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Refrig erant Report 18

A-501-18
Refrigerant Report

Page Contents
Essential revisions/supplements vs. 17th edition
3 General aspects on refrigerant developments
3 Introduction

4 Alternative refrigerants (overview)

6 Environmental aspects
6 Global Warming and TEWI factor
7 Eco-Efficiency

8 HCFC refrigerants
8 R22 as transitional refrigerant

9 HFC and HFO refrigerants


9 R134a as a substitute for R12 and R22 Lubricants for HFCs
11 Alternatives to R134a
11 R152a an alternative to R134a (?)
11 "Low GWP" HFO refrigerants R1234yf and R1234ze(E)

13 Refrigerant blends
15 Service blends as substitutes for R502
16 Service blends as substitutes for R12 (R500)

17 HFC Alternatives for R502 and R22


17 R404A and R507A as substitutes for R502 and R22
18 R407A, R407B and R407F as substitutes for R502 and R22
19 R422A as substitute for R502 and R22

20 HFC Alternatives for R22


20 R407C as substitute for R22
21 R410A as substitute for R22
22 R417A, R417B, R422D and R438A as substitutes for R22
22 R427A as substitute for R22
23 R32 as substitute for R22

24 HFO/HFC blends as alternatives to HFCs

27 Halogen free refrigerants


27 NH3 (Ammonia) as alternative refrigerant
28 R723 (NH3/DME) as an alternative to NH3
29 R290 (Propane) as substitute for R502 and R22
31 Propylene (R1270) as an alternative to Propane
32 CO2 as an alternative refrigerant and secondary fluid

36 Special applications

38 Refrigerant properties

40 Application ranges Lubricants

This edition supersedes all previous issues.


General aspects on refrigerant developments

Introduction high global warming potential (GWP) will in been introduced. Meanwhile, another, more
future be subject to use restrictions or bans. extensive assessment method has been de-
This will affect primarily R404A and R507A, veloped under the aspect of "Eco-Efficiency".
Stratospheric ozone depletion as well as for which alternatives with lower GWP are Hereby, both ecological (such as TEWI) and
atmospheric greenhouse effect due to refrig- already being offered. However, in order to economical criteria are taken into account
erant emissions have led to drastic changes achieve the legal objectives, substitutes for (see also page 7).
in the refrigeration and air conditioning tech- further refrigerants and increased use of nat-
nology since the beginning of the 1990s. Therefore it is possible that the assessment
urally occurring substances (NH3, CO2,
of refrigerants with regard to the environment
This is especially true for the area of com- hydrocarbons) will become necessary.
can differ according to the place of installa-
mercial refrigeration and A/C plants with This requires comprehensive testing of these tion and drive method.
their wide range of applications. In former refrigerants, suitable oils and accordingly
years the main refrigerants used for these Upon closer evaluation of substitutes for the
adjusted systems.
systems were ozone depleting types, namely originally used CFC and HCFC as well as for
R12, R22 and R502; for special applications Therefore a close co-operation exists with HFCs with higher GWP, the options with
R114, R12B1, R13B1, R13 and R503 were scientific institutions, the refrigeration and oil single-substance refrigerants are very limited.
used. industries, component manufacturers as well They include, for example, R134a, whose
as a number of innovative refrigeration and comparably low GWP will allow its use for a
With the exception of R22 the use of these air conditioning companies. longer time to come. Furthermore this
chemicals is not allowed any more in indus- includes the hydro fluoro olefins (HFO)
trialised countries. In the European Union, A large number of development tasks have
been completed. For alternative refrigerants R1234yf and R1234ze(E) with a GWP < 10,
however, an early phase-out was already which so far have been available to only a
enforced in several steps (see page 8). suitable compressors are available.
limited extent and for which no long-term
The main reason for this early ban of R22 Besides the development projects BITZER experience is available as yet.
contrary to the international agreement is the actively supports legal regulations and self
ozone depletion potential although it is only commitments concerning the responsible Direct alternatives (based on fluorinated
small. use of refrigerants as well as measures to hydrocarbons) for almost all refrigerants of
Since 2010, phase-out regulations got effec- increase system and components efficiency. higher volumetric refrigerating capacity and
tive in other countries as well, in the USA for pressure level than R134a can only be "for-
instance. The following report deals with potential mulated" as blends. However, taking into
measures of a short to medium-term change account thermodynamic properties, flamma-
Due to this situation enormous conse- towards technologies with reduced environ- bility, toxicity and global warming potential,
quences result for the whole refrigeration mental impact in medium and large size the list of potential candidates is very limited.
and air conditioning sector. BITZER therefore commercial refrigeration and air-conditioning Blends of reduced GWP include in addition
committed itself to taking a leading role in systems. Furthermore, the experience which to R134a, R1234yf and R1234ze(E) primarily
the research and development of environ- exists is also dealt with and the resulting the refrigerants R32, R125 and R152a.
mentally benign system designs. consequences for plant technology.
Besides halogenated refrigerants, Ammonia
After the chlorine-free (ODP = 0) HFC refrig-
erants R134a, R404A, R407C, R507A and (NH3) and hydrocarbons are considered as
substitutes as well. The use for commercial
R410A have become widely established for applications, however, is limited by strict
many years in commercial refrigeration, air- Serveral studies confirm that the vapour
compression refrigeration plants normally safety requirements.
conditioning and heat pump systems, mean-
while new challenges have come up. They used in the commercial field are far superior Carbon dioxide (CO2) becomes more impor-
concern primarily the greenhouse effect. The in efficiencyto all other processes down to a tant as an alternative refrigerant and second-
aim is a clear reduction of direct emissions cold space temperature of around -40C. ary fluid, too. Due to its specific characteris-
caused by refrigerant losses and indirect The selection of an alternative refrigerant and tics, however, there are restrictions to a
emissions by particularly efficient system the system design receives special signifi- general application.
technology. cance, however. Besides the request for The illustrations on the next pages show a
In this area, applicable legal regulations are substances without ozone depletion poten- structural survey of the alternative refriger-
already in force, such as the EU Regulation tial (ODP=0) especially the energy demand ants and a summary of the single or blended
on F-Gases No. 517/2014 (see BITZER of a system is seen as an essential criterion substances which are now available. After
brochure A-510) and a series of regulations due to its indirect contribution to the green- that the individual subjects are discussed.
already ratified or in preparation as part of house effect. On top of that there is the
direct global warming potential (GWP) due to Refrigerant properties, application ranges
the EU ErP Ecodesign Directive. Similar reg- and lubricant specifications are shown on
ulations are also in preparation or have refrigerant emission.
pages 38 to 41.
already been implemented in North America Therefore a calculation method has been
and other regions. developed for the qualified evaluation of a For reasons of clarity the less or only re-
system which enables an analysis of the gionally known products are not specified in
Even though indirect emissions caused by this issue, which is not intended to imply any
energy production are considerably higher total influence on the greenhouse effect.
inferiority.
than direct (CO2-equivalent) emissions In this connection the so-called "TEWI" fac-
caused by HFC refrigerants, refrigerants with tor (Total Equivalent Warming Impact) has

3
Alternative refrigerants overview

Alternative Refrigerants

Transitional/Service Medium and Long


Refrigerants* Term Refrigerants

HCFC/HFC HFC "Low GWP" Halogen free


partly chlorinated chlorine free Refrigerants

Single Single Single Single


Substances Blends Substances Blends Substances Blends Substances Blends
e.g. R22 predominantly e.g. R134a e.g. R404A R234yf R1234yf/ e.g. NH3 e.g. R600a/
R123 R22-Based R125 R507A R1234ze(E) R1234ze(E)/ R290 R290
R124 R32 R407-Series HFC R1270 R290/
R142b R143a R410A R600a R170
R152a R417A7B R170
R422A /D R744 R723
R427A
* Service refrigerants contain HCFC as blend component. They are therefore subject to the same legal regulations as R22 (see page 8).
As a result of the continued refurbishment of older installations, the importance of these refrigerants is clearly on the decline. For some of them, production has already been
discontinued. However, for development-historic reasons of service blends, these refrigerants will continue to be covered in this Report.
Fig. 1 Structural classification of refrigerants

HFC refrigerants 09.14

Former Alternatives
Refrigerants

ASHRAE Trade name Composition Detailed


Classification (with blends) Information
R12 R134a pages
(R500) R152a 1
9...11, 16, 38...41
R437A 4 ISCEON MO49 Plus DuPont R125/134a/600/601
R404A various R143a/R125/R134a
pages
R502/R22 R507A various R143a/125
17...19, 38...41
R422A ISCEON MO79 DuPont R125/134a/600a
R407A Mexichem, Arkema R32/125/134a
R407C various R32/125/134a
R407F Performax LT Honeywell R32/125/134a
R410A various R32/125
pages
R22 R417A ISCEON MO59 DuPont R125/134a/600
18...23, 38...41
R417B Solkane 22L Solvay R125/134a/600
R422D ISCEON MO29 DuPont R125/134a/600a
R427A Forane 427A Arkema R32/125/143a/134a
R438A ISCEON MO99 DuPont R32/125/134a/600/601a
R114 R236fa pages
R12B1 R227ea 36, 38...41
R410A various R32/125 pages
R13B1 ISCEON MO89 DuPont R125/218/290 37, 38...41
R23
R13 pages
R508A KLEA 508A Mexichem R23/116
R503 37, 38...41
R508B Suva 95 DuPont R23/116

