International Journal of Refrigeration 26 (2003) 865–872

www.elsevier.com/locate/ijrefrig

From mine to refrigeration: a life cycle inventory

analysis of the production of HFC-134a
A. McCullocha, A.A. Lindleyb,*
a
School of Chemistry, University of Bristol, Bristol BS8 1TR, UK
b
Ineos Fluor Ltd., PO Box 13, The Heath, Runcorn WA7 4QF, UK

Received 30 July 2002; received in revised form 26 May 2003; accepted 23 June 2003

Abstract
A life cycle inventory analysis has been conducted for the production of HFC-134a (1,1,1,2-tetrafluoroethane,
CH2FCF3)1 through from basic raw materials (crude oil, natural gas, sulphur and fluorspar) to the pure product
delivered to industrial customers. The analysis was based on real industrial operations in Japan, USA and UK. It
showed that production required limestone, water and transition metal catalysts, in addition to the basic raw materials,
and that the energy required to provide these raw materials in a form that can be used at the plants and to process them
through intermediates into HFC-134a is the equivalent of 4.52 tonnes of CO2 per tonne of product. Environmental
releases associated with HFC-134a included waste salt brine (to the sea), mine tailings (mainly ‘‘country’’ rock landfilled
at the mine) and small quantities of calcium sulphate and spent catalyst (both sent to landfill). In addition, greenhouse
gases amounting to the equivalent of 2.1 tonnes of CO2 per tonne of product were emitted to the atmosphere from the
plants studied, an effect very much smaller than that estimated in previous studies mainly because the real release rates
from current processes are very much less than those assumed in prior work. The global warming potential2 of
HFC-134a is 1300, meaning that, during the first 100 years following the release of one tonne, the effect on climate
change is equivalent to 1300 tonnes of carbon dioxide. Consequently, the 6.6 tonnes of carbon dioxide equivalent,
emitted during production in the form of energy required and other greenhouse gases, is of relatively little importance
and the key requirement to reduce environmental impact is containment during use.
# 2003 Elsevier Ltd and IIR. All rights reserved.
Keywords: Refrigerant; R134a; Process; Production; TEWI

De la mine aux applications frigorifiques : analyse de la

production de R134a fondée sur un inventaire tenant compte
du cycle de vie
Mots cle´s : Frigorigène ; R134a ; Procédé ; Production ; TEWI

* Corresponding author. Tel. +44-1928-513145; fax +44-
1928-511418.
E-mail address: andrew.lindley@ineosfluor.com (A.A.
Lindley).
1
HFCs, or Hydrofluorocarbons, are compounds compris-
ing hydrogen fluorine and carbon only.
2
The Global Warming Potential (GWP) of a material is
defined as the integrated radiative forcing over 100 years following
an assumed release of 1kg divided by the integrated radiative for-
cing over the same period from release of 1 kg of carbon diox-
ide. Radiative forcing is the specific increase in infrared
absorption in Wm
2 ppb
1 (Watts per square metre at the
Earth’s surface per part per billion concentration of the mate-
rial). All effects beyond 100 years are disregarded; thus Global
Warming Potential captures all of the effect of an HFC but less
than 40% of the total effect from CO2.

0140-7007/$35.00 # 2003 Elsevier Ltd and IIR. All rights reserved.

