with nitrogen.

Notwithstanding all these measures, a quantification of the environmental

impact of SF6 insulated equipment remains an important task. The use of the
GWP alone is not sufficient to correctly judge the environmental relevance
of SF6 as this figure merely refers to a molecular property and does not
contain any information about the quantitative role of the gas in a
technology. Using the GWP alone therefore may be severely misleading. A
meaningful judgement requires a systems approach, which is now available
in the form of a standardised procedure referred to as an Environmental
Life Cycle Assessment (LCA).

3.2 Basics of environmental life cycle assessment

The quantitative assessment of the environmental impact of a technology is a

complex task in which technical, ecological, health hazard and other aspects
are interwoven. This task can be solved by a standardised procedure, of
which the basic features are outlined briefly here for the particular case of
gas insulated power equipment.

The procedural basis for LCA is documented in the international standard

series ISO 14040 [11]. Expressed in a simplified manner, an LCA is carried
out in the following 5 steps:-

(1) Choose a representative functional unit of the technology with

specified performance, e.g. a GIS bay with a given voltage and switching
performance, or a unit length of a GIL with a given transmission voltage
and power, or even an entire regional electric power supply system.

(2) Define the “horizon” of the study, e.g. which of its life cycle phases
(such as manufacturing, transport, erection, operation, decommissioning
and scrapping) are considered, which material production, energy
generation and transport scenarios are assumed, which types of
environmental impact are assessed, and which methodological approach
is to be applied.

7
(3) Establish a life cycle inventory (LCI) that quantifies all relevant
material and energy flows into the system and all emissions and waste
flows out of it, e.g:-
(a) the materials required and energies consumed to produce the
equipment, such as SF6, conductor and enclosure metals, insulator
materials, materials for support constructions and civil works,
materials for control equipment etc…
(b) the emissions and waste caused by producing these materials and by
the manufacturing processes,
(c) the energy losses in the equipment during its operational lifecycle
(for gas insulated equipment mainly ohmic losses in conductor and
enclosure), and
(d) the energy losses and emissions associated with the
decommissioning, scrapping and recycling of the equipment at its
end of life.

(4) The Life Cycle Impact Assessment (LCIA) phase derives from the LCI
data the corresponding environmental impacts such as emissions relevant
to climate. All impact data are quantitatively aggregated in units of
primary fuels consumed and the associated CO2 emitted so that a total
global warming potential (GWP) can be assigned.

(5) The Life Cycle Interpretation phase combines the LCI and LCIA data
to derive conclusions and recommendations in the framework of the
horizon of the study.

(6) Finally, the ISO standard requires a review of the study by an

independent institution before it can be disclosed.

A special form of an environmental lifecycle assessment is a comparative

assertion in which the environmental impacts of two competing systems of
equal performance are compared in relative terms. An example for a detailed
comparative assertion of an entire regional power supply system is described
in Ref. 12. It evaluates the environmental impact of the system with and
without the use of SF6, and concludes that the full use of SF6 reduces the
total energy consumption and the various atmospheric impact parameters by
about 20 to 30 %.

3.3 SF6 emissions from equipment with SF6-N2 mixtures

A comparative assertion conducted according to the standard ISO 14040 is a

complex task that requires a detailed design, extensive numerical evaluations
and a detailed environmental database. To illustrate its basic working
8
principles, we will consider a specific case, the SF6 emissions from systems
operating with undiluted SF6 and with SF6-N2 mixtures.

As a reference system, we consider a single phase coaxial gas insulation

system filled with undiluted SF 6 at pressure po. This system has a specific
performance in terms of rated voltage and current. Replacing the undiluted
SF6 by a mixture with an SF6 concentration  reduces the insulation
performance. To keep the performance of the reference system, the system
has to be re-designed. For the simplest possible redesign, we increase the gas
pressure* po to the value pmix such that the loss of insulation performance of
the mixture is compensated by a pressure increase.* To determine the
required pressure increase we use the fact that the insulation performance of
gases is proportional to their critical field Ecr, which in turn is proportional to
the gas pressure p so that

Ecr = (E/p)cr,mix p = (E/p)cr,o f() p (1)

where (E/p)cr,o is the pressure reduced critical field of undiluted SF 6 and f()
is a dimensionless correction function characterising the insulation synergy
of the gas mixture (see Fig. 4.1).

To maintain the same insulation performance, we require Ecr,mix (pmix) =

Ecr,SF6(po). This yields
pmix/po = 1/f(
(2)

The quantity of SF6 required is thus reduced by the factor

MSF6,mix/MSF6,o =  pmix/po = /f( (3)

The consequences of this redesign for the emission of SF 6 into the

atmosphere are twofold.

Firstly, the SF6 inventory contained in the equipment is reduced by the factor
/f( This inventory is the relevant quantity for handling losses and
accidental releases. Secondly, the leakage rate of SF6 through sealings and
other small porosities is driven by the partial pressure of the SF6. It is thus
proportional to 
pmix, so that it is reduced, with respect to undiluted SF6
insulation, by the factor

mix /o =  pmix/po =
/f(




*
(Note: Some care is required even with this simple approach as increasing pressure may make the equipment
more susceptible to defect failure.)
9
i.e. by the same factor as the inventory Eq. 3. Thus, provided that the
handling efficiency of the SF6 mixtures is the same as for undiluted SF6, both
handling and leakage losses of SF6 from the system are reduced by the factor
/f( As this factor increases slightly more than proportionally with  one
arrives at the following conclusions:-

(1) Diluting SF6 in a mixture can reduce SF6 emissions, e.g. an SF6
concentration of 10% can reduce the SF6 emissions by about 85%.

(2) Using nitrogen to dilute SF6 reduces the environmental impact

associated with gas emissions, whereas using CF4 has no
environmental advantage because CF4 is also a strong greenhouse
gas.

The above statements are only valid if the mixture is handled with the same
efficiency as undiluted SF6.

3.4 Summary

An assessment of the environmental performance of SF6 mixtures is based on

an assessment of the use and handling of undiluted SF6. SF6 must not be
deliberately released and must be systematically reused and recycled, for
which procedures are available. A systems approach to determine the
environmental effect of SF6 insulated equipment is the Environmental Life
Cycle Assessment (LCA).

A framework procedure for LCA is documented in the international standard

ISO 14040. A special form of LCA is a comparative assertion, in which the
environmental impacts of two competing systems of equal performance are
compared in relative terms. Such a comparison for a system with and
without SF6 concluded that the full use of SF6 reduces the total energy
consumption and the effect on the atmosphere by 20 to 30%.

Although a full LCA or even a comparative assertion of a system containing

a mixture of SF6 with another gas is beyond the scope of this document, the
basic principles are presented by comparing one aspect, the emissions from a
system operating with undiluted SF6 to one with an SF6-N2 mixture. The
comparison concludes that SF6-N2 mixtures reduce the release of SF6 and the
associated environmental impact. For example, an SF6 concentration of 10%
reduces the SF6 emissions by 85%. This conclusion is only valid if the
mixture is handled with the same efficiency as undiluted SF6. Note that SF6-
CF4 mixtures have no environmental advantage over undiluted SF6 because
CF4 is also a strong greenhouse gas.
10
4. FUNCTIONAL PERFORMANCE

4.1 Insulation

The intrinsic insulation performance of an SF6 mixture can be characterised,

to a first approximation, by its pressure reduced critical or limit field (E/p) cr
[13], which only depends on the gases contained in the mixture and their
composition. It can be shown that (E/p)cr is the essential parameter
controlling the design of gas insulation systems not only for ideally smooth
electrodes but also in the presence of insulation defects such as electrode
surface roughness and conducting particles [14].
Fig.4.1 shows the normalised dielectric strength functions f() according to
Eq. 1 for SF6 mixtures with nitrogen and with CF4.

0.9 SF6-N2
0.8

0.7 SF6-CF4
0.6
f

0.5

0.4

0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Fig. 4.1 Normalised dielectric strength functions f() of SF6 mixtures with
nitrogen and with CF4 as a function of the SF6 volume concentration .
It is seen that:-

(1) The insulation performance of SF6 mixtures with nitrogen and with
CF4 is always lower than that of undiluted SF6.