Fig. 2 Substitutes for CFC and HCFC refrigerants (chlorine free HFCs)

4
Alternative refrigerants overview

HFO and HFO/HFC Blends


Current Alternatives
Refrigerants

ASHRAE Trade name Composition Detailled


Classification (with blends) Information
R1234yf 1 various
R1234ze(E) 1 various
R513A Opteon XP10 DuPont R1234yf/134a pages 2426 ,
R134a R450A Solstice N-13 Honeywell R1234ze(E)/134a 3841
ARM-42 1 Arkema R1234yf/152a/134a
AC5X Mexichem R32/1234ze(E)/134a

R449A Opteon XP40 DuPont R32/125/1234yf/134a


R448A Solstice N-40 Honeywell R32/125/1234yf/1234ze(E)/134a pages 2426 ,
R404A/R507A*
ARM-32b Arkema not disclosed 3841
LTR4X Mexichem R32/125/1234ze(E)/134a

DR-91 DuPont not disclosed


R22/R407C* Solstice N-20 Honeywell R32/125/1234yf/1234ze(E)/134a pages 2426
ARM-32c Arkema not disclosed

R32 1 various
Opteon XL41 1 DuPont R32/1234yf
R410A R447A 1 Solstice L-41 1 Honeywell R32/125/1234ze(E) pages 2426
ARM-71a 1 Arkema not disclosed
HPR1D 1 Mexichem R32/1234ze(E)/CO2

* Due to the large number of different HFO/HFC blends and the potential changes in development products, the above list for R404A/R507A and R22/R407C alternatives only
contains non-flammable blends of GWP < 1500.
On pages 24 to 26, HFO/HFC blends are extensively discussed. Further options are also dealt with.
Fig. 3 "Low GWP" Refrigerants and blends

Halogen free refrigerants 09.14

Current Alternatives
Refrigerants

ASHRAE Trade name Formula Detailed


Classification Information

R290/600a 1 C3H8/C4H10 pages


R134a
R600a 1 3 C4H10 29, 38...41

R717 1 2 NH3
R404A
R723 1 2 5
NH3 + R-E170 pages
R507A
R290 1 C 3H 8 27...31, 38...41
R22
R1270 1 C 3H 6

1 pages
R124 R600a C4H10
36, 38...41

R410A
no direct alternatives available
M089

1 pages
R23 R170 C 2H 6
37, 38...41

3 pages
Various R744
32...35, 38...41

Fig. 4 Alternatives for HCFC and HFC refrigerants (halogen free refrigerants)

Explanation of Fig. 2 to 4 1 Flammable 3 Large deviation in refrigerating capacity and 4 Service refrigerant 5 Azeotrope
2 Toxic pressures to the previous refrigerant with zero ODP

5
Environmental aspects

Global Warming and As this is a high proportion of the total bal- ous refrigerant charges, leakage losses and
ance it is also necessary to place an in- energy consumptions.
TEWI Factor
creased emphasis upon the use of high This example is simplified based on an
efficiency compressors and associated overall leak rate as a percentage of the
As already mentioned in the introduction a equipment as well as optimized system refrigerant charge. As is known the practi-
method of calculation has been developed, components, in addition to the demand cal values vary very strongly whereby the
with which the influence upon the global for alternative refrigerants with favourable potential risk with individually constructed
warming effect can be judged for the opera- (thermodynamic) energy consumption. systems and extensively branched plants
tion of individual refrigeration plants
When various compressor designs are is especially high.
(TEWI = Total Equivalent Warming Impact).
compared, the difference of indirect CO2 Great effort is taken worldwide to reduce
All halocarbon refrigerants, including the emission (due to the energy requirement) greenhouse gas emissions and legal
non-chlorinated HFCs belong to the cat- can have a larger influence upon the total regulations have partly been developed
egory of the greenhouse gases. An emis- effect as the refrigerant losses. already. Since 2007, the "Regulation on
sion of these substances contributes to the certain fluorinated greenhouse gases"
global warming effect. The influence is how- A usual formula is shown in Fig. 5, the TEWI
which also defines stringent requirements
ever much greater in comparison to CO2 factor can be calculated and the various areas
for refrigeration and air-conditioning sys-
which is the main greenhouse gas in the of influence are correspondingly separated.
tems has become valid for the EU.
atmosphere (in addition to water vapour). In addition to this an example in Fig. 6 Meanwhile, the revised Regulation No.
Based on a time horizon of 100 years, the (medium temperature with R134a) shows 517/2014 entered into force and will
emission from 1 kg R134a is for example the influence upon the TEWI value with vari- become applicable as of January 2015.
roughly equivalent to 1430 kg of CO2
(GWP100 = 1430).
It is already apparent from these facts that TEWI = TOTAL EQUIVALENT WARMING IMPACT
the reduction of refrigerant losses must be
one of the main tasks for the future. TEWI = ( GWP x L x n ) + ( GWP x m [ 1- recovery ] ) + ( n x Eannual x )

On the other hand, the major contributor to Leakage Recovery losses Energy consumption
a refrigeration plants global warming effect direct global warming potential indirect global
is the (indirect) CO2 emission caused by warming potential
energy generation. Based on the high per- GWP = Global warming potential [ CO2-related acc. to IPCC IV ]
centage of fossil fuels used in power sta- L = Leakage rate per year [ kg ]
tions the average European CO2 release is n = System operating time [ Years ]
around 0.45 kg per kWh of electrical energy. m = Refrigerant charge [ kg ]
A significant greenhouse effect occurs over recovery = Recycling factor
the lifetime of the plant as a result of this. Eannual = Energy consumption per year [ kWh ]
= CO2-Emission per kWh (Energy-Mix)
Fig. 5 Method for the calculation of TEWI figures

Comparison
Example with 10% higher
energy consumption
Medium temperature R134a 300
SST -10 C +10%

SCT +40 C +10%


E
m 10 kg // 25 kg 200 E N
N E E
L[10%] 1 kg // 2,5 kg
TEWI x 10 3

E E N R
N G
CAP 13,5 kW E
R E
Y
G R
E 5 kW x 5000 h/a R Y G
RL = Impact of
100 G Y
b 0.45 kg CO2/kWh Y recovery
losses
a 0.75 RL RL

n 15 years RL RL LL = Impact of
LL LL leakage
GWP 1430 (CO2 = 1) LL LL losses
10kg 25kg 10kg 25kg
time horizon 100 years Refrigerant charge [m]
Fig. 6 Comparison of TEWI figures (example)

6
Environmental aspects

Eco-Efficiency With this evaluation approach, the entire life Efficiency, the higher it lies in the top right
cycle of a system is taken into account in quadrant and conversely, it becomes less
terms of: efficient in the bottom left sector.
As mentioned above, an assessment based
on the specific TEWI value takes into account ecological performance in accordance The diagonals plotted into the system of
the effects of global warming during the with the concept of Life Cycle Assess- coordinates represent lines of equal Eco-
operating period of a refrigeration, air-con- ment as per ISO 14040, Efficiency. This means that systems or pro-
ditioning or heat pump installation. Hereby, cesses with different life cycle costs and
economic performance by means of
however, the entire ecological and economi- environmental impacts can quite possibly
a Life Cycle Cost Analysis.
cal aspects are not considered. exhibit the same Eco-Efficiency.
This means that the overall environmental
But apart from ecological aspects, when
impact (including direct and indirect emis-
evaluating technologies and making invest-
sions), as well as the investment costs,
ment decisions, economical aspects are
operating and disposal costs, and capital
highly significant. With technical systems,
costs are taken into account.
the reduction of environmental impact fre-
quently involves high costs, whereas low The studies also confirm that an increase of
costs often have increased ecological con- Eco-Efficiency can be achieved by investing
sequences. For most companies, the in- in optimized plant equipment (minimized
vestment costs are decisive, whereas they operating costs). Hereby, the choice of re-
are often neglected during discussions frigerant and the associated system tech-
about minimizing ecological problems. nology plays an important role.
For the purpose of a more objective as- Eco-Efficiency can be illustrated in graphic
sessment, studies* were presented in 2005 representation (see example in Fig. 8). For * Study 2005: Compiled by Solvay Management
Support GmbH and Solvay Fluor GmbH, Hannover,
and 2010, using the example of supermar- this, the results of the Eco-Efficiency evalu- together with the Information Centre on Heat
ket refrigeration plants to describe a con- ation are shown on the x-axis in the system Pumps and Refrigeration (IZW), Hannover.
cept for evaluating Eco-Efficiency. It is of coordinates, whilst the results of the life Study 2010: Compiled by SKM ENVIROS, UK,
commissioned by and in cooperation with EPEE
based on the relationship between added cycle cost analysis are shown on the y-axis. (European Partnership for Energy and Environment).
value (a product's economic value) and the This representation shows clearly that a Both projects were supported by an advisory group
resulting environmental impact. system exhibits an increasingly better Eco- of experts from the refrigeration industry.