doi:10.1016/S0140-7007(03)00095-1
866 A. McCulloch, A.A. Lindley / International Journal of Refrigeration 26 (2003) 865–872
1. Introduction
HFC-134a is a common fluorinated greenhouse gas3
that is used extensively in a range of functions: princi-
pally refrigeration and air conditioning but also in
blowing plastic matrix foams and propelling medical
and technical aerosols. Leakage from installations and
the act of using aerosols will have an effect on the
environment in the form of a forcing of climate change.
The extent of this effect will be proportional to the
amount emitted and the GWP of HFC-134a. The value
of the latter parameter sets the greenhouse effect of
releasing 1 kg of HFC-134a equivalent to that from
releasing 1300 kg of carbon dioxide (CO2) calculated
over the first 100 years following the release of both [1].
The balance between releases of refrigerant green-
house gases and energy efficiency of the equipment in
which they are used have been extensively examined in
various reports on Total Equivalent Warming Impact4
[2–9] and the purpose of this work is to build on these
and the prior work of Campbell and McCulloch [10,11]
that examined the climate change implications of man-
ufacturing refrigerants from the point of view of pro-
duction energy content (embedded energy). This is the
energy required to convert raw materials into the fin-
ished product; it includes all energy related inputs,
including efficiency losses, but should not include the
energy equivalent of raw materials that are chemically
converted into the finished product.
Previous studies of this topic have relied on informa-
tion from regulatory sources; Banks and colleagues used
submissions to the UK government under Integrated
Pollution Control regulations [12]. McCulloch and
Campbell used a compendium of emissions from a
number of producers [11]. In both cases the information
related to processes without treatment systems to remove
controlled substances from the normal process vents. In
all cases the regulatory limits represent maxima beyond
which sanctions will be taken by the authorities, hence
real plants operate with much lower emissions. Further-
more, the introduction of vent treatment (which is now
3
A greenhouse gas is a material that will, if released, parti-
tion into the atmosphere and will increase absorption of infra-
red radiation in the lower atmosphere. Greenhouse gases
included in the Kyoto Protocol are carbon dioxide, methane,
nitrous oxide, HFCs, perfluorocarbons and sulphur hexa-
fluoride. In addition, the UN Framework Convention on Cli-
mate Change includes materials such as hydrocarbons and
sulphur oxides that are secondary greenhouse gases.
4
Total Equivalent Warming Impact (TEWI) is a restricted
sub-set life-cycle analysis that counts the energy requirements
of a system over its whole service life and the direct releases of
greenhouse gases and expresses that total as the equivalent
mass of CO2 (using GWP as the conversion factor for releases
of other greenhouse gases). The TEWIs of systems can be
directly compared as a metric of relative sustainability.
more commonplace) has resulted in a step-change
reduction in emissions by a factor in the region of 100.
Here we present a more complete inventory analysis of
the raw material and energy inputs and by-product
emissions into the environment during the manufacture
of HFC-134a using actual data from real operations.
The energy requirements will augment the GWP of
HFC-134a because the CO2 released from generating
this energy will be additional to the direct effect from
release of the HFC. However, the additional CO2 needs
to be placed in the context of the GWP of 1300.
2. Boundaries
The study is based on an analysis of the operations of
Ineos Fluor Ltd., a company headquartered in UK
which produces HFC-134a in three locations (UK, USA
and Japan) by fluorination of trichloroethene using
hydrogen fluoride in a gas phase process over a hetero-
geneous catalyst. This route is used by nearly all of the
producers of HFC-134a and the competing process
(hydrogenolysis of CFC-114a) has been shown to have
very similar energy-related emissions [11] so that the