11
(2) SF6 with a high percentage of admixed nitrogen (~ 80 – 95%)
exhibits a strong insulation synergy, i.e. an influence of the SF6
greater than in proportion to its concentration.

(3) SF6 – CF4 mixtures do not exhibit this synergy.

The practical insulation performance of an SF6 mixture is determined by the

presence of insulation defects and depends on the waveform of the applied
voltage. Generally, mixtures with an SF6 content exceeding a few per cent
behave as strongly electronegative gases [15]: Similar to undiluted SF 6 they
have an approximately linear dependence of the effective ionisation
coefficient on the electric field. As a consequence, the sensitivity of the
insulation performance to defects, such as electrode roughness and particles,
and its dependence of the waveform of the applied voltage obey similar laws
as for undiluted SF6.

At equal gas pressure, N2/SF6 mixtures are less sensitive to defects than
undiluted SF6. The relative reduction of the dielectric strength by particles is
approximately related to the reduction of the critical field [14,16,17].

As for the waveform of the applied voltage, it seems that there is no

significant difference in the statistical aspects of breakdown [18]. However,
it is still unknown whether the standard LI (1,2/50) waveshape is the most
critical one. It is expected that the breakdown minimum occurs at front times
in the range 1 to 10 s, as for undiluted SF6. As a consequence, insulation
testing procedures for SF6 mixtures are expected to remain the same as for
undiluted SF6.

With regard to PD measurements and PD diagnostics, it can be stated that the

signal emission of the main type of defect - the mobile particle - is the same
as for undiluted SF6. It has the same frequency spectrum up to 2 GHz. Fixed
defects on live parts or on surfaces of insulating components have a signal
emission that is constant over the range of SF6 content between 20 and 100
%. At lower SF6 content the emission is reduced for frequencies above 600
MHz [19].

Signal damping has been confirmed to be independent of the gas

composition as expected. The following values were found: 2,5 dB/100m for
50 MHz, 8,7 dB/100m for 300 MHz and higher attenuation at higher
frequencies [20].

12
It can thus be concluded that:-

Insulation testing and PD testing of equipment filled with SF6 mixtures

are the same as for undiluted SF6.

Gas insulated lines (GIL) are expected to become one of the major
applications of SF6 / Nitrogen mixtures in the future. As they exhibit some
specific features due to their extended length, their insulation co-ordination
and testing will be briefly discussed. This topic is being treated in the CIGRE
GIL Joint Working Group SC 33/21/23. Some ideas have already been
published in Ref. 21.

The type test shall be carried out on a portion of GIL around 20 m long. It
gives a guarantee of the insulation levels (U w) based on 20 m of GIL for the
3 standard test voltage waveforms AC, LI and SI.

The on-site test shall be performed on portions of GIL from 300 to 1000 m
length with the 3 standard shapes AC, LI and SI but at levels (U ES) lower
than those of the type test. It is proposed to apply UES = 0,8 Uw

During the on-site test the voltage enhancement within the GIL during LI-
testing has to be considered. It is proposed to apply only an AC-test as
recommended in Ref. 6 with a test level UES (AC) = 0,8x0,5xLIWL followed
by a PD test.

For example, oscillating impulse voltages can be applied [22]. For a GIL
length of 1000 m a front duration of 30 s has to be realised by a sufficient
coil inductance to obtain equal crest voltages in the whole GIL. In the case of
a front duration of 10 ms, as often used in GIS, there are deviations of more
than 10 % along the GIL.

Of course, it is especially important in GIL to locate flashovers. Location

systems based on electric signals, e.g. UHF or VHF, or on acoustic signals
can be applied to GIL[22].

4.2 Interruption in switchgear

Circuit-breakers have to interrupt service currents (up to several 1000 A),

small currents - such as capacitive currents - (several amperes to several 100
A), as well as short-circuit currents of several tens of kiloamperes. Two
kinds of short-circuit currents have to be considered, depending on the
distance of the short-circuit from the circuit-breaker: Short-line-fault currents
that demand a high thermal interruption performance because of the high rate
13
of rise of the recovery voltage (RRRV) and terminal-fault currents that
demand a high dielectric interruption performance because of the high peak
recovery voltage.

For cold climate applications in which the SF6 partial pressure is reduced to
prevent liquefaction of the gas, a derating of the short-circuit interruption
performance results, which is illustrated by the data in Table 4.1 for the case
of a 145 kV circuit-breaker.

To realise operating temperatures that are even lower than those shown in
Table 4.1 (e.g. -50°C) and to compensate the derating at least in part, SF 6/N2
and SF6/CF4.are usually admixed. Table 4.2 shows the performance
improvement obtained in this way at various test duties.

Table 4.1: Example for the influence of the SF6 gas pressure on the
interruption performance of a high-voltage circuit-breaker

Arc- Pressure Min. operating Interruption

quenchin temperature performance
g gas
SF6 0.6 MPa -30 °C 145 kV/40 kA
(normal application
range)
-40 °C
SF6 0.45 (special low 145 kV/31.5 kA
MPa temperature
applications)

Table 4.2: Performance of high-voltage circuit-breakers with SF6/N2 and

SF6/CF4.mixtures in comparison to undiluted SF6.

Tests SF6/N2 (e.g. 60/40) SF6/CF4(e.g. 60/40)

SLF Worse
(short-line- (approximately Approximately equal
fault) corresponding to the
SF6 partial pressure)
TF Worse Slightly worse
(terminal-
fault)
Dielectric Worse Worse
(capacitive (see Fig. 4.1) (see Fig. 4.1)
switching)

14
Pure nitrogen or low SF6 partial pressures result in an extreme derating of the
interruption performance [23,24] due to the much reduced arc cooling
efficiency and dielectric strength, with the consequence that such mixtures
cannot be efficiently used in circuit breakers that were originally designed
for undiluted SF6.

Disconnectors have to handle currents up to 1 A. For this they need no

special arc-extinguishing arrangements. An adequately large contact gap is
sufficient to interrupt these currents. The switching performance of
disconnectors is mainly determined by the dielectric properties of the gas
mixture (see Fig. 4.1) and by the dielectric design of the contact
arrangement. For some mixtures the switching characteristics of the gas may
also be important.

Switching disconnectors have to interrupt rated currents, typically up to

several thousand amperes. As the rise of the recovery voltage is relatively
low, switching disconnectors designed for undiluted SF6 can normally also
interrupt the current thermally when operating with SF6 mixtures. However,
as arcing times in SF6 mixtures tend to be longer, a reduction of the dielectric
performance may occur which may require a redesign of the arc
extinguishing zone.

It can thus be concluded that:-

In switchgear the replacement of undiluted SF6 by an SF6 mixture

results in an interruption performance derating.

If the performance is to be maintained, an increase of the operating

pressure and/or redesign are required.

4.3 Fault arcing

Internal arcs within SF6-insulated equipment are normally the severest fault
condition. They are caused by a short-circuit between the live parts of the
equipment and the grounded enclosure. The fault current can reach several
tens of kA with durations of several 100 ms. The arc in the enclosure causes
a rise of pressure which eventually leads to the bursting of the rupture
diaphragms provided for that very purpose and, in extreme cases, even burn-
through of the enclosure.

15
The pressure rise p scales with the arc energy
ui dt introduced into the
enclosure divided by the enclosure volume V.

p = ( –1)
ui dt /V (5)

Here,  is the adiabatic exponent of the gas which is 1.4 for nitrogen, 1.07 for
SF6 and correspondingly takes intermediate values in mixtures. The voltage u
developed by an internal arc depends, among other parameters, on the
enclosure geometry, the gas, the current and the used materials. It is
empirically found to range between 0.8 and 1.4 kV, depending on the
enclosure design, which determines the arc-length. Fig.4.2 shows the
pressure rise according to Eq. 5. This relation is used to dimension the
mechanical strength of the enclosure for a given internal arc current and
arcing-time.