Concept of Eco-Efficiency
y
nc
ie

Life Cycle Assessment


fic

Life-Cycle-Cost Analysis
Ef
o-
Ec

(including investment according to ISO 14040


ng
si
ea

costs, cost of operation,


cr
in
Cost advantage

capital costs)
y
nc
ie
fic
Ef

Eco-Efficiency
o-
Ec
ng
si
ea

considers
cr
de

economical and ecological

aspects
Environmental advantage

Fig. 7 Concept of Eco-Efficiency Fig. 8 Example of an Eco-Efficiency evaluation

7
HCFC Refrigerants

R22 as transitional refrigerant With regard to components and system BITZER can supply a widespread range of
technology a number of particularities are reciprocating, screw and scroll compres-
to follow as well. Refrigerant R22 has ap- sors for R22.
Although chlorine free substitutes like
proximately 55% higher refrigerating cap-
R134a and R404A/R507A (Figs. 1 and 2)
acity and pressure levels in comparison
have extensively made their way as substi-
to R12**. The significantly higher discharge
tutes, in many international fields R22 is still
gas temperature is also a critical factor
used in new installations and for retrofitting
compared to R12 (Fig. 9) and R502**.
of existing systems.
Similar relationships in terms of thermal
Reasons are relatively low investment costs,
load are found in the comparison with HFC
especially compared with R134a systems,
refrigerants R134a, R404A/R507A (pages 9
but also in its large application range, fa-
and 17).
vourable thermodynamic properties and
low energy requirement. Additionally there
is world wide availability of R22 and the Resulting design criteria
proven components for it, which is not yet
Particularly critical due to the high dis-
guaranteed everywhere with the chlorine * Not allowed for new equipment in Germany and
charge gas temperature are low tempera- Denmark since January 1st, 2000 and in Sweden
free alternatives.
ture plants especially concerning thermal as of 1998.
Despite of the generally favourable proper- stability of oil and refrigerant, with the dan- Since January 1st, 2001 restrictions apply to the
other member states of the EU as well. The meas-
ties R22 is already subject to various re- ger of acid formation and copper plating. ures concerned are defined in the ODS Regulation
gional restrictions* which control the use Special measures have to be adopted 1005/2009 of the EU commision on ozone deplet-
ing substances amended in 2009. This regulation
of this refrigerant in new systems and for therefore, such as two stage compression, also governs the use of R22 for service reasons
service purposes due to its ozone deple- controlled refrigerant injection, additional within the entire EU.
tion potential although being low. cooling, monitoring of discharge gas tem- Since 2010, phase-out regulations in other
countries, such as the USA, are valid.
perature, limiting the suction gas superheat
and particularly careful installation. ** Already banned in most countries.

170 25
R22
t c +50 t c +60
160 20

R12 t c +40
150 t c +60 15
R502
140
Discharge gas temp. [C]

t c +50
10
Pressure [bar]

130 R22
t c +40

120 6
R12
110 4

100
2
90

80 1
-40 -30 -20 -10 0 10 -40 -20 0 20 40 60
Evaporation [C] Temperature [C]

Fig. 9 R12/R22 comparison of discharge gas temperatures of Fig. 10 R12/R22/R502 comparison of pressure levels
a semi-hermetic compressor

8
HFC and HFO refrigerants

R134a as substitute for R22. There are also limitations in the appli- Lubricants for R134a and other HFCs
cation with low evaporating temperatures to
R12 and R22
be considered. The traditional mineral and synthetic oils are
Comprehensive tests have demonstrated not miscible (soluble) with R134a and other
R134a was the first chlorine free (ODP = 0) that the performance of R134a exceeds HFCs described in the following and are
HFC refrigerant that was tested compre- theoretical predictions over a wide range of therefore only insufficiently transported
hensively. It is now used world-wide in compressor operating conditions. around the refrigeration circuit.
many refrigeration and air-conditioning units Temperature levels (discharge gas, oil) are Immiscible oil can settle out in the heat
with good results. As well as being used as even lower than with R12 and, therefore, exchangers and prevent heat transfer to
a pure substance R134a is also applied as substantially lower than R22 values. There such an extent that the plant can no longer
a component of a variety of blends (see are thus many potential applications in air- be operated. New lubricants were devel-
"Refrigerant blends", from page 13). conditioning and medium temperature re- oped with the appropriate solubility and
frigeration plants as well as in heat pumps. have been in use for many years. These
R134a has similar thermodynamic Good heat transfer characteristics in evapo- lubricants are based on Polyol Ester (POE)
properties to R12: rators and condensers (unlike zeotropic and Polyalkylene Glycol (PAG).
blends) favour particularly an economical
Refrigerating capacity, energy demand, They have similar lubrication characteristics
use.
temperature properties and pressure levels to the traditional oils, but are more or less
are comparable, at least in air-conditioning R134a is also characterized by a compara- hygroscopic, dependent upon the refriger-
and medium temperature refrigeration bly low GWP (1430). In view of future use ant solubility.
plants. This refrigerant can therefore be restrictions (e.g. EU F-Gas Regulation), this This demands special care during manufac-
used as an alternative for most former R12 refrigerant will continue to be applicable for turing (including dehydrating), transport,
applications. a longer time to come. storage and charging, to avoid chemical
reactions in the plant, such as hydrolysis.
For some applications R134a is even pre-
ferred as a substitute for R22, an impor- PAG based oils are especially critical with
tant reason being the limitations to the use respect to water absorption. Moreover, they
of R22 in new plants and for service. How- have a relatively low dielectric strength and
ever, the lower volumetric refrigerating cap- for this reason are not very suitable for
acity of R134a (see Fig. 11/2) requires a semi-hermetic and hermetic compressors.
larger compressor displacement than with They are therefore mainly used in car A/C

110 110

105 100 tc 5 0 C
COP t c 50C
COP tc 4 0 C
Relation R134a to R22 (=100%)
Relation R134a to R12 (=100%)

t c40C
100 90

0 C 0 C
t c4 t c5
95 80

Qo
90 70
t c 40 C
Qo
t c 50 C
85 60

t oh 20C t oh 20C
80 50
-30 -20 -10 0 10 -20 -10 0 10 20
Evaporation [C] Evapration [C]

Fig. 11/1 R134a/R12 comparison of performance data of Fig. 11/2 R134a/R22 comparison of performance data of
a semi-hermetic compressor a semi-hermetic compressor

9
HFC and HFO refrigerants

systems with open compressors, where The normal metallic materials used in CFC Here, the characteristics of ester oils are
specific demands are placed on lubrication plants have also been proven with ester very favourable. Under certain conditions
and optimum solubility is required because oils; elastomers must sometimes be match- they can be used with CFC refrigerants,
of the high oil circulatation rate. In order to ed to the changing situation. This is espe- they can be mixed with mineral oils and tol-
avoid copper plating, no copper containing cially valid for flexible hoses where the erate a proportion of chlorine up to a few
materials are used in these systems either. requirements call for a minimum residual hundred ppm in an R134a system.
The rest of the refrigeration industry prefers moisture content and low permeability. The remaining moisture content has, how-
ester oils, for which extensive experience ever, an enormous influence. The essential
The plants must be dehydrated with partic-
is already available. The results are positive requirement therefore exists for very thor-
ular care and the charging or changing of
when the water content in the oil does not ough evacuation (removal of remaining
lubricant must also be done carefully. In
much exceed 100 ppm. chlorine and dehydration) and the installa-
addition relatively large driers should be
tion of generously dimensioned driers.
Compressors for factory made A/C and provided, which have also to be matched to
Doubtful experience has been found, with
cooling units are increasingly being charged the smaller molecule size of R134a.
systems where the chemical stability was
with Polyvinyl Ether (PVE) oils. Although
already insufficient with R12 operation e.g.
they are even more hygroscopic than POE, Meanwhile, many years of very positive
with bad maintenance, small drier capacity,
on the other hand they are very resistant to experience with R134a and ester oils
high thermal loading. The increased deposi-
hydrolysis, thermally and chemically stable, have been accumulated. For this re-
tion of oil decomposition products contain-
possess good lubricating properties and frigerant, BITZER offers an unequalled ing chlorine often occurs here. These prod-
high dielectric strength. Unlike POE they do wide range of reciprocating, screw, and ucts are released by the working of the
not tend to form metal soap and thus the scroll compressors. highly polarized mixture of ester oil and
danger of capillary clogging is reduced. R134a and find their way into the compres-
Converting existing R12 plants
sor and regulating devices. Conversion
Resulting design and construction At the beginning this subject had been dis- should therefore be limited to systems
criteria cussed very controversially, several conver- which are in a good condition.
sion methods were recommended and ap-
Suitable compressors are required for plied. Today there is a general agreement Restrictions for R134a in mobile
R134a with a special oil charge, and adapt- on technically and economically matching air-conditioning (MAC) systems
ed system components. solutions.
In future, a new EU Directive on "Emissions
from MAC systems" will ban the use of
R134a in new systems. Several alternative
technologies are already being developed.
See the pertaining explanations on pages
11, 12 and 35.
25