route studied should be a good but not perfect global
model. The analysis takes into account the small differ-
ences in manufacturing procedure at each location and
the energy requirements for movement of raw materials
to the plants and product between locations and to the
customers. Results are presented as a single set of values
regardless of the origin of the material; with a globally
traded substance such as this fluorocarbon, it is not
possible to discriminate material used by a particular
customer by place of origin.
The major processes involved in the manufacture of
HFC-134a are shown in Fig. 1; the process procedures
are summarised here and described in detail below. The
basic carbon raw materials are crude oil and gas which
yield ethylene via pyrolysis of a potentially wide range
of natural gas and refinery products (from methane to
heavy oil). The crude oil is assumed to be transported to
the refinery by VLCC (Very Large Crude Carrier) and
the ethylene sent out by pipeline to the plant using it.
Ethylene can be converted, as described by Campbell
and McCulloch [10], into trichloroethene. The pro-
cesses involve chlorination to dichloroethane and fur-
ther conversion by chlorination into trichloroethene
and tetrachloroethene. Chlorine is produced in con-
ventional chlor-alkali plant by electrolysis of brine in
membrane and in mercury cells according to location
of the plant. It is assumed that, in these stages, mate-
rials are transported by pipeline with virtually no
energy penalty.
The source of fluorine is fluorspar, a mineral form of
calcium fluoride mined in many regions of the world,
including Central America and S.E. Asia and Europe. It
 A. McCulloch, A.A. Lindley / International Journal of Refrigeration 26 (2003) 865–872
Fig. 1. Block diagram showing the major stages and intermediate materials in the conversion of crude oil and other minerals into
HFC-134a.
was assumed that shipments to US, Japanese and Eur-
opean hydrogen fluoride facilities were carried in bulk
solids carriers. Acid grade fluorspar is converted to
anhydrous hydrogen fluoride (HF) in reaction with
oleum, a mixture of sulphuric acid and sulphur trioxide.
This, in turn, is made from sulphur that is brought in
bulk from (say) Poland or southern USA. where it was
mined by the Frasch process. Material and energy
inputs into these processes were considered.
It has previously been shown that construction energy
input and environmental impact, when spread over a 20
year plant lifetime and productive capacity in the region
of 10,000 tonnes year
1, amounts to an insignificant
value per tonne of product [13] and this aspect is not
considered further here.
3. Processes
3.1. Manufacture of HFC-134a
A block diagram of the processing stages is shown in
Fig. 2. The reactions are accomplished at elevated tem-
perature and pressure, in two stages, over a solid metal
867
oxide catalyst (based on chromia). Overall, the process
can be represented by:
CHCl ¼ CCl2 þ 4HF ! CH2 FCF3 þ 3HCl ð1Þ
The first stage reactor converts trichloroethene to
HCFC-133a (CF3CH2Cl, 1,1,1-trifluoro-2-chloro-
ethane). The conversion can be completed in one pass
with minimal recycle and, for the manufacture of
HFC-134a, the HCFC-133a is not isolated and removed
from the process. The second stage, substitution of the
last remaining chlorine substituent by fluorine, is much
more difficult. The reaction equilibrium is biased toward
the starting materials and so it requires removal of the
hydrogen chloride, together with large recycles of the
reagents. The complete process is totally enclosed,
intermediate reagents are physically retained within the
equipment and releases to atmosphere are minimal. In
the plants currently operated nearly all of the streams
that might potentially go into the atmosphere are trea-
ted by thermal oxidation.
The single alternative process involves hydrogenolysis
of CFC-114a (CF3CFCl2, 1,1,1,2-tetrafluorodi-
chloroethane) but emissions and energy requirements
have been shown to be similar to the process described
868 A. McCulloch, A.A. Lindley / International Journal of Refrigeration 26 (2003) 865–872