In reality the pressure rise is measured to be lower than the one predicted by
Eq. 5 and Fig. 4.2. The main reasons are that part of the arc energy is taken
up by the enclosure and that the specific heat of the SF6 starts to depend on
the temperature above about 1600 K. The first effect increases with
increasing surface area and with higher temperatures of the heated gas. A
detailed calculation procedure is described in Ref. 25. Fig. 4.3 shows the
result of the calculation together with measured values and with the limiting
curve according to Eq. 5 for reference. It is seen that at low energy input the
deviation is relatively small. For higher energy input the influence increases
and the dependence of the pressure rise on energy is no longer linear.
9

8 100% N2 / 0% SF 6
pressure in enclosure in MPa

5 90% N2 / 10% SF6

4
80% N2 / 20% SF6
3
50% N2 / 50% SF6
2
0% N2 / 100% SF6
1

0
0 5 10 15 20 25
W/Vol. in MJ/m³

Fig. 4.2: Pressure rise as a function of arc-energy per unit volume (filling
pressure 700 kPa, energy dissipation neglected)

16
 5

4.5 without energy-dissipation

pressure in in enclosure in MPa

4

3.5

3
with energy-dissipation
2.5

1.5 measured values

0.5

0
0 5 10 15 20 25
W/Vol. in MJ/m³

Fig. 4.3: Pressure rise as a function of arc-energy per unit volume starting
from a filling pressure of 700 kPa. Gas mixture 80% N2 / 20% SF6. Current
50 kA and Volume V = 650 l. Broken curve: without energy-dissipation;
solid curve: with energy dissipation, crosses: measured values.

4.4 Gas deterioration

During equipment operation and gas handling the gas mixture may be
subject to various deterioration processes that affect its functional
performance once certain levels are exceeded. The major contaminants, their
origins and their deteriorating effects on the functionality of the equipment in
SF6-N2 mixtures are summarised in Table 4.4.

For SF6-CF4 mixtures no particular differences with respect to undiluted SF 6

are observed as both molecules are rather similar from a molecular and
chemical point of view. In the following, the discussion will focus therefore
on nitrogen admixtures.

The most critical deterioration process is a reduction of the SF 6 concentration

in the mixture. It may occur due to SF6 consumption by arc decomposition
and due to SF6 sorption in filters during gas handling. A method to quantify
SF6 consumption by arcing in switchgear is described in Ref. 14. Typically,
for a 50-50 SF6–N2 mixture, between 0.2% to 1.5% of the SF6 is decomposed
in circuit breaker arc interruption for arc currents in the range 5 to 50 kA.
For switchgear operating at low ambient temperatures the SF6 concentration
is typically around 50 % so that this kind of SF6 consumption will normally
17
not constitute a problem. The same applies to the loss of SF6 by sorption in
filters during gas handling as long as the gas composition is checked and, if
necessary, corrected before reuse.

The opposite process to SF6 consumption is SF6 enrichment due to loss of

nitrogen. It might occur by diffusion through leaks because the smaller
nitrogen molecule diffuses more easily through sealings and polymers than
the larger SF6 molecule. Never the less, diffusion is insignificant with
respect to flow through small leaks in enclosures and the leak rates for
nitrogen and SF6 will be essentially identical at typical operating pressures.
A loss of nitrogen leads to both an increase in the SF6 concentration and a
reduction of the total pressure. Quantitatively, the latter degrades the
insulation capability more sensitively so that, paradoxically, SF 6 enrichment
due to nitrogen loss would lead to a reduction of the dielectric performance
when the associated pressure loss is not compensated.

Humidity has the same effect in mixtures as in undiluted SF6. When its
concentration becomes so high that water vapour can condense on insulator
surfaces, electrolytically conducting surface layers are created and lead to
surface flashover. Humidity control in SF6 mixtures should therefore be the
same as in undiluted SF6 [4, 26].

18
Table 4.3: Major contaminants, origins and deteriorating effects in SF6-N2
mixtures.

Contaminant Main origin Deteriorating Critical

effect concentration
Non-reactive
gases Loss of N2 by Reduction of
SF6 enrichment diffusion insulation by
loss of Concentration of SF6
pressure should not fall below
a certain limit with
N2 enrichment Loss of SF6 by arc Reduction of respect to value for
decomposition and insulation which equipment is
adsorption in filters. and/or designed
switching
Air Air contamination by performance
handling errors,
leakage
Excess CF4
Arc erosion of
polymers
Reactive gases
- WF6, SF4, SF6 decomposition
by arcing. Corrosion
(mainly by >1000 ppmv (total)
- SOF2 SO2, HF Hydrolysis with H2O. HF)

- SOF4, SO2F2 Partial discharges

Humidity
H2O Desorption from Condensation
polymers. on insulators Dew point > -5 oC
resulting in
flashover.
Leakage from outside
Switching dust
CuF2, WOF4; Arc erosion of
WO2F2, switchgear contacts. To be
removed by
Arcing dust dust filters
FeF3, AlF3 Arc erosion of
conductor, enclosure

Gas decomposition by discharges is qualitatively similar to that in undiluted

SF6, in which it has been extensively studied and quantified (e.g. [27, 28,
29]). SF6 mixtures are subject to similar decomposition mechanisms but as
the admixed gases introduce further atomic species, further reaction products

19
might be generated. As the discussion here is restricted to the admixture
gases nitrogen N2 and CF4, and as CF4 is already a common decomposition
product in undiluted SF6, it is sufficient to discuss nitrogen as a new reaction
partner.

A recent study of the decomposition of SF6 - N2 mixtures with 10 % SF6

content under partial discharges [30] indicates that the production rates for
the toxic sulphur fluorides and oxifluorides (SF4, SOF2, SOF4, SO2F2,…)
tend to be lower than in pure SF6 and that that the formation rates of nitrogen
containing compounds (NF3, SF5NF2, (SF5)2NF) are much lower than for the
sulphur(oxi)fluorides. The latter are thus irrelevant from a toxic risk point-
of-view.

There are presently no reliable experimental data available for decomposition

of SF6 mixtures by arcs but it can be expected that it will be similar to pure
SF6 because it is controlled by chemical reactions of the reactive gas
component (SF6) with arc eroded materials from contacts and nozzles.
However, it is believed that further work is still being done in this area.

It can thus be concluded that :-

- The major decomposition products in SF6-N2 mixtures are the same

as in undiluted SF6.

- “Surprising” new toxic decomposition products are not to be

expected in relevant quantities.

- The formation rates of arc decomposition products are expected not

to exceed those for undiluted SF6.

- Nitrogen behaves approximately as a chemically inert admixture gas.

4.5 Leakage
From a functional point of view the leakage of both SF 6 and admixture gas is
important. According to IEC 60694, leakage of equipment has to be less than
1% p.a. Modern equipment shows values clearly smaller than 0.5% p.a., on
the order of 0.2% p.a.. Although the leakage flow of each gaseous
component of the mixture is proportional to its partial pressure, this fact does
not play a significant part during equipment operation because of the very
low leakage rates.

20
Other than the recalibration of SF6 density monitors, there are no practical
consequences for gas monitoring and service intervals of equipment filled
with SF6 mixtures.

For topping up, i.e. for filling in small gas quantities, pre-mixed gas should
be used.

4.6 Summary

The insulation performance of SF6 mixtures with nitrogen or CF4 is always

lower than that of undiluted SF6. Therefore in switchgear, the direct
replacement of undiluted SF6 with an SF6 mixture results in a derating of the
interruption performance. To maintain the same performance, either the
operating pressure must be increased or the switchgear must be redesigned.
Note that mixtures with nitrogen exhibit a strong synergy, an enhanced
dielectric strength over the proportion of SF6, whereas mixtures with CF4 do
not. For gas mixtures with more than a few per cent SF6, diagnostic testing
for insulation performance and partial discharge remains the same as for
undiluted SF6.

Fault arcing in an SF6 mixture will result in a greater pressure rise than in
undiluted SF6, for the same conditions. Apart from the temporary pressure
rise, there will also be decomposition products. The major decomposition
products in SF6 mixtures are the same as in undiluted SF6, and the total
production tends to decrease with decreasing SF6 content.