20

15

10
Supplementary BITZER information
Pressure [bar]

concerning the use of R134a


6 (see also http://www.bitzer.de)
R22
4 Semi-hermetric reciprocating com-
pressors KP-104 ECOLINE Series
R12 Technical Information KT-620
2 HFC Refrigerant R134a
Technical Information KT-510
R134a
1 Polyolester oils for reciprocating
compressors
-40 -20 0 20 40 60 Special edition
Temperature [C]
A new generation of compact screw
compressors optimised for R134a
Fig. 12 R134a/R12/R22 comparison of pressure levels

10
HFC and HFO refrigerants

Alternatives to R134a R152a an alternative Low GWP HFO refrigerants


to R134a (?) R1234yf and R1234ze(E)
For mobile air-conditioning systems (MAC)
with open drive compressors and hose The ban on the use of R134a in mobile air-
Compared to R134a, R152a is very similar
connections in the refrigerant circuit, the conditioning systems within the EU has trig-
with regard to volumetric cooling capacity
risk of leakages is considerably higher than gered a series of research projects. Apart
(approx. -5%), pressure levels (approx.
with stationary systems. With a view to re- from the CO2 technology (page 35), new
-10%) and energy efficiency. Mass flow,
ducing direct emissions in this application refrigerants with very low GWP values and
vapour density and thus also the pressure
area, an EU Directive (2006/40/EC) has similar thermodynamic properties as R134a
drop are even more favourable (approx.
therefore been passed. Within the scope of have been developed.
-40%).
the Directive, and starting 2011, type appro-
vals for new vehicles will only be granted if R152a has been used for many years as a In early 2006, two refrigerant mixtures were
they use refrigerants with a global warming component in blends but not as a single introduced under the names "Blend H"
potential (GWP) of less than 150. Conse- substance refrigerant till now. Especially (Honeywell) and "DP-1" (DuPont). INEOS
quently, this excludes R134a (GWP = 1430) advantageous is the very low global warm- Fluor followed with another version under
which has been used so far in these ing potential (GWP = 124). the trade name AC-1. In the broadest
systems. sense, all of these refrigerants were blends
R152a is flammable due to its low of various fluorinated molecules.
Meanwhile, alternative refrigerants and new fluorine content and classified in safety
technologies were developed and tested. group A2. As a result, increased safety During the development and test phase it
This also involved a closer examination of requirements demand individual design became obvious that not all acceptance cri-
the use of R152a. solutions and safety measures along with teria could be met, and thus further exami-
the corresponding risk analysis. nations with these blends were discontinued.
For quite some time the automotive indus- Consequently, DuPont* and Honeywell*
try has agreed on so-called "Low GWP" For this reason, the use of R152a in MAC bundled their research and development
refrigerants. The latter is dealt with as fol- systems is rather unlikely. activities in a joint venture which focused on
lows. 2,3,3,3-tetrafluoropropene (CF3CF = CH2).
The CO2 technology which was preferred This refrigerant, designated R1234yf, be-
for this type of application for a long time longs to the group of hydro fluoro olefins
has not yet been introduced for different (HFO). These refrigerants are unsaturated
reasons (see pages 12 and 35). HFCs with a chemical double bond.
The global warming potential is extremely
low (GWP100 = 4). When released to the
atmosphere, the molecule rapidly disinte-
grates within a few days, resulting in a very
low GWP. This raises certain concerns
regarding the long-term stability in refrigera-
tion circuits under real conditions. However,
extensive testing has demonstrated the
required stability for mobile air-conditioning
systems.
R1234yf is mildly flammable as measured
by ASTM 681, but requires significantly
more ignition energy than R152a, for
instance. Due to its low burning velocity
and the high ignition force, it received a
classification of the new safety group "A2L"
according to ISO 817.
In extensive test series, it has been shown
that a potentially increased risk of the
refrigerant flammability in MAC systems can
be avoided by implementing suitable con-

11
HFC and HFO refrigerants

structive measures. However, some investi- Further applications for From the group of hydro fluoro olefins,
gations (e.g. by Daimler-Benz) also show an HFO refrigerants another substance under the name
increased risk. This is why various manu- R1234ze(E) is available, which until now
The use of R1234yf in other mobile air-
facturers have intensified again the devel- has been used predominantly as blowing
conditioning applications is also being con-
opment of alternative technologies. agent for polyurethane foam and propel-
sidered, as well as in stationary A/C and
lant. R1234ze(E) differs from R1234yf by
Toxicity investigations have shown very heat pump systems. However, this must
having a different molecular structure. Its
positive results, as well as compatibility take into account the charge limitations for
thermodynamic properties also provide
tests of the plastic and elastomer materials the A2(L) refrigerants (e.g. EN378), which
favourable conditions for the use as refrig-
used in the refrigeration circuit. will restrict their use accordingly. Additional
erant. Its global warming potential is also
Some lubricants show increased chemical concerns are those regarding the long-
very low (GWP100 = 7).
reactivity which, however, can be sup- term stability in refrigeration circuits, given
pressed by a suitable formulation and/or the usually very long life cycles of such Often there is a degree of uncertainty con-
addition of "stabilizers". systems. cerning flammability. In safety data sheets,
R1234ze(E) is declared as non-flammable.
Operating experiences gained from labora- For applications requiring the use of refrig-
However, this only applies to transport and
tory and field trials to date allow a positive erants of safety group A1 (neither flammable
assessment, particularly with regard to per- storage. When used as a refrigerant, a
nor toxic), R134a alternatives of lower GWP
formance and efficiency behaviour. For the higher reference temperature of 60C for
based on HFO/HFC blends have already
usual range of mobile air-conditioning oper- flammability tests is valid. At this tempera-
been developed. They have been tested for
ation, refrigerating capacity and coefficient ture, R1234ze(E) is flammable and there-
some time in real systems.
of performance (COP) are within a range of fore classified in the same safety group
5% compared with that of R134a. There- R1234yf, as well as R1234ze(E), described A2L as R1234yf.
fore, it is expected that simple system below, are also used as base components
R1234ze(E) is sometimes called an R134a
modifications will provide the same per- in HFO/HFC blends. In view of legal regula-
substitute, but its volumetric refrigerating
formance and efficiency as with R134a. tions for the reduction of F-Gas emissions
capacity is more than 20% below that of
(e.g. EU F-Gas Regulation), these blends
The critical temperature and pressure levels R134a or R1234yf. Moreover, the boiling
have been developed as "Low GWP" alter-
are also similar, while the vapour densities point (-18C) considerably limits its use for
natives to R404A/R507, R22/R407C and
lower evaporation temperatures. Therefore,
and mass flows are approximately 20% R410A. Some of these refrigerants have
the preferred use of positive displacement
higher. The discharge gas temperature with already been tested with regard to refriger-
compressors is for high temperature appli-
this application is up to 10 K lower. ating capacity and efficiency as parts of
cations. For further information, see page
the "Alternative Refrigerants Evaluation
With a view to the relatively simple conver- 36, "Special applications".
Program" (AREP) initiated by AHRI and
sion of mobile air-conditioning systems, this
have also been used in trial systems. For
technology prevailed up to now over the further information on HFO/HFC blends,
competing CO2 systems. see page 24.
However, as already explained before, due
to the flammability of R1234yf, investiga-
tions focus on other technical solutions.
They include, among others, CO2 systems.