Fig. 2. Block diagram of the production stage of the HFC-134a process showing principal chemical and service requirements and
process outputs.

here [10,11]. Because the systems are totally enclosed
and because it is a general condition of operation for
these relatively new plants that vent gases are treated,
the processes do not emit ozone depleting substances5 or
greenhouse gases in controlled vents. Almost all of the
releases are as so-called fugitive emissions, mainly asso-
ciated with filling containers for transport of the pro-
duct where the small leakages cannot be captured and
treated.
Typically about 1.3 tonnes of trichloroethene and 0.8
tonnes of HF are required for each tonne of HFC-134a,
but the process also requires electrical power, heat (in
the form of steam or natural gas), nitrogen and air, and
water in amounts that depend on the way that indivi-
dual plants are operated. On average these amount to
1.2 MWh of electrical energy and 28 GJ of heat energy
5 that sanctioned by the USEPA [14].
Ozone Depleting Substances are materials that can be
transported into the stratosphere and there decompose to
release chlorine or bromine. These decomposition products
react with stratospheric ozone and deplete the concentration in
the ozone layer. Ozone depleting substances are controlled
under the Montreal Protocol.
(from all sources), 0.5 tonnes of nitrogen and 13 m3 of
water per tonne of HFC-134a.
The principal co-product is hydrochloric acid which can
be sold as such and, in this analysis, is treated as neutral in
that it attracts none of the process inputs; all of these are
counted in the values assigned to HFC-134a. Any
requirement for alkali to neutralise unsold hydrochloric
acid is similarly assigned to the HFC-134a product.
Other by-product materials that may be released into
the environment are fluorinated VOCs, which are green-
house gases, and spent catalyst. In general, the former are
removed from process vent streams by thermal oxidation
and the fuel, water and alkali requirements for this are
included in the analysis. However, the small amounts of
VOC greenhouse gases that escape without the possibility
of being oxidised (losses from container filling and fugi-
tive emissions from plant flanges etc are typical examples)
were specifically estimated using methods consistent with
Although manufacture of the catalyst requires chro-
mium oxide, nitric acid and alkali, the quantities
involved are small in comparison to the principal raw
materials and present no special issues relative to the
scale of manufacture of HFCs. The major environ-
 A. McCulloch, A.A. Lindley / International Journal of Refrigeration 26 (2003) 865–872
mental effect is in disposal of spent catalyst. It may be
regenerated in situ many times but, eventually, this
becomes impossible and it has to be replaced. Spent
catalyst, at an average rate of 1 kg tonne
1 of product is
essentially an inert transition metal oxyfluoride that is
treated as special waste and sent to secure landfill; a
waste disposal landfill that has been suitably engineered
to obviate leaching of the contents by environmental
water or wind-borne release of waste in the form of
dust. The requirement there is to contain the waste but
not necessarily to treat it in any way.
The product is transferred between plants and to
major customers in ISO standard demountable tanks
each with a typical carrying capacity of 21.5 tonnes.
Shipments between plants are mainly sea borne by con-
tainer ships in the region of 60,000 tons. Customers
receive the product mainly by road. Because movement
of HFC-134a and the raw materials directly associated
with it are a relatively small portion of the total move-
ment of goods and materials, it seems appropriate to
include only the energy cost of shipping the raw mate-
rials and product in these calculations.
3.2. Hydrogen fluoride
This was assumed to be manufactured in a standard
rotary kiln process by reaction of fluorspar (CaF2,
calcium fluoride) with oleum (a mixture of concentrated
sulphuric acid and sulphur trioxide) [15]:
CaF2 þ H2 SO4 ! 2HF þ CaSO4 ð2Þ
This reaction requires a temperature of over 300  C
and heat is generally provided by burning natural gas.
There is a relatively small requirement for electrical
power, mainly to rotate the kiln and provide other mix-
ing. The 3.5 tonnes of solid calcium sulphate (CaSO4)
co-produced finds several uses in civil engineering; it is
sold as synthetic anhydrite for use in hydraulic cements
and screeds and also for landfill engineering. The resi-