Gas monitoring for pressure or density should be no different for SF6

mixtures than for undiluted SF6, except that density monitors may need to be
recalibrated. The rate of leakage is practically independent of the gas in the
equipment.

5. HANDLING DEFINITIONS AND CRITERIA

5.1. Definition of technical terms

SF6 mixtures are available for use in electric power equipment in premixed
form supplied by gas suppliers (“new” SF 6 mixture), as component gases
(“new” gases) in separate containers from which they have to be mixed on-
site by an adequate mixing procedure, as a mixture that has been previously
recovered from equipment, purified and checked to be suited for reuse.

21
As in the case of undiluted SF6, it should be noted that:-

Used SF6 mixtures must not be stored in containers labelled to contain

new SF6 or new SF6 mixtures.

In the following, the terminology for handling and recycling used SF6
mixtures will be used, in line with the CIGRE SF6 Recycling Guide [4], see
Table 5.1.

Prior to handling, the gas has to be assigned to one of three categories for
used gas mixtures, which define the handling modalities and personnel
protection measures.

Non-arced gas is gas from equipment for which it is known that no arcing
has occurred. Such gas does not constitute a toxic hazard, and personnel
protection measures are not required.

Normally arced gas that has been exposed to normal switching in

switchgear may contain gaseous and solid decomposition products
(“switching/arcing dust”). Personnel who have to open equipment containing
such gas have to be protected by gloves, safety goggles and dust filter masks.

Heavily arced gas that has experienced internal arcing or circuit breaker
failure requires handling by personnel wearing gloves, safety goggles,
protective overalls and respirators.

Thus:-
The safety measures defined for undiluted SF6 cover those for SF6
mixtures.

Gas mixture handling operations on-site include evacuation of the air from
the equipment prior to filling it with the gas mixture, recovering the gas from
the equipment, its reclaiming (purification), subsequent quality checking,
intermediate storage and, finally, reuse on-site or off-site. The totality of
these functions are provided by devices which are referred to as reclaimers.
Devices which are only capable of recovering the mixture, without purifying
it, will be referred to as recoverers.

After having been processed by the reclaimer the gas mixture has to undergo
a quality check, as a result of which it can be assigned to one of the two
reuse categories “suited for reuse” or “not suited for reuse” in electric power

22
equipment. The criteria for this assignment are limit contamination levels
(see Section 5.3).

Gas that is not suited for reuse requires transportation to a site where further
treatment is possible. For this purpose it has to be assigned to a transport
category. Two transport categories are proposed, “non-toxic” and “toxic and
corrosive”, based on limit contamination levels of toxic and corrosive
decomposition products (see Section 5.3).

23
Table 5.1. Summary of technical terms used in recycling SF6 – N2 mixtures

Recovery
Evacuation
Filling
Purification Reclaim
Gas Storage ing
handling Quality check
operations Composition Recycling
correction
Reuse
Transportation
Further treatment off-
site
- N2-SF6 separation
- Final disposal

Used gas categories: - non-arced

- normally arced
- heavily arced

Gas Usage categories: - suited for reuse

categories - not suited for reuse

Transport - non toxic

categories: - toxic and corrosive

Limit contamination - for reuse

levels - for transportation
Criteria
Loss rate per
handling cycle

The gas mixture handling devices mentioned above are subdivided into the
following categories:

24
- Mixing and composition control devices which serve to produce the
mixture from the component gases or to correct the composition of an
already existing mixture,

- Storage and transport containers for which a distinction has to be

made for storage on-site and storage for transportation,

- Recoverers which only serve to recover a gas mixture from equipment

without being able to reclaim it for reuse,

- Reclaimers which can recover a gas mixture from equipment, purify it,
check its quality for reuse and refill it into equipment,

- SF6-separators which can extract the SF6 from the mixture,

- SF6 destruction devices which can transform SF6 chemically into

environmentally benign substances

The main characteristics of the above devices are summarised in Table 5.2.
Details are described in Sections 6.2 – 6.7.

Table 5.2: Main characteristics of SF6-N2 mixture handling devices and

recommended performance figures.

Residual recovery pressure < 5 kPa1) 2)

Residual evacuation pressure <100 Pa1)
Storage capability [m3 STP] According to equipment
Storage pressure [MPa] size
---------
Typical processing time3) t[hours] for V[m3] 3)
Gas loss ratio4) < 1%
Additional recommended features:

Failsafe operation control

Connection to standard gas cylinders for
storage
Oil-free compressors, pumps, sealings etc.
Gas hoses with maximal diameter and
minimal length

25
1)
As for undiluted SF6, see CIGRE SF6 Recycling Guide
2)
1 mbar is recommended and feasible with modern equipment
3)
To be specified for specific gas volume V and connecting piping (length and diameter)
4)
In this case, the ratio of residual recovery pressure to filling pressure (see Section 5.2).

5.2 Environmental handling efficiency criterion

The key environmental criterion for all gas handling processes is the gas
release rate associated with a gas handling operation cycle. It is defined as
the ratio

Quantity of gas mixture lost to the atmosphere

 = ---------------------------------------------------------- (6)
Quantity of gas mixture handled

This rate measures the care with which the gas is handled. A benchmark
value for 
is 1%, given by standard handling technology of undiluted SF6
[4].

As an example, recovering gas from a filling pressure of 500 kPa down to a

residual recovery pressure of 5 kPa corresponds to 
= 5 kPa / 500 kPa = 1%.

5.3 Reuse criteria

Reuse criteria have already been defined for undiluted SF6 in the CIGRE SF6
Recycling Guide [4] and are now in the process of being implemented in the
international standard IEC 60480 [10]. The values proposed in the CIGRE
SF6 Recycling Guide have been used to specify analogous figures for SF 6
mixtures. The results are summarised in Table 5.3 and Fig. 5.1. They are
expressed in terms of volume concentrations referred to the total gas mixture.
Except for the concentration of non-reactive gases, the reuse criteria remain
identical with those for undiluted SF 6. For the admixture gases N2 and CF4,
the reuse criterion has to be re-formulated as these gases are now intended
components of the mixture. Instead of specifying a limit concentration of
these components it is practical to specify limits for the SF6 concentration.

It is proposed that:-

The mixture is acceptable for reuse if its SF6 volume concentration

complies with the specifications of the equipment manufacturer.

26
 Table 5.3: Reuse criteria for SF6 mixtures based on the corresponding
criteria for undiluted SF6 as proposed in the CIGRE SF6 Recycling Guide.

Contaminant Limit concentration

SF6 content SF6 concentration must comply
(complement of with the specifications of the
non-reactive equipment manufacturer
gases like CF4,
air and N2)
Reuse Suited
Criteria Reactive gases < 50 ppmv total or, for
(SF4, WF6, equivalently, reuse
SOF2, SO2, HF, < 12 ppmv SO2+SOF21)
SOF2, SO2F2)
Dew point Td = - 15oC at the
2)
Humidity H2O filling pressure.

1) SO2 + SOF2 as easily detectable indicator gases

2) Non-liquefied mixtures, see Fig. 5.1.

Figure 5.1: Humidity criteria for the reuse of SF6 mixtures: Maximum
admissible humidity concentrations as a function of the total filling pressure.
Solid curve: threshold above which condensation of humidity results in
insulation degradation (Dew point = -5 oC). Dotted curve: maximum
27
admissible concentration for reuse proposed in [4] (Dew point = -15 oC).
Broken curve: requirement for new SF6 [33].

5.4 Transport criteria

As with SF6, the transport criteria for SF6 mixtures have to be established
according to the concentration of toxic and corrosive decomposition products
as these are the only components that determine the health hazard associated
with the gas mixture.

The resulting transport criteria are summarised in Table 5.4. Note that the
ADR classification refers to Europe. Outside Europe the local transport
authorities should be consulted.

Also, note that the transport classification for used SF6 mixtures that meet the
reuse criteria specified in Section 5.3 are the same as for unused mixtures.