12
Refrigerant blends

Refrigerant blends A difference is made between the so called BITZER has accumulated extensive
"azeotropes" (e.g. R502, R507A) with ther- experience with refrigerant blends.
modynamic properties similar to single sub- Laboratory and field testing was com-
Refrigerant blends have been developed for stance refrigerants, and "zeotropes" with menced at an early stage so that basic
existing as well as for new plants with pro- "gliding" phase changes (see also next sec- information was obtained for the opti-
perties making them comparable alternatives tion). The original development of "zeo- mizing of the mixing proportions and
to the previously used substances. tropes" was mainly concentrated on special for testing suitable lubricants. Based
applications in low temperature and heat on this data, a large supermarket plant
It is necessary to distinguish between three with 4 BITZER semi-hermetics in par-
categories: pump systems. Actual system construction
allel could already be commissioned
remained, however, the exception. in 1991.
1. Transitional or service blends The use of these blends in the most
A somewhat more common earlier practice
Most of these blends contain HCFC R22 varied systems has been state-of-the-
was the mixing of R12 to R22 in order to
as the main constituent. They are primarily art for many years generally with
improve the oil return and to reduce the
intended as service refrigerants for good experiences.
discharge gas temperature with higher
older plants with view on the use ban of
pressure ratios. It was also usual to add R22
R12, R502 and other CFCs. General characteristics of zeotropic
to R12 systems for improved performance,
Corresponding products are offered by blends
or to add hydrocarbons in the extra low
various manufacturers, the practical ex-
temperature range for a better oil transport. As opposed to azeotropic blends (e.g.
perience covering the necessary steps
R502, R507A), which behave as single sub-
of conversion procedure are available. This possibility of specific "formulation"
stance refrigerants with regard to evapora-
of certain characteristics was indeed the
However, the same legal requirements tion and condensing processes, the phase
basis for the development of a new genera-
apply for the use and phase-out regula- change with zeotropic fluids occurs in a
tion of blends.
tions of these blends as for R22 (see "gliding" form over a certain range of tem-
page 8). In section "Introduction" (page 3), it was perature.
already explained that no direct single-sub-
2. HFC blends This "temperature glide" can be more or
stance alternatives (on the basis of fluori-
These are substitutes for the refrigerants less pronounced, it is mainly dependent
nated hydrocarbons) exist for the previously
R502, R22, R13B1 and R503. Above all, upon the boiling points and the percentage
used and current refrigerants of higher volu-
R404A, R507A, R407C and R410A, are proportions of the individual components.
metric refrigeration capacity than R134a.
being used to a great extent. Certain supplementary definitions are also
This is why they can only be "formulated"
One group of these HFC blends also con- being used, depending on the effective val-
as blends. However, taking into account
tains hydrocarbon additives. The latter ues, such as "near-azeotrope" or "semi-
thermodynamic properties, flammability,
exhibit an improved solubility with lubri- azeotrope" for less than 1 K glide.
toxicity and global warming potential, the
cants, and under certain conditions they list of potential candidates is strongly limited. This means in practice already a small
allow the use of conventional oils. In many increase in temperature in the evaporation
cases, this opens up possibilities for the For the previously developed CFC and
phase and a reduction during condensing.
conversion of existing (H)CFC plants to HCFC substitutes, the range of substances
In other words, based on a certain pressure
chlorine-free refrigerants (ODP = 0) with- was still comparably large, due to the fact
the resulting saturation temperatures differ
out the need for an oil change. that substances of high GWP could also be
in the liquid and vapour phases (Fig. 13).
used. However, for formulating blends with
3. HFO/HFC blends significantly reduced GWP, in addition to To enable a comparison with single sub-
as successor generation of HFC refriger- R134a, R1234yf and R1234ze(E), primarily stance refrigerants, the evaporating and
ants. It concerns blends of new "Low refrigerants R32, R125 and R152a can be condensing temperatures have been often
GWP" refrigerants (e.g. R1234yf) with used. Most of them are flammable. They defined as mean values. As a consequence
HFCs. The fundamental target is an addi- also exhibit considerable differences with the measured subcooling and superheating
tional decrease of the global warming respect to their boiling points, which is why conditions (based on mean values) are
potential (GWP) as compared to estab- all "Low GWP" blends of high volumetric unreal. The effective result related to dew
lished halogenated substances (see refrigerating capacity have a substantial and bubble temperature is less in each
page 24). temperature glide (see following section). case.
Two and three component blends already
have a long history in the refrigeration trade.

13
Refrigerant blends

25

20

Isotherms 15
t cm B B1
C1
C t g
e

10
Lin
le

D e w line
Pressure

bb

Pressure [bar]
R502
Bu

D1 D t om
4
t g A A1 R404A

2
t g Temperature glide
t cm Mean condensing temperature
t om Mean evaporating temperature
1
-40 -20 0 20 40 60
Enthalpy Temperature [C]

Fig. 13 Evaporating and condensing behavior of zeotropic blends Fig. 14 Pressure level of R404A in comparison to R502

These factors are very important when A further characteristic of zeotropic refriger- Further conditions/recommendations con-
assessing the minimum superheat at the ants is the potential concentration shift cerning the practical handling of blends
compressor inlet (usually 5 to 7 K) and the when leakage occurs. Refrigerant loss in must also be considered:
quality of the refrigerant after the liquid the pure gas and liquid phases is mainly
The plant always has to be charged with
receiver. non-critical. Leaks in the phase change
liquid refrigerant. When vapour is taken
areas, e.g. after the expansion valve, within
With regard to a uniform and easily com- from the charging cylinder shifts in con-
the evaporator and condenser/receiver are
prehensible definition of the rated com- centrations may occur.
considered more significant.
pressor capacity, the revised standards
It is therefore recommended that soldered Since all blends contain at least one
EN12900 and AHRI540 are applied. Evapo-
or welded joints should be used in these flammable component, the entry of
rating and condensing temperatures refer
sections. air into the system must be avoided.
to saturated conditions (dew points).
A critical shift of the ignition point can
Extended investigations have in the mean-
Evaporating temperature according to occur under high pressure and evacu-
time shown that the effect of leakage leads
point A (Fig. 13). ating when a high proportion of air is
to less serious changes in concentration
present.
Condensing temperature according to than was initially thought. It is in any case
point B (Fig. 13). certain that the following substances of The use of blends with a significant tem-
safety group A1 (see page 38) which are perature glide is not recommended for
In this case the assessment of the effective
dealt with here cannot develop any flam- plants with flooded evaporators. A large
superheat and subcooling temperatures will
mable mixtures, either inside or outside the concentration shift is to be expected in
be simplified.
circuit. Essentially similar operating condi- this type of evaporator, and as a result
It must however be considered that the tions and temperatures as before can only also in the circulating refrigerant mass
actual refrigerating capacity of the system be obtained by supplementary charging flow.
can be higher than the rated compressor with the original refrigerant in the case of a
capacity. This is partly due to an effectively small temperature glide.
lower temperature at the evaporator inlet.

14
Service blends

Service blends with the miscibility with traditional lubricants as R143a and R218 still have a high global
basic component R22* as hydrocarbons have especially good solu- warming potential (GWP).
bility characteristics.
substitutes for R502 Resulting design criteria/
For these blends two variations are offered Converting existing R502 plants
As a result of the continued refurbishment in each case. When optimizing the blend
of older installations, the importance of variations with regard to identical refrigerat- The compressor and the components which
these refrigerants is clearly on the decline. ing capacity as for R502 the laboratory are matched to R502 can remain in the sys-
For some of them, production has already measurements showed a significantly in- tem in most cases. The limitations in the
been discontinued. However, for develop- creased discharge gas temperature (Fig. application range must however be con-
ment-historic reasons of service blends, 15), which above all, with higher suction sidered: Higher discharge gas temperature
these refrigerants will continue to be cov- gas superheat (e.g. supermarket use) leads as for R502 with R402B**, R403A** and
ered in this Report. to limitations in the application range. R408A** or higher pressure levels with
R402A** and R403B**.
These refrigerants belong to the group of On the other hand a higher proportion of
"Service blends" and are offered under the R125 or R218, which has the effect of re- Due to the good solubility characteristics of
designations R402A/R402B* (HP80/ HP81 ducing the discharge gas temperature to R22 and R290 an increased danger exists,
DuPont), R403A/R403B* (formerly the level of R502, results in somewhat high- that after conversion of the plant, possible
ISCEON 69S/69L) and R408A* (Forane er cooling capacity (Fig. 16). deposits of oil decomposition products
FX10 Arkema). containing chlorine may be dissolved and
With regard to material compatibility the find their way into the compressor and reg-
The basic component is in each case R22, blends can be judged similarly to (H)CFC ulating devices. Systems where the chemi-
the high discharge gas temperature of refrigerants. The use of conventional refrig- cal stability was already insufficient with
which is significantly reduced by the addi- eration oil (preferably semi or full synthetic) is R502 operation (bad maintenance, low drier
tion of chlorine free substances with low also possible due to the R22 and R290 capacity, high thermal loading) are particu-
isentropic compression exponent (e.g. proportions. larly at risk.
R125, R143a, R218). A characteristic fea-
Apart from the positive aspects there are
ture of these additives is an extraordinarily
also some disadvantages. These sub-
high mass flow, which enables the mixture
stances can also only be seen as alterna-
to achieve a great similarity to R502.
tives for a limited time. The R22 proportion
has (although low) an ozone depletion poten- * When using blends containing R22 legal regu-
R290 (Propane) is added as the third com- lations are to be observed, see also page 8.
ponent to R402A/B and R403A/B to improve tial. The additional components R125, ** Classification according to ASHRAE nomenclature.