dual quantities that cannot be sold, for example on the
occasions when the quality of this by-product does not
match specification, are counted as solid waste for
landfill.
3.3. Sulphuric acid
A standard double absorption ‘‘contact’’ process is
assumed in which sulphur is burnt in air to sulphur
dioxide (SO2) that is oxidised further to sulphur trioxide
(SO3) over a vanadium pentoxide catalyst [16]. The
calorific value of sulphur combustion is recovered by
raising steam which provides most of the energy to
drive the gas flow through the plant with a significant
fraction left over for use in neighbouring processes.
The energy exported is credited to sulphuric acid
production:
869
S þ O2 ! SO2 ðþ1=2O2 Þ -vanadium pentoxide
! SO3 ð3Þ
The catalyst for the process has been developed over
many decades and now lasts several years. Like the cata-
lyst used in HFC-134a manufacture, the principal poten-
tial impact on the environment arises during disposal.
The spent catalyst amounts to 20 g tonne
1 of sulphuric
acid product and is disposed of in secure landfill or
returned to the catalyst manufacturer for reprocessing. In
this calculation it is assumed to be landfilled.
Much (20 million tonnes year
1) of the sulphur tra-
ded for sulphuric acid manufacture has been recovered
from crude oil and natural gas desulphurisation [17].
However, a significant amount (14 million
tonnes year
1) is mined by the Frasch process in which
it is obtained from underground deposits by melting
with superheated water. Principal sources for European,
North American and Japanese plants are Poland and
Texas/Louisiana. This process requires large amounts of
hot water and has significantly higher energy require-
ments than recovery processes [18]. It is also assumed to
be transported molten to the sulphuric acid plant by sea
in 20,000 tonne bulk tankers and thence moved a total
of 20 km by road. This is thought to represent a typical
situation with high energy requirements; use of recov-
ered sulphur and storage and shipping as a solid powder
would tend to reduce the energy load but may not
represent a realistic worst case.
Thus each tonne of sulphur requires in the region of
3.36 GJ of natural gas to heat the water to extract it
(equivalent to 0.17 tonnes of CO2) and 0.025 tonnes of
fuel oil (0.075 tonnes of CO2) for transportation,
assuming 17 days at sea.
3.4. Calcium fluoride
This is mined as fluorspar (CaF2) and requirements
for USA, Europe and Japan come mainly from China
and Europe [19,20]. However, the notional basis for the
calculation was an historical UK mining and milling
operation that, with the exception of transportation,
should serve as a model for operations elsewhere. Mine
capacity is nominally 100,000 tonnes year
1 as finished
dry acid grade calcium fluoride. As mined, the fluorspar
will contain country rock and other inert impurities,
together with varying amounts of lead, silver or zinc
ores. These are separated and recovered from the cru-
shed and milled fluorspar mainly by froth flotation
using, as collecting agent, a soap such as oleic acid or
sodium stearate at a rate of 0.25 kg tonne
1 [21]. This is
adsorbed onto the refined fluorspar and is subsequently
carbonised in the HF kiln; residues being associated
with the synthetic anhydrite product.
Recovery from run-of-mine is assumed to be 50%, the
waste being mainly ground up country rock that goes to
a tailings dam. As described by Campbell and McCul-
870 A. McCulloch, A.A. Lindley / International Journal of Refrigeration 26 (2003) 865–872
loch [10], the process requires 5.54 kg tonne
1 of fuel
oil, 34.6 kWh tonne
1 electricity and 0.9 Gj tonne
1 of
natural gas. For fluorspar sourced from locations other
than UK, the main additional input arose from sea
borne transportation (assumed to be in 50,000 tonne
bulk solids carriers) from either China or Mexico.
3.5. Trichloroethene
Trichloroethene (CHCl¼CCl2, trichloroethylene) is a
common industrial solvent with global sales of some
200,000 tonnes year
1 [22]. The quantity converted into
HFC-134a is significantly less than this but would be
produced by the same process. In Campbell and
McCulloch [10] we suggested a model process which
proceeded via dichloroethane that gives results similar
to the ‘‘average’’ European process [23].
Based on the data of Elkin [24], chlorination of ethylene
to dichloroethane (ethylene dichloride) proceeds at about
95% efficiency and so will require 0.296 tonnes of ethylene
and 0.755 tonnes of chlorine per tonne of product.
CH2 ¼ CH2 þ Cl2 ! CH2 ClCH2 Cl ð4Þ