Table 5.4: Transport criteria for SF6 mixtures

Classification Criterion ADR Classification

Non-toxic < 200 ppmv (total)1) UN 3163 2)

< 50 ppmv (SOF2 + SO2)

Toxic and Corrosive > 200 ppmv (total) UN 33082)

> 50 ppmv (SOF2+SO2)

1) Based on present ADR regulations which refer to Europe. In any case we recommend
to confirm the packaging and labelling requirements with the local transport
authorities.
2) Regulation for liquefied gas adopted as worst case

It is expected that most of the gas mixtures recovered from electric power
equipment can be purified and corrected for reuse on-site if appropriate
reclaimers are available.

Gas that is classified as non-reusable or that cannot be checked for

reusability on-site can, in most cases, be cleaned of the reactive
decomposition products by passing it through a filter. The gas can then be
transported as non-toxic compressed gas for further treatment off-site. When
28
the reactive decomposition products cannot be removed or their
concentration cannot be checked on-site, the gas has to be considered toxic
and corrosive and has to be stored and transported as such for safety.

5.4 Summary

The technical terms for handling SF6 mixtures are in line with the
terminology described in the CIGRE SF6 Recycling Guide for used SF6. As
a result, the safety measures defined for undiluted SF6 also correspond to
SF6 mixtures. The key environmental criterion for all gas handling processes
is the gas release rate: the benchmark value for standard handling of SF6 is
1%.

The criteria for reuse of SF6 mixtures are based on the limit concentrations of
contaminants. These are similar to the values for undiluted SF6 except that
the admixture gas is now an intentional component and so must have a
concentration appropriate to the application. Most of the gas mixtures
recovered from electrical equipment should be capable of being treated on
site for reuse.

The transport classification of an SF6 mixture depends on the concentration

of toxic and corrosive contaminants in the mixture. Wherever SF6 mixtures
are to be transported, the local transport authorities should be consulted on
the requirements for labels and packaging.

6 HANDLING EQUIPMENT AND PROCESSES

6.1 Mixing and composition control

Mixing and composition control devices serve to mix SF6 with other gases
from separate reservoirs (e.g. cylinders) in the desired proportion or to
correct the SF6 concentration of an available mixture to the desired value.

For small equipment volumes, gases from separate reservoirs can be mixed
manually by filling to the designated SF 6 partial pressure and then topping-
up with the admixture gas to the desired total pressure. The composition of a
mixture already contained in equipment can be corrected by adding one or
the other component gas. When using these procedures, the gas cannot be
considered as sufficiently mixed until after a waiting period, a characteristic
mixing time tmix. An upper limit for this time is the time for diffusive mixing,
the slowest mixing process which is approximately

29
 tmix = L2/D (7)

where L is the longest segment length of the enclosure and D [m2/s] is the
mutual diffusivity of the mixed gases. D is given approximately by the
relation

D = k/p (8)

where k is a constant, k ~ 1 Pa.m2/s for SF6-nitrogen mixtures [31], and p

[Pa] is the total pressure. For example, in a segment length of 1 m at a
pressure of 300 kPa, the mixing time would be several days. A detailed
discussion of diffusive mixing can be found in [41].

In extended structures such as large GIS and GIL, tmix may be unacceptably
long due to the large segment length L of the equipment. In this case a
dynamic mixing device is required to mix the component gases, or to correct
the mixture composition, before they pass through the inlet valve to the
equipment. Such devices are commercially available for SF6-N2 mixtures
[32,33]. They use microprocessor regulated proportional valves and
temperature control, and can be programmed to the desired mixture
composition and filling pressure. They can process both component gases
and mixtures.

The correction of the gas composition in large scale equipment by topping up

one or the other gaseous component is problematic because the mixing
process and gas sampling are difficult to control [31]. This form of
correction should only be used when appropriate knowledge and procedures
are available for the specific case.

As gas filling into power equipment is not associated with losses to the
atmosphere the associated loss rate  is practically zero, unless handling
errors occur.

6.2 Gas quality checking and monitoring

The quality check of reclaimed gas mixtures consists, as in the case of

undiluted SF6, in measuring the SF6 concentration and the concentrations of
humidity and reactive decomposition products. The devices for these
measurements are the same as for undiluted SF6. For measuring the SF6
concentration, the SF6 per cent meters used for undiluted SF6 can be used
directly and have the appropriate accuracy.

30
The sequence in which the gas quality check measurements should be carried
out to minimise working time is shown in Fig. 6.1. The figure also indicates
the gas category assignment as a result of the measurements.

When the reclaimed mixture complies with the criteria for reuse with respect
to reactive decomposition products and humidity, a non-compliance of the
SF6 concentration is not a reason to discard it. If adequate means to correct
the composition are available (see section 6.5,) the mixture can be rendered
reusable by correcting the composition upon refilling the equipment.

Gas and SF6 %

humidity correction
filter
at refilling

Recovered React. Td < -15
C Suited

or < 12 ppmv
reclaimed decomp . (SO2+SOF2 humidity for
prod. equival.) reuse
SF6 mixture

Transport
as:
Not suited React. < 50 ppmv
for decomp . non-
reuse prod. (SO2+SOF2 toxic
equival.)

toxic
and
corrosive

Fig. 6.1: Optimal sequence of gas quality check measurements and gas
category assignment for SF6 mixtures.

6.3 Recoverers

Recoverers are devices that only serve to remove gas mixtures from power
equipment and to store it in transportable form, e.g. in cylinders, so that it
can be transported off-site for further treatment. Recoverers only require a
pre-filter to protect the compressor from excessive dust and corrosive
decomposition products. They are able to recover the gas mixture down to a
residual recovery pressure of less than 5 kPa.

Recoverers have the advantage of relatively low investment and service costs
and only require modest operation expertise. By using a recoverer, the more
complicated processes of gas purification and gas quality checking are
delegated to an adequately equipped SF6 service centre off-site.

31
The components of a recoverer (valves, piping, pre-filter, compressor,
controls etc.) can be obtained from suppliers of SF6 recycling equipment who
can also assemble them into a system.

The first essential performance parameter of a recoverer is its processing

speed, which is best quantified as the time T rec required to reach a specified
residual recovery pressure prec when recovering a given gas volume V
through a specified connecting piping (length and cross section). For
example,

Trec = 2 h for recovering V = 5 m3 down to pres = 5 kPa through a hose of

length 5 m with cross section 12 cm2.

The second essential performance parameter is the loss rate of the recovery
process, which is the ratio of the residual recovery pressure to the filling
pressure of the equipment:
 = prec/ pf (9)

The residual recovery pressure prec is thus the key figure determining the
environmental efficiency of the recoverer.

Recoverers that have been designed for undiluted SF6 can, in principle, also
be used for recovering SF6 mixtures. Nevertheless, because of the different
adiabatic exponent of the mixture, the maximal compression pressure and the
storage volume may have to be re-rated to avoid compressor failure.

6.4 Storage and transport containers

SF6 mixtures can be stored as uniform mixtures in high-pressure containers

in gaseous form provided that the SF6 component does not liquefy, as this is
a form of separation. Liquefaction extracts SF6 from the gas phase and
reduces the SF6 concentration there. The maximum pressure pcomp to which a
mixture can be compressed without SF6 liquefaction depends on the SF6
volume concentration  and the ambient temperature T. It can be calculated
from the vapour pressure curve of SF6 (see Fig. 6.4) and is given in Fig. 6.2
for three ambient temperatures. A few examples will illustrate how to
interpret Fig. 6.2.

At 5 MPa, typical of compressors used for handling undiluted SF6, SF6

mixtures can only be stored at ambient temperatures above 20 oC if they
contain less than 40 % SF6.

32
Dilute SF6 mixtures, e.g. 10 % SF6, must not be compressed beyond 2 MPa
at an ambient temperature of 20 oC.

Mixtures with 50% SF6 must not be compressed to more than 4 MPa at an
ambient temperature of 20 oC.

When working in a cold environment the storage pressure has to be greatly

reduced. At – 20oC, mixtures with 50% SF6 can only be stored up to 1.4
MPa without liquefying.