170
R22
165
115
160 t o -35C
t o -35C tc 40C
155 t c 40C 110 t oh 20C
Comparison of performance [%]

t oh 20C
Discharge gas temp. [C]

150
105
145

140
R403A

100
135

130 95
R402B (HP81)

R402B (HP81)
R402A (HP80)

R402A (HP80)

R502
R408A (FX10)

R408A (FX10)
R403A (69S)

R403B (69L)

R403A (69S)

R403B (69L)

125
90
R403B

R502

R502

120

115 85
0 20 40 60
Content of R218 [%] Qo COP
Fig. 15 Effect of the mixture variation upon the discharge Fig. 16 Comparison of the performance data of a semi-hermetic
gas temperature (example: R22/R218/R290) compressor

15
Service blends

Before conversion generously dimensioned The main components are the HCFC re- Resulting design criteria/
suction gas filters and liquid line driers frigerants R22, R124 and/or R142b. Converting existing R12 plants
should therefore be fitted for cleaning and Either HFC R152a or R600a (Isobutane)
Compressors and components can mostly
after approximately 100 hours operation an is used as the third component. Operation
remain in the system. However, when us-
oil change should be made; further checks with traditional lubricants (preferably semi
ing R413A and R437A the suitability must
are recommended. or full synthetic) is also possible due to the
be checked against HFC refrigerants. The
major proportion of HCFC.
The operating conditions with R502 (in- actual "retrofit" measures are mainly re-
cluding discharge gas temperature and A further service blend was offered under stricted to changing the refrigerant (possibly
suction gas superheat) should be noted so the designation R413A (ISCEON49 oil) and a careful check of the superheat
that a comparison can be made with the DuPont), but replaced by R437A by the end setting of the expansion valve.
values after conversion. Depending upon of 2008. However, for development-historic A significant temperature glide is present
the results regulating devices should possi- reasons of service blends, R413A will con- due to the relatively large differences in the
bly be reset and other additional measures tinue to be covered in this Report. The con- boiling points of the individual substances,
should be taken as required. stituents of R413A consist of the chlorine which demands an exact knowledge of the
free substances R134a, R218, and R600a. saturation conditions (can be found from
Supplementary BITZER information In spite of the high R134a content the use vapour tables of refrigerant manufacturer) in
concerning the use of retrofit blends of conventional lubricants is possible be- order to assess the effective suction gas
(see also http://www.bitzer.de) cause of the relatively low polarity of R218 superheat.
and the favourable solubility of R600a.
Technical Information KT-650 In addition the application range must also
Retrofitting of R12 and R502 R437A is a blend of R125, R134a, R600 be observed.
refrigerating systems to alterna- and R601 with similar performance and Different refrigerant types are required for
tive refrigerants properties as R413A. This refrigerant also high and low evaporating temperatures or
has zero ODP. distinct capacity differences must be con-
sidered (application ranges see page 40).
However, due to the limited miscibility of
This is due to the steeper capacity charac-
R413A and R437A with mineral and alkyl-
teristic, compared to R12.
benzene oils, oil migration may result in
systems with a high oil circulation rate Due to the partially high proportion of R22
and/or a large liquid volume in the receiver especially with the low temperature blends,
Service blends as for example if no oil separator is installed. the discharge gas temperature with some
substitutes for R12 (R500) refrigerants is significantly higher than with
If insufficient oil return to the compressor is
R12. The application limits of the compres-
observed, the refrigerant manufacturer rec-
sor should therefore be checked before
Although as experience already shows, ommends replacing part of the original oil
converting.
R134a is also well suited for the conversion charge with ester oil. But from the compres-
The remaining application criteria are simi-
of existing R12 plants, the general use for sor manufacturer's view, such a measure
lar to those for the substitute substances
such a "retrofit" procedure is not always requires a very careful examination of the
for R502 which have already been men-
possible. Not all compressors which have lubrication conditions. For example, if in-
tioned.
previously been installed are designed for creased foam formation in the compressor
the application with R134a. In addition a crankcase is observed, a complete change * By using R22 containing blends the legal require-
conversion to R134a requires the possibility to ester oil will be necessary. Moreover, ments are to be followed, see also page 8.
to make an oil change, which is for exam- under the influence of the highly polarized
ple not the case with most hermetic type blend of ester oil and HFC, the admixture of
compressors. or conversion to ester oil leads to increased
dissolving of decomposition products and
Economical considerations also arise, espe-
dirt in the pipework. Therefore, generously
cially with older plants where the effort in
dimensioned suction clean-up filters must
converting to R134a is relatively high. The
be provided.
chemical stability of such plants is also
For further details, see the refrigerant manu- Supplementary BITZER information
often insufficient and thus the chance of
facturer's "Guidelines". concerning the use of retrofit blends
success is very questionable.
(see also http://www.bitzer.de)
Therefore "Service blends" are also avail-
able for such plants as an alternative to Technical Information KT-650
R134a and are offered under the designa- Retrofitting of R12 and R502
tions R401A/R401B (MP39/MP66 DuPont), refrigerating systems to alternative
R409A (Forane FX56 Arkema, Solvay). refrigerants
16
HFC Alternatives for R502 and R22

R404A and R507A as Due to the similar boiling points for R143a something of a hitch. It is however improved
and R125, with a relatively low proportion compared to R502 and with regard to the
substitutes for R502
of R134a, the temperature glide with the favourable energy demand also leads to a
and R22 ternary blend R404A within the relevant reduction of the TEWI value. Other improve-
application range is less than one Kelvin. ments are possible in this respect due to
These blends are chlorine free substitutes The characteristics within the heat ex- further developed system control.
(ODP = 0) for R502 as well as for R22 in changers are not therefore very different as
medium and low temperature ranges. with azeotropes. The results obtained so far Nevertheless, due to their high global
from heat transfer measurements show warming potential (GWP), the use of R404A
A composition which was already launched and R507A will no longer be allowed in the
favourable conditions.
at the beginning of 1992 is known under EU in new installations from 2020. This has
the trade name "Suva" HP62 (DuPont). R507A is a binary substance combination already been settled in the F-Gas Regula-
Long term use has shown good results. which even gives an azeotropic characteris- tion No. 517/2014 to be applied from 2015.
Further blends were traded as "Forane" tic over a relatively wide range. The condi- However, the concurrent requirement on
FX70 (Arkema) and "Genetron" AZ50 (Allied tions therefore tend to be even better. the phase-down in connection with a strict
Signal/Honeywell) or "Solkane" 507 (Solvay). The performance found in laboratory tests quota system will lead to an earlier phase-
In the mean time HP62 and FX70 have (Fig. 18) gives hardly any difference be- out in many applications. For more detailed
been listed in the ASHRAE nomenclature tween the various substances and show a information, please refer to BITZER
as R404A and AZ50 as R507A. large amount of agreement with R502. This brochure A-510.
The basic components belong to the HFC also explains the high market penetration of
In the US there are also initiatives (EPA rec-
group, where R143a belongs to the flam- these substitutes they are essentially
ommendation) to phase out R404A and
mable category. Due to the combination "standard" in commercial refrigeration sys-
R507A from 2016. Other regions will proba-
with a relatively high proportion of R125 the tems in Europe and North America.
bly follow.
flammability is effectively counteracted and Questions concerning material compatibility
also in the case of leakage. are manageable; experience with other Alternatives with lower GWP are the HFC
HFCs justifies a positive assessment. POE blends dealt with in the following (from
A feature of all three ingredients is the very
oils can be used as lubricants; the suitability page 18) as well as HFO/HFC blends being
low isentropic compression exponent which
of various alternatives is being investigated developed and evaluated (from page 24).
results in a similar, with even a tendency to
be lower, discharge gas temperature to as well (see pages 9/10). Halogen free refrigerants or cascade
R502 (Fig. 17). The efficient application of The relatively high global warming potential systems using different refrigerants are
single stage compressors with low evapo- (GWP100 = 39223985) which is mainly also an option for specific applications
rating temperatures is therefore guaranteed. determined by the R143a and R125 is (from page 27).
Discharge gas temp. of R404A relative difference to R502 [K]

t o -35C
+10 105 tc 40C
t oh 20C
Comparison of performance [%]

t oh 20C 100

0
95

t c 55C
90
-10
t c 40C
85
R404A

R507A

R404A

R507A
R502

R502

-20 80
-40 -30 -20 -10
Evaporating [C] Qo COP
Fig. 17 R404A/R502 comparison of discharge gas temperatures of a semi- Fig. 18 Comparison of performance data of a semi-hermetic
hermetic compressor compressor