1
Process energy requirements are 9.5 Gj tonne and,
for this calculation, were assumed to be natural gas.
Further conversion of the dichloroethane is accom-
plished in a separate process, again described by Elkin
[24], whence the principal products are trichloroethene
and tetrachloroethene.
CH2 ClCH2 Cl þ 2Cl2 ! CHCl ¼ CCl2 þ 3HCl ð5Þ
CH2 ClCH2 Cl þ 3Cl2 ! CCl2 ¼ CCl2 þ 4HCl ð6Þ
Hydrogen chloride (HCl) is a major co-product of
this stage of this process (0.92 tonnes tonne
1) and, in
many cases, can be used on site in further processing or
in oxychlorination reactions. For this reason it is
assumed to attract an energy credit, set at the energy
value of the chlorine content which amounts to 1.78
MWh tonne
1 [10]. Additional requirements for energy
in the form of natural gas and steam, and caustic soda
solution boost the process energy requirement for a
tonne of trichloroethene to 32 GJ, taking full credit for HCl
recovery. If the HCl were not recovered, for example if it
were converted into hydrochloric acid (as in the HFC-134a
production step), this would rise to about 52 GJ tonne
1, a
value consistent with the 50.9 GJ tonne
1 derived indepen-
dently for an average European process [23].
3.6. Chlorine, alkali and hydrogen by electrolysis
In Europe, the electrolysis of sodium (or potassium)
chloride brine is commonly accomplished in mercury
cells that give gaseous chlorine (Cl2) and sodium amal-
gam as the primary products. The amalgam is decom-
posed to yield sodium hydroxide (NaOH, caustic soda)
and hydrogen and the mercury is recycled. European
capacity for chlorine production by this route is 6900 kt
year
1 [25]. The alternative, membrane, process oper-
ates without use of mercury, the sodium hydroxide
being generated directly in the cathode compartment of
the cell. In either case, the overall reaction is:
2NaCl þ 2H2 O
2 electrons
! Cl2 þ 2NaOH ð7Þ
The inventory calculation is based on the ‘‘electro-
chemical unit’’, essentially one tonne of total products,
divided into 0.464 tonnes of chlorine, 0.523 tonnes of
sodium hydroxide and 0.013 tonnes of hydrogen. If the
latter is treated simply as a fuel (with a calorific value of
286 GJ tonne
1), the energy recovered from it and the
requirements for brine, water and electrical power may
be split between the two main products [10,26]. For each
tonne of alkali (caustic soda as 100% NaOH), 3.13
tonnes of water, 1.13 tonnes of sodium chloride (NaCl)
and 1.13 MWh of electricity are required. Hydrogen co-
product is equivalent to a credit of 1.75 GJ of energy.
Some 3.26 tonnes of waste brine is generated that con-
tains 0.04 g of mercury if the mercury cell process is
used and none in the case of the membrane process [27].
This difference is reflected in the chloralkali sourced for
production in USA and Japan. The equivalent values
for a tonne of chlorine are: 3.53 tonnes water, 1.27
tonnes NaCl, 2.06 MWh, 1.97 GJ hydrogen fuel credit
and 3.8 tonnes waste brine.
3.7. Ethylene
Ethylene (C2H4, ethene) is the largest individual pet-
rochemical product. It is made by pyrolysing mixed
hydrocarbon feedstock (anything from natural gas to
heavy oil) in plants of several hundred thousand tonnes
year
1, with co-production of propene and other valu-
able chemical raw materials. In general, plants are situ-
ated close to the oil refineries that provide the feedstock
and the ethylene is distributed to users by pipeline [28].
For this analysis, the data calculated by Boustead for
ethylene from the plants feeding into the North Eur-
opean Pipeline was used [29]. In this, almost the same
mass of natural gas as oil products was used as feed-
stock and the principal other requirement was a total of
25.9 GJ tonne
1 of energy (including the primary energy
used for electrical power). The process also requires
water (1.6 tonnes tonne
1) and releases small amounts of
sulphur dioxide, oxides of nitrogen and volatile organic
hydrocarbons to the atmosphere and small amounts of
solid to landfill (ash and mineral waste).
3.8. Shipping and transport
The fuel requirements to ship HFC-134a product,
crude oil, fluorspar and sulphur round the world were
 A. McCulloch, A.A. Lindley / International Journal of Refrigeration 26 (2003) 865–872
calculated from the data in Ewart [30], showing that the
fuel usage (F tonnes day
1) is linearly related to the size
of the vessel (T tons deadweight):
F ¼ 7:76 þ 3:29  10
4  T R2 ¼ 0:963