20
Maximal storage pressure pcomp [MPa]

15 o
+20 C
o
0 C
10 o
-20 C

0
0 50 100
SF6 concentration  [% ]

Fig.6.2: Maximal storage pressure pc of an SF6 mixture as a function of the

SF6 concentration.

The most convenient pressure containers for SF6 mixtures are standard
compressed gas cylinders of the nitrogen type. Their major advantages are:-

- low cost
- compactness
- transportability
- low risk when large quantities of gas have to be stored (the cylinders can
be connected by manifold tubing to form stationary or truck-mounted
cylinder batteries).

33
Larger storage tanks can also be used if they are suited for the desired
storage pressure and comply with storage and/or transport regulations.

34
6.5 Reclaimers

Besides fulfilling all the functions of recoverers, reclaimers have the

additional capability to purify the gas mixture and to correct its composition,
if necessary, so that it can be reused on-site.

The basic structure of a mixture reclaimer is shown in Fig. 6.3. Its main
elements are a vacuum pump to evacuate the air from the equipment prior to
filling it with SF6, a compressor or compressor set to recover the SF 6 mixture
from the equipment and compress it into a storage container, a dust filter to
remove solid particles from the recovered gas, a gas/humidity filter to
remove reactive gaseous decomposition products and humidity, and a storage
tank for the purified gas. An additional pre-filter can be inserted at the input
of the reclaimer when “heavily arced” gas has to be processed. Note that the
gas mixture should never be compressed into the reclaimer tank to a pressure
at which the SF6 will start to liquefy.

Another essential element of a mixture reclaimer is a dynamic mixture

composition correction device as described in Section 5.5 (“mixer” in the
Fig. 6.3). While filling equipment, such a device allows the addition of either
SF6 or admixture gas to the reused mixture to adjust the mixture composition
to the desired value. A further integral part of a reclaimer is the measuring
equipment required to check the gas mixture for reusability.

SF6 - N2 recover
EQUIPMENT PREFILTER

VACUUM DUST FILTER

PUMP
COMPRESSOR(S)
Mixer
refill
and
SF6 % corr. GAS / HUMIDITY
FILTER

SF6 N2 STORAGE

Fig. 6.3: Basic structure of an SF6 mixture reclaimer, shown with nitrogen as
the admixture gas.

Reclaimers for undiluted SF6 have been developed through the last three
decades and are commercially available for all application ranges in T&D
35
equipment. Reclaimers for SF6 mixtures are commercially available too.
Within certain limitations, reclaimers designed for undiluted SF 6 can be
retrofitted to be used for SF6 mixtures.

6.6 SF6 separators

Although from an economic point of view it is advantageous to handle SF6

mixtures as mixtures, separation of the SF6 may be necessary under certain
circumstances. The physical principles that can be used for SF6 separation
are listed in Table 6.1.

Table 6.1: Basic physical principles for separating SF6 from mixtures.

Basic principle Method Comments

High compression
and low
Condensation of SF6 by temperatures
Condensation compressing and required to reach
cooling the mixture; low loss rate;
extraction of the SF6 removal of solid SF6
condensate condensate at low
temperatures is
problematic

No experience,
Sorption Selective sorption though commercial
devices are
available.

Experienced
a) Membrane technology,
separation Commercial devices
available.
Diffusion Highly developed
for military
applications,
b) Thermodiffusion especially isotope
c) Gas centrifuges separation.

SF6 condensation

36
The separation of SF6 by condensation and extraction of the condensate may
be an effective separation process particularly when sufficiently high
compression pressures and/or low cooling temperatures are used. In this
process, however, the gas phase above the liquefied SF6 still contains an
appreciable amount of SF6, which determines the loss rate of the separation
process.

Quantitatively, this process is characterised by the compression pressure

pcomp and the cooling temperature Tc. The controlling relation is the vapour
pressure curve of SF6, which is shown in Fig. 6.4 [34]. It gives, on the left
side scale, the vapour pressure pv of SF6, i.e. the partial SF6 pressure above
which SF6 condensation begins, as a function of the cooling temperature Tc.
The right side scales show the total pressures at which the SF6 would
condense from a mixture. The two scales are valid for a 10 % and a 50 % SF6
mixture, respectively.

It is seen that almost 20 MPa are required to start SF6 condensation from a
10% SF6 mixture at ambient temperature 20 oC whereas 4 MPa are sufficient
to start condensation from a 50 % SF6 mixture at ambient temperature.
However, the start of condensation does not mean that all the SF6 condenses.
The fraction of the SF6 that actually condenses increases with increasing
compression pressure and with decreasing cooling temperature. A further
important feature of the process is that the SF6 condensate is only liquid
down to the melting point of SF6, which is Tm = - 51 oC (broken line in Fig.
6.4). Below this temperature the SF6 condenses in solid form as “SF6 snow”,
the extraction of which may pose considerable practical problems.

Reference (43) treats the cases of SF6-N2 mixtures containing 50% SF6 or
more, and discusses the factors limiting the efficiency of its separation and
how it can be improved.

37
 10000 100 20
10
solid liquid

Total pressure of 10% SF6 mixture [MPa]

Total pressure of 50% SF6 mixture [MPa]

SF6 vapor pressure [kPa]

1000 10

gaseous 1

100 1

0.1

10 0.1

1 0.01
-100 -50 0 50

temperature T [
C]
Fig. 6.4: Vapour pressure curve of SF6. Pressure scale on the left side refers
to undiluted SF6 or to the SF6 partial pressure. Pressure scales on the right
refer to the total pressure of a 10 % and a 50 % SF6 mixture. Left of the
broken line (melting temperature) SF6 condenses in solid form.

The vapour pressure curve pv(Tc) gives the SF6 partial pressure in the gas
above the liquid phase and thus quantifies the SF6 concentration res that
remains in the gas phase:-

res= pv (Tc) / pcomp (10)

As the SF6 quantity contained in the gas phase is proportional to res pcomp 

and the SF6 quantity originally contained in the mixture is proportional to 

pcomp, the fraction of SF6 remaining in the gas phase is:-

 = res /= pv (Tc) /( pcomp) (11)

which is the loss rate of the condensation method for separating SF 6.

It is seen that the loss rate decreases with the cooling temperature Tc and with
increasing compression pressure pcompr and initial SF6 concentration  of the
mixture.

Fig. 6.5 shows a plot of the loss rate  as a function of the cooling
temperature Tc for compression pressures pcomp of 5 and 20 Mpa and for a
38
50% (solid curves) and a 10 % SF6 mixture (broken curves). It is seen that
the benchmark value of 
= 1% can only be reached at cooling temperatures
Tc below the melting point Tm of SF6. This would entail a high cooling cost
and, in addition, create the problem of extracting SF6 as “SF6 snow” .

Practical limit values for the loss rate can be obtained by assuming a cooling
temperature of Tc = -40 oC, which can be reached with standard refrigeration
devices and allows the extraction of SF6 as a liquid. At this temperature, the
vapour pressure of SF6 is pv (Tc = -40 oC)= 350 kPa. The loss rates for
compression pressures of 5 and 20 Mpa are shown in Table 6.2.

Table 6.2: Loss rate for SF6 separation by condensation at -40 oC as a

function of initial SF6 concentration and compression pressure.

Compression pressure 10 % SF6 50% SF6

5 MPa 70% 14%
20 MPa 17.5% 3.5%

Therefore from a practical point of view it can be concluded that:-

The separation of SF6 from mixtures by compression, SF6 liquefaction

and liquid extraction-

(1) is feasible at high SF6 concentrations (> 30%), and

(2) is not efficient at low SF6 concentrations (< 30 %).

For high SF6 concentrations, the corresponding equipment is commercially

available and can extract high purity SF6 (>99%). The residual gas,
however, contains so much SF6 that it cannot be released into the
atmosphere. It may either be reused for low percentage applications or must
be processed further, maybe in combination with another separation process.