17
HFC Alternatives for R502 and R22

Resulting design criteria R407A/R407B/R407F as tion the isentropic compression exponent is


even higher than with R22. To match the
The system technology can be based on substitutes for R502 and R22
characteristics at the level of R404A and
the experience with R502 over a wide area. R507A therefore requires relatively high pro-
On the thermodynamic side, a heat ex- Alternatively to the earlier described substi- portions of R125 and R134a. The flamma-
changer between the suction and liquid line tutes additional mixture versions have been bility of the R32 is thus effectively suppressed,
is recommended as this will improve the developed based on R32 which is chlorine at the same time the large differences in the
refrigerating capacity and COP. free (ODP = 0) and flammable like R143a. boiling points with a high proportion of
The refrigerant R32 is also of the HFC type R134a leads to a larger temperature glide.
BITZER offers the whole program of and initially seen as a candidate for R22
reciprocating, scroll and screw com- alternatives (page 20). However, due to ex- The main advantage of R32 is the extra-
pressors for these blends. tent of blend variations comparable thermo- ordinarily low global warming potential
dynamic characteristics to R404A/R507A (GWP100 = 675) so that even in combina-
Converting existing (H)CFC plants can also be obtained. tion with R125 and R134a it is significantly
lower than with the R143a based alterna-
Experience gained in investigative programs Such kind of refrigerants were at first in the tives mentioned above (R407A: GWP100 =
shows that qualified conversions are pos- market under the trade name KLEA 60/61 2107, R407F: GWP100 = 1825).
sible. However, major expenditure may be (ICI) and are listed as R407A/R407B* in the
necessary depending on the system de- ASHRAE nomenclature. With that they also comply with the require-
sign. ment of the new EU F-Gas Regulation
Honeywell has developed another blend which from 2020 will only allow refrigerants
Supplementary BITZER information with the trade name Performax LT (R407F of GWP < 2500.
concerning the use of HFC blends according to ASHRAE nomenclature) and
Measurements made with R32 containing
(see also http://www.bitzer.de) introduced it into the market. The R32
blends do show certain capacity reductions
share is ten percentage points higher than
Technical Information KT-651 "Retro- the one in R407A while the R125 propor-
compared to R404A and R507A, with low
fitting of R22 systems to alternative evaporating temperatures, the COP howev-
tion is lower accordingly.
refrigerants" er shows less deviation and is even higher
Technical Information KT-510 The necessary conditions, however, for in medium temperature applications (Fig. 20).
Polyolester oils for reciprocating alternatives containing R32 are not quite as
compressors favourable compared to the R143a based * Meanwhile, R407B is no longer available in the mar-
ket. Due to the historical development of HFC
substitutes as dealt with earlier. The boiling blends this refrigerant will, however, still be consid-
point of R32 is very low at -52C, in addi- ered in this Report.

50
Discharge gas temp. of R407A/F relative difference to R404A [K]

to -10C
t c 40C
105 tc 45C
40 toh 20C
100
Comparison of performance [%]

30
R4 95
07F

20 90
R40
7A

80
10
R407A

R404A

R407A
R407F

R407F
R404

75
0
-40 -30 -20 -10 0
Evaporation [C] Qo COP
Fig. 19 R407A, R407F/R404A comparison of discharge gas temperature of a Fig. 20 Comparison of performance data of a semi-hermetic compressor
semi-hermetic compressor

18
HFC Alternatives for R502 and R22

Whether these favourable conditions are Conversion of R404A/R507A systems suction gas superheat this can be negative
confirmed in real applications is subject Larger differences in thermodynamic prop- due to increased refrigerant solution if ester
to the system design. erties (e.g. mass flow, discharge gas tem- oil is used.
perature) and the temperature glide of
An important factor is the significant tem- The material compatibility is comparable to
R407A/F may require the replacement of
perature glide which can have a negative the blends mentioned previously, the same
control components and if necessary retro-
influence upon the capacity/temperature applies to the lubricants, as well. On ac-
difference of the evaporator and condenser. fitting of additional compressor cooling
count of the good solubility of R600a, con-
With regard to the material compatibility, when existing systems are converted.
ventional lubricants can also be used under
R32 blends can be assessed similarly to In newly built systems a specific design of
favourable circumstances.
R404A and R507A; the same applies to the components and system must be made.
In particular, advantages result during the
lubricants.
BITZER offers a comprehensive program conversion of existing R502 and R22 sys-
Despite the relatively high proportion of of semi-hermetic reciprocating compres- tems as mentioned above. However, for
R125 and R134a in the R32 blends the dis- sors for R407A und R407F. plants with high oil circulation rates and/or
charge gas temperature is higher than with large liquid charge in the receiver, it is
the R143a based alternatives. This is in Supplementary BITZER information possible for oil migration to occur for
particular valid for R407F. As a result cer- concerning the use of HFC blends example if no oil separator is installed.
tain limitations occur in the application (see also http://www.bitzer.de)
If insufficient oil return to the compressor is
range as well as the requirement for addi-
Technical Information KT-651 observed, the refrigerant manufacturer rec-
tional cooling of compressors when operat-
Retrofitting of R22 systems to ommends replacing part of the original oil
ing at high pressure ratios.
alternative refrigerants charge with ester oil. But from the com-
2-stage compressors can be applied very pressor manufacturer's view, such a meas-
efficiently where especially large lift condi- ure requires a very careful examination of
tions are found. An important advantage the lubrication conditions. For example, if
thereby is the use of a liquid subcooler. increased foam formation in the compres-
R422A as substitute sor crankcase is observed, a complete
Resulting design criteria for R502 and R22 change to ester oil* will be necessary. Un-
der the influence of the highly polarized
The experience with R404A/R507A and
Amongst other aims, R422A (ISCEON blend of ester oil and HFC, the admixture of
R22 can be used for the plant technology
MO79 DuPont) was developed in order to or conversion to ester oil leads to increased
in many respects, considering the tempera-
obtain a chlorine-free refrigerant (ODP = 0) dissolving of decomposition products and
ture glide as well as the difference in the
for the simple conversion of existing medium dirt in the pipework. Therefore, generously
thermodynamic properties.
and low temperature refrigeration systems dimensioned suction clean-up filters must
using R502 and R22. be provided.
Converting existing R22 plants
For further details, see the refrigerant man-
For this, it was necessary to formulate a
Practical experiences show that qualified ufacturer's "Guidelines".
refrigerant with comparable performance
conversions are possible. Compared to R22
and energy efficiency to that of R404A, From a thermodynamic point of view a heat
the volumetric refrigeration capacity is near-
R507A, and R22, which also permits the exchanger between suction and liquid line
ly similar while the refrigerant mass flow is
use of conventional lubricants. is recommended, thereby improving the
only slightly higher. These are relatively
cooling capacity and coefficient of perform-
favourable conditions for the conversion of This pertains to a zeotropic blend of the
ance. Besides this the resulting increase in
medium and low temperature R22 systems. basic components R125 and R134a with a
operating temperatures leads to more fa-
small addition of R600a. Due to its relatively
The main components can remain in the vourable lubricating conditions (lower solu-
high R134a percentage, the temperature
system provided that they are compatible bility).
glide (Fig. 34) lies higher than for R404A,
with HFC refrigerants and ester oils. How-
but lower than other refrigerants with the
ever, special requirements placed on the
same component blends such as R417A * General proposal for screw compressors and liquid
heat exchanger with regard to the signifi- chillers when used with DX evaporators with internal-
and R422D (see page 22).
cant temperature glide must be considerd. ly structured heat exchanger pipes. Furthermore, an
individual check regarding possible additional meas-
A conversion to ester oil is also necessary, The adiabatic exponent, compared to ures will be necessary.
which leads to increased dissolving of R404A and R507A, is smaller and therefore
decomposition products and dirt in the the discharge gas and oil temperatures of
pipework. Therefore, generously dimen- the compressor, too. Under extreme low BITZER compressors are suitable for
sioned suction clean-up filters must be pro- temperature conditions this can be advan- R422A. An individual selection is pos-
vided. tageous. In cases of low pressure ratio and sible upon demand.

19
HFC Alternatives for R22

HFC alternatives for R22 R407C as substitute With that R407C also complies with the
requirement of the new EU F-Gas Regula-
for R22
tion which from 2020 will only allow refrig-
As the HCFC refrigerant R22 (ODP = 0.05) erants with GWP < 2500.
is accepted only as a transitional solution, a Blends of the HFC refrigerants R32, R125
number of chlorine-free (ODP = 0) alternati- and R134a are seen as the favourite can- The high temperature glide is a disadvan-
ves have been developed and tested exten- didates for shortterm substitution for R22 tage for usual applications which requires
sively. They are already being used on a their performance and efficiency are very appropriate system design and can have a
large range of applications. similar (Fig. 21). At first two blends of the negative influence on the efficiency of the
same composition have been introduced heat exchangers (see explanations on
Experience shows, however, that none of pages 13/14).
under the trade names AC9000* (DuPont)
these substitutes can replace the refrigerant
and KLEA66* (ICI). They are listed in the Due to the properties mentioned, R407C is
R22 in all respects. Amongst others there
ASHRAE nomenclature as R407C. In the preferably an R22 substitute for air-condi-
are differences in the volumetric refrigerat-
meantime there are also further blend vari- tioning systems and (within certain limita-
ing capacity, restrictions in possible appli-
eties (e.g. R407A/R407F) with somewhat tions) also for medium temperature refriger-
cations, special requirements in system
differing compositions, whose properties ation. In low temperature refrigeration, be-
design or also considerably differing pres-
have been optimized for particular applica- cause of the high proportion of R134a, a
sure levels. So various alternatives come
tions (see page 18). significant drop in refrigerating capacity and
under consideration according to the par-
ticular operating conditions. Unlike the R502 substitutes with identical COP is to be expected. There is also the
blend components (see pages 18/19), the danger of an increased R134a concentra-
Apart from the single-component HFC tion in the blend in evaporators, with con-
R22 substitutes under consideration con-
refrigerant R134a, these are mainly blends sequential reduction in performance and
tain higher proportions of R32 and R134a.
(different compositions) of the components malfunctioning of the expansion valve (e.g.
A good correspondence with the properties
R32, R125, R134a, R143a, and R600(a). insufficient suction gas superheat).
of R22 in terms of pressure levels, mass
The following description mainly concerns
flow, vapour density and volumetric refriger- Material compatibility can be assessed as
the development and potential applications
ating capacity is thus achieved. In addition, similar to that of the blends discussed pre-
of these. The halogen-free substitutes NH3,
the global warming potential is relatively low viously; the same applies to the lubricants.
propane and propylene as well as CO2
(GWP100 = 1774), which is a good presup-
should also be considered, however, spe-
position for favourable TEWI values. * Previous trade names are not used any more.
cific criteria must be applied for their use
(described from page 27).

110 25

20
105
t c 4 0 C 15
Qo
Relation R407C to R22 (=100%)

t c5 0 C R407C
100
tc 4 0 C 10
R22
COP
Pressure [bar]

tc 50 C
95
6

90 4

85
2

toh 20C
80 1
-20 -10 0 10 20 -40 -20 0 20 40 60
Evaporation [C] Temperature [C]
Fig. 21 R407C/R22 comparison of performance data of a semi-hermetic Fig. 22 R407C/R22 comparison of pressure levels
compressor

20
HFC Alternatives for R22

Resulting design criteria R410A as substitute Because of the negligible temperature glide
(< 0.2 K), the general usability can be seen
With regard to system technology, previous for R22
similar to a pure refrigerant.
experience with R22 can only be utilized to
a limited extent. The distinctive temperature In addition to R407C, there is a near azeo- The material compatibility is comparable to
glide requires a particular design of the tropic blend being offered with the ASHRAE the previously discussed blends and the
main system components, e.g. evaporator, designation R410A. It is widely used already, same applies for the lubricants. However,
condenser, expansion valve. In this context mainly in air conditioning applications. the pressure levels and the higher specific
it must be considered that heat exchangers loads on the system components need to
should preferably be laid out for counter- An essential feature indicates nearly 50% be taken into account.
flow operation and with optimized refriger- higher volumetric cooling capacity (Fig.
ant distribution. There are also special re- 23/1) in comparison to R22, but with the Resulting design criteria
quirements with regard to the adjustment of consequence of a proportional rise in sys-
The fundamental criteria for HFC blends
regulating devices and service handling. tem pressures (Fig. 23/2).
also apply to the system technology with
Furthermore, the use in systems with flood- At high condensing temperatures, energy R410A, however the extreme high pressure
ed evaporators is not recommended as this consumption/COP initially seems to be less levels have to be considered (43C con-
would result in a severe concentration shift favourable than with R22. This is mainly densing temperature already corresponds
and layer formation in the evaporator. due to the thermodynamic properties. On to 26 bar abs.).
the other hand, very high isentropic efficien-
Compressors and other system compo-
cies are achievable (with reciprocating and
BITZER can supply a widespread range nents designed for R22 are not suitable for
scroll compressors), whereby the differ-
of semi-hermetic reciprocating, screw this refrigerant or only to a limited extent.
ences are lower in reality.
and scroll compressors for R407C. The availability of suitable compressors and
Added to this are the high heat transfer
system components has been secured in
Converting existing R22 plants coefficients in evaporators and condensers
the meantime.
determined in numerous test series, with
Because of the above mentioned criteria, resulting especially favourable operating When considering to cover usual R22 appli-
no general guidelines can be defined. conditions. With an optimized design, it is cation ranges, the significant differences in
Each case must therefore be examined quite possible for the system to achieve a the thermodynamic properties (e.g. pres-
individually. better overall efficiency than with other sure levels mass and volume flow, vapour
refrigerants. density) must be evaluated.

150
Qo 35
tc 4 0 C 30
140
25
tc 50C R410A
Relation R410A to R22 (=100%)

130 20

15
120
Pressure [bar]

R22

10
110

6
100
COP tc 40C
4
90 3
tc 50C
toh 20C
80 2
-20 -10 0 10 20 -40 -20 0 20 40 60
Evaporation [C] Temperature [C]

Fig. 23/1 R410A/R22 comparison of performance data of a semi-hermetic Fig. 23/2 R410A/R22 comparison of pressure levels
compressor

21
HFC Alternatives for R22

This also requires considerable construc- A refrigerant also belonging to the category R427A as a substitute for R22
tional changes to compressors, heat ex- of HFC/HC blends was introduced in 2009
changers, and controls, as well as meas- under the trade name ISCEON MO99
This refrigerant blend was introduced some
ures of tuning vibrations. (DuPont) ASHRAE classification R438A.
years ago under the trade name Forane
This formulation was selectively designed
In addition, safety requirements are con- FX100 (Arkema). In the meantime it is listed
for a higher critical temperature for applica-
cerned also affecting the quality and dimen- in the ASHRAE nomenclature as R427A.
tions in hot climate areas. The base com-
sions of piping and flexible tube elements
ponents are R32, R125, R134a, R600 and The R22 substitute is offered for the con-
(for condensing temperatures of approx.
R601a. version of existing R22 systems for which
60C/40 bar).
a Zero ODP solution is requested. This re-
Like R407C, all four substitute refrigerants
Another criterion is the relatively low critical frigerant is an HFC mixture with base com-
are zeotropic blends with a more or less sig-
temperature of 73C. Irrespective of the ponents R32/R125/R143a/R134a.
nificant temperature glide. In this respect the
design of components on the high pressure
criteria described in connection with R407C In spite of the blend composition based on
side, the condensing temperature is thus
are also valid. pure HFC refrigerants, the manufacturer
limited.
states that a simplified conversion proced-
Apart from similar refrigeration capacity
ure is possible.
For R410A, BITZER offers a series of there are fundamental differences in thermo-
semi-hermetic reciprocating compres- dynamic properties and in oil transport be- This is positively influenced by the R143a
sors and scroll compressors. haviour. The high proportion of R125 caus- proportion. Accordingly, when converting
es with R417A/B and R422D a higher mass from R22 to R427A, all it takes is a re-
flow than with R407C, a lower discharge placement of the original oil charge with
gas temperature and a relatively high super- ester oil. Additional flushing sequences are
R417A/417B/422D/438A heating enthalpy. These properties indicate not required, as proportions of up to 15%
as substitutes for R22 that there are differences in the optimization of mineral oil and/or alkyl benzene have no
of system components and a heat exchanger significant effect on oil circulation in the
The same as for R422A (page 19), one of the between liquid and suction lines is of advan- system.
aims for these developments was to provide tage.
However, it must be taken into account that
chlorine-free refrigerants (ODP = 0) for the
Despite the predominant proportion of HFC under the influence of the highly polarized
simple conversion of existing R22 plants.
refrigerants the use of conventional lubri- mixture of ester oil and HFC increased dis-
R417A was introduced to the market sever- cants is possible to some extent because solving of decomposition products and dirt
al years ago, and is also offered under the of the good solubility properties of the in the pipework is caused. Therefore, gen-
trade name ISCEON MO59 (DuPont). This hydrocarbon constituent. However, in sys- erously dimensioned suction clean-up filters
substitute for R22 contains the blend com- tems with a high oil circulation rate and/or must be provided.
ponents R125/R134a/R600, and therefore a large volume of liquid in the receiver oil
Regarding refrigerating capacity, pressure
differs considerably from e.g. R407C with a migration may result.
levels, mass flow and vapor density R427A
correspondingly high proportion of R32.
In such cases, additional measures are is relatively close to R22. During retrofit
Meanwhile, a further refrigerant based on necessary. For further information on oil essential components such as expansion
identical components, but with a higher return and lubricants, see the previous sec- valves can remain in the system.
R125 content, has been offered under tion on "R422A as substitute for R502 and Due to the high proportion of blend compo-
the trade name Solkane 22L (Solvay) R22" (page 19). nents with low adiabatic exponent the dis-
ASHRAE