1
An allowance of a further 3 tonnes day was
included for days in port, which were assumed to be
20% of the total ship time. Load factors varied from
50% for the dedicated carriers to 80% for a container
liner.
Road transport of the typical 21.5 tonne payloads
was assumed to be accomplished with a diesel usage of
2.8 km l
1 (8 miles per gallon) with no backloading,
with rail transport at 0.06 kWh tonne km
1, again not
backloaded.
4. Conclusion
The purpose of this paper was to place emissions into
the environment during the manufacture of HFC-134a
into the context of the environmental impact that might
arise from its use and ultimate disposal. Globally aver-
aged over plants in UK, USA and Japan, manufacture
of each tonne of HFC-134a requires:
0.39 tonnes of fluorspar,
0.15 tonnes of crude oil,
0.17 tonnes of natural gas,
0.21 tonnes of limestone,
0.16 tonnes of sulphur,
3.1 tonnes of sodium or potassium chloride and
25 tonnes of water.
The energy required to provide these raw materials in
a form that can be used at the plants and to process
them through intermediates into HFC-134a is the
equivalent of 4.48 tonnes of CO2 per tonne of product.
This value includes all energy related inputs from pri-
mary fuels using the conversion factors shown in Jaques
[31] and excludes the CO2 equivalent of the feedstock
carbon sources (the crude oil and natural gas shown
above). It also includes the CO2 released when limestone
is converted to lime by calcination [32]. Energy require-
ments to transport the raw materials amount to 0.02
tonnes of CO2 tonne
1 HFC-134a and are included in
this value.
The energy cost of transporting product to the custo-
mers is somewhat larger than that for the raw materials
and is equivalent to a further 0.04 tonnes CO2 tonne
1
HFC-134a.
Environmental releases associated with each tonne of
HFC-134a are:
9.3 tonnes of waste salt brine (to the sea),
0.39 tonnes of mine tailings (mainly ‘‘country’’ rock)
landfilled at the fluorspar mine,
871
30 kg of calcium sulphate (to landfill),
1 kg of ‘‘special waste’’ (mainly spent catalyst) to
landfill,
2 kg of sulphur dioxide,
ð8Þ
3 kg of hydrocarbon VOCs,
0.2 g of mercury in compounds released into the
atmosphere and
0.04 g of mercury released into sea water
and greenhouse gases amounting to the equivalent of
2.1 tonnes of CO2.
None of the raw materials presents a particular
environmental issue; requirements for the manufacture
of HFC-134a are minor relative to global industrial
demand and the materials themselves do not present
special problems of extraction. Of the byproducts and
wastes that are produced, the waste catalyst would
arguably be of most concern. However, it is an insoluble
compound of chromium, oxygen and fluorine that is
buried in secure landfill from which leaching into the
environment should not occur. The total mercury
released per tonne of HFC-134a is less than 1/10th that
in a normal dental filling. In all of the plants it is dis-
charged to seawater and will augment the pre-existing
natural background (the concentration in the effluent is
about 50 times background and the dilution factor
should be several thousand-fold).
HFC-134a is a greenhouse gas with a Global Warm-
ing Potential equal to 1300 (tonnes of CO2 per tonne of
HFC). The energy required to obtain and convert the
raw materials and deliver the product, plus the effect
from other greenhouse gases released during conversion
would be equivalent to 6.6 tonnes of CO2 per tonne of
HFC-134a, or 0.4% of the potential impact from release
of the HFC itself. Containment of HFC-134a during use
and adequate provisions for disposal without significant
release into the atmosphere are therefore far more
important to minimise environmental impact than any
further measures that could be taken during the pro-
duction phase. This does not obviate the objective to
continue to minimise emissions from production.
Acknowledgements
The authors are indebted to the management of Ineos
Fluor Ltd. for permission to publish proprietary data
and to the two reviewers for their helpful comments.
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