39
 10%, 50 bar 10%, 200 bar 50%, 50 bar
release rate [%] 100

50%, 200 bar

10

1
-60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60
cooling temperature [
C]

Fig. 6.5: SF6 loss rate 
as a function of the cooling temperature Tc for the
compression/SF6 liquefaction separation process for mixtures with  = 10 %
and 50 % SF6 and for compression pressures pcomp of 5 MPa and 20 MPa.

Selective sorption

Selective adsorbers (molecular sieves or Zeolites) are commonly used for

gas separation in pressure swing adsorption processes, e.g. to remove
chlorinated compounds from air. Molecular sieves adsorbing SF 6 are
described in Ref. 35. In these substances the pore size can be designed such
that SF6 (molecular diameter 0.522 nm) is adsorbed and nitrogen (molecular
diameter 0.258 nm) passes through. Special hydrophobic molecular sieves of
this type have also been synthesised to allow the removal of SF 6 from a
mixture with nitrogen down to a residual concentration of only 10 ppmv
[36].

Membrane separation

Membrane separation is a well established gas separation technology and is

becoming commercially available for SF6 separation at reasonable process
speed. Membranes have been used for more than ten years as on-site gas
separation processes. During the last five years membrane separation
technology has gone through an enormous improvement process as new
membrane materials have become available. This has enabled the widespread
application of on-site gas separation.
40
For the separation of SF6 from nitrogen, modular membrane systems are now
available that can be assembled as mobile separation devices with gas
throughput rates between 1 and 300 m3/h at arbitrary SF6 concentrations
[37]. This process is efficient for 5 to 95% of SF6 mixtures and particularly
efficient at low SF6 concentrations.

Thermal-diffusion or gas centrifuges

These processes are used for separating uranium isotopes and would
certainly be effective for separating SF6 from nitrogen as these two gases
differ greatly in molecular weight, but there is presently no practical
experience for this application. Due to their military applications, these
methods are not easily available.

Combined processes.

Process combinations are frequently used to optimise performance and cost.

It can be expected that this is also true for the separation of SF 6 from
mixtures. Practical solutions combining some of the above processes,
although presently not yet available, may eventually emerge.

6.7 Final disposal

Gas mixtures containing environmentally critical gases such as SF6 and CF4
eventually have to be destroyed when they cannot be rendered reusable or
when they are no longer needed. This destruction has to occur in an
environmentally acceptable way; i.e. these gases have to be transformed into
environmentally benign substances. For the destruction of SF 6, a typical
chemical process is the reaction

SF6 + 4 CaO -> 3 CaF2 + CaSO4 (12)

where CaO is lime, CaF2 is fluorspar and CaSO4 is gypsum, all of which are
environmentally benign materials. Similar reactions are available for the
destruction of CF4.

Such decomposition reactions can be technically realised in several different

ways:-
Thermal SF6 decomposition

This is presently the only industrially and commercially available process

[38]. The SF6 is injected as a co-flow into a high temperature flame where it
41
reacts with the oxidation products of the burning fuel (containing oxygen and
hydrogen) to form products such as HF, SO2 and SOF2. These products are
neutralised by flue gas treatment to form such substances as fluorspar and
gypsum according to the above reaction Eq. 12. SF6 mixtures could be
treated in the same way, though at higher energy cost. It may therefore be
preferable to enrich the SF6 in the mixture by a separation process before
destruction.

A more economic alternative to burning SF6 in special kilns might be the

injection of gas mixtures containing SF6 and/or CF4 as co-flow into domestic
waste incinerators with adequate flue gas treatment. This process is presently
under study.

Chemisorption of SF6

In this concept, the gas mixture is brought in contact with a substance that is
capable of reacting with SF6 to form products with much lower or no
environmental impact. From the chemical literature it is known that SF6 and
CF4 are thermodynamically unstable at sufficiently high temperatures and
can react with a number of metals and metal oxides. Some such reactions
were studied in Ref. 39 for SF6. It was shown that activation temperatures
above 500 °C were required to obtain sufficiently high reaction rates.

Surface decomposition of SF6

As with metal oxides, SF6 and CF4 can also react with metals. As an
example, it has been shown that SF 6 decomposes very slowly at copper
surfaces above 250 oC [40]. It is not clear if this process is a chemical
reaction with the metal or if catalysis is also involved.

Discharge decomposition of SF6

It has been demonstrated that destruction reactions for fluorocarbons can be

activated in a microwave discharge [41]. Such a process might also be
applicable to SF6 and SF6 mixtures.

It can thus be concluded that:-

An environmentally acceptable method for the final destruction of SF6

and/or CF4 containing gas mixtures is feasible and commercially
available.

42
6.8 Commercial equipment and services

Equipment for handling SF6 mixtures is now becoming commercially

available. Also, existing handling equipment for undiluted SF6 may be
retrofitted to work with SF6 mixtures. SF6 separation is technically feasible
and is commercially available for limited application ranges, although more
development work is required, specifically for mixtures with low SF6
content. The final destruction of SF6 and CF4 is feasible and limited services
are commercially available.

For a rapid implementation of the environmentally acceptable handling of

SF6 mixtures it is important to provide a network of information and services
to users. Some of this information can be found on the Internet as provided
by SF6 producers, handling equipment manufacturers and SF6 service
enterprises. A CIGRE homepage has now been established to collect such
information and provide contact lists of handling equipment manufacturers
and services. <www.cigre-sc23.org>

6.9 Summary

Devices for mixing and controlling gas composition are required for
handling SF6 in mixtures. Filling electrical equipment with premixed gases
or by dynamic mixing of component gases is preferable to filling with
undiluted gases which relies on diffusive mixing in the equipment.

Recovery devices only extract gas from equipment to storage containers.

Reclaimers act as recovery devices and can also purify the gas and correct its
composition. Checking the quality of reclaimed gas with respect to humidity
and decomposition by-products is essentially the same for SF 6 mixtures as
for undiluted SF6.

Care should be taken to store SF6 mixtures intended for reuse so that the SF6
does not condense thereby partially separating the mixture. The maximum
storage pressure without liquefaction is a function of the ambient
temperature and the SF6 concentration, essentially the vapour pressure of
SF6.

Intentional separation of SF6 from a mixture requires dedicated equipment,

which is commercially available. Cryogenic condensation is applicable for
SF6 concentrations down to about 30%, but the residual gas still contains a
significant concentration of SF6. For lower SF6 concentrations, membrane
separation and selective sorption are more suitable. Of all the methods,

43
membrane separation is probably the most promising and efficient
technology for arbitrary SF6 concentrations.

Finally, if reclamation or separation is not feasible, then disposal of a gas

mixture may be the only option. An environmentally acceptable method for
disposal is destruction or chemical transformation of the component gases,
for example by burning, to produce substances with less environmental
impact. Methods of burning SF6 are commercially available and would be
applicable to SF6 mixtures, though at higher energy cost.

44
7. CONCLUSIONS

(1) The main rationale for using SF6 mixtures, aside from low temperature
applications and lower gas costs, is the reduction of the environmental
impact by reducing SF6 emissions. The degree of environmental impact
reduction obtainable by using SF 6 mixtures instead of undiluted SF6 has
to be quantified by environmental life cycle analysis (LCA) according
to the Standard ISO 14040.

(2) The established handling and recycling technology for undiluted SF6,
which has been commercially available for a few decades, can normally
not be directly used to handle the SF6 mixtures discussed in this
document.

(3) A restricted handling concept is available in which SF6 mixtures can be

reused without separating the SF6. The key element for this concept is a
dynamic mixing and composition correction device, which is
commercially available.

(4) Some of the existing handling equipment for undiluted SF6 can be
upgraded to handle SF6 mixtures within the above restricted concept.

(5) SF6 can be separated from mixtures by various processes and process
combinations. Corresponding equipment with low loss rate is now
becoming commercially available.

(6) If disposal of SF6 mixtures is required, environmentally acceptable final

destruction of SF6 mixtures is feasible and commercially available.

45
8. REFERENCES

[1] Radiative Forcing of Climate Change", the 1994 report of the scientific
assessment working group of IPCC, p.28.

[2] L.G. Christophorou, I. Sauers et.al., “ Recent Advances in Gaseous

Dielectrics at Oak Ridge National Laboratory”, IEEE Trans. Electr.
Insul.,19 (6) (1984), 550-566“

[3] L. Niemeyer, “A systematic search for insulation gases and their

environmental evaluation”, 8th Internat. Sympos. on Gaseous
Dielectrics, Virginia Beach, June 1998

[4] CIGRE WG 23-10, “ SF6 Recycling Guide”, ELECTRA 173 (1997)

43-69

[5] Cicerone, “Atmospheric carbon tetrafluoride:A nearly inert gas”,

Science, 206 (1979). p. 59-61

[6] L. G. Christophorou and R. J. Van Brunt, “SF6-N6 mixtures”, IEEE

Trans. Dielectr. Electr. Insul., 2 (5) 1995, 952-1003

[7] X. Waymel “Low SF6 concentration SF6/N2 mixtures for GIL”, 8th
Internat. Sympos. on Gaseous Dielectrics, Virginia Beach 1998,
Plenum, 345-351

[8] Koch, H., “Future aspects of gas insulated transmission line (GIL)
applications”, CIGRE SC23.99 (COLL) IWD, Zurich 1999

[9] CIGRE WG 23-10, “ SF6 and the global atmosphere”, ELECTRA 164
(1996) 121-130

[10] IEC (International Electrotechnical Commission) Standard 60480

“Guide to the checking and treatment of SF 6 taken from electrical
equipment”, presently under revision

[11] ISO Standard 14040 Environmental management – life cycle

assessment – principles and framework, 1st ed. 1997

[12] Zahn, B. and Ruess, E., “Economical and ecological system

comparison for the electricity supply of an urban area”, CIGRE
SC23.99 (COLL) IWD, Zurich 1999

46
[13] Boeck, W., Pfeiffer, W.: "Conduction and Breakdown in Gases".
Wiley Encyclopaedia of Electrical and Electronics Engineering, J.G:
Webster ed., (1999)

[14] Niemeyer, L.: “Gaseous insulation”, Wiley Encyclopaedia of

Electrical and Electronics Engineering, J.G: Webster ed., 1999, Vol.8,
p.238-258

[15] Gallimberti, I. Et al., “Corona formation and propagation in weakly

and strongly attaching gases”, Proc. 8th Internat. Conf. On Gas
Discharges, Oxford 1985, Pergamon, p.587-594

[16] Imano, A.M.; Schurer, R.; Feser, K.: “The Influence of a Conducting
Particle on a Spacer on the Insulation Properties in SF6/N2 Mixtures”,
ISH 1999, London, paper 3.233.

[17] Diessner, A.; Finkel, M.; Grund, A.; Kynast, E.: “Dielectric Properties
of N2/SF6 Mixtures for Use in GIS or GIL”, ISH 1999, London, paper
3.67.

[18] Graf, R.; Boeck, W.: “Statistical Breakdown Behaviour of N2-SF6 Gas
Mixtures under LI Stress”, ISH 1999, London, paper 3.96.

[19] Schöffner, G.; Boeck, W.: “PD Measurements in N2-SF6 Gas Mixtures
With the UHF Method”, ISH 1999, London, paper 5.86.

[20] Okubo H. et al.: “Partial Discharge Measurement in Long Distance

Transmission Line (GIL)”, 10th ISH Montreal 1997.

[21] Sabot, A.: “Insulation Co-ordination of 420 kV Gas Insulated Lines

(GIL)”, CIGRE 1998, Report 21/23/33-02.

[22] Diessner,A.; Koch, H., Kynast, E.; Schelle, A.: “Progress in High
Voltage Testing of Gas Insulated Transmission Lines”. 10th ISH
Montreal 1997, Vol.4, pp.41-43
.
[23] Grant.D.M.etal “Comparative interruption studies of gas blast arcs in
SF6-N2 and SF6-He mixtures”, 4th International conference on gas
discharges and their applications, Proc. Pp48-51.

[24] H. Knobloch: “The comparison of arc-extinguishing capability of

sulphur hexafluoride (SF6) with alternative gases in high-voltage
circuit-breakers”, Gaseous Dielectrics VIII, edited by L.G.
47
 Christophorou, J.K. Olthoff, 1998 Kluwer Academic / Plenum
Publishers, New York, pp. 565-571

[25] Babusci, G. et al.: “Assessment of the behaviour of gas-insulated

systems in presence of an internal arc”. CIGRE, 37th Session, Paris
1998, Joint Session 21/23/33

[26] IEEE Standard 1125-1993 “Guide to moisture measurement and

control in SF6 gas insulated equipment”

[27] Boudene, C. and Clouet, J. L., “Identification and study of some

properties of compounds resulting from the decomposition of SF6
under the effect of electrical arcing in circuit breakers”, Rev. Gener.
d’Electricite, Special Issue 1974, p. 45-78

[28] Siddangangappa M. C. and Van Brunt R. J. “Decomposition products

from corona in SF6/N2 and SF6/O2 mixtures”, 8th Int. Conf. On Gas
Discharges and Their Application, pp. 247-250, 1985

[29] James, R.D. et al.,”Investigation of S2F10 production and mitigation

in compressed SF6 insulated power systems”, IEEE Electr. Insul.
Mag., 9,(1993) p.29-40

[30] L. Vial, A M Casanovas et al:“Decomposition products from negative

and 50 Hz ac corona discharges in compressed SF6 and SF6/N2
(10:90) mixtures. Effect of water vapour added to the gas”, J. Phys. D:
Appl. Phys. 32 (1999) 1681-1692

[31] J. Castonguay,”Mixing rates and diffusion of various gases and

moisture into SF6”, 5th Internat. Sympos. on Gaseous Dielectrics,
Knoxville 1987, Pergamon, 526-535

[32] SF6-N2 mixing device, DILO product information

[33] M.Pitroff, A.Schutte, A.Meier, “SF6 Re Use Concept and New

Applications” 8th International Sumposium on Gaseous Dielectrics, 2-
5 June 1998, Virginia Beach, USA.

[34] IEC (International Electrotechnical Commission) standard 60376

(1973) “Specification and acceptance of new sulphur hexafluoride”

[35] Berg D. and Hickam, W. M., “Sorption of sulphur hexafluoride by

artificial zeolites”, J. Phys. Cem. 65 (1961) p. 1911-13
48
[36] Otten, W. et. Al.,”Einsatzmöglichkeiten hydrophober Zeolithe in der
Adsorptionstechnik”, Chem. Ing. Techn. (1992), No. 10, p. 915-925

[37] Cooperation of AGA and Solvay, <www.solvay-fluor.com>

[38] Thermal destruction of SF6 and SF6 mixtures is presently offered by

the companies Solvay (D) and SAKAB (SE).

[39] A.A. Opalovsky and E. U. Lobkov, “Interaction of sulphur

hexafluoride with metals and oxides”, J. Fluorine Chem., 2, (1972/73),
349-359

[40] F. Chu and R. Massey, “Thermal decomposition of SF6 and SF6-air

mixtures in substation environments”, 3rd Internat. Sympos. on
Gaseous Dielectrics, Knoxville 1982, Pergamon, 410-417

[41] G. A. Askar’yan et. al., “Efficient chlorofluorocarbons (CFCs)

destruction in a microwave discharge”, 11th Intern. Conf. on Gas
Discharges and their Applications, Tokyo, 1995, II-438

[42] J.Castonguay and I.Dionne, “S2F10 and other heavy gaseous

decomposition byproducts formed in SF6 and SF6 –gas mixtures
exposed to electrical discharges”, 7th Internat. Sympos. On Gaseous
Dielectrics, Knoxville, 1994, Plenum, pp. 449-464

[43] G.R.Mitchel, J.Castonguay and N.G. Trinh, “Practical

thermodynamics of SF6 recovery from SF6/N2 or SF6/air mixtures”,
Proceedings of the Symposium on Gas-insulated Substations:
Technology and Practise, Toronto, 1985, Pergamon Press, pp. 437-
442.

49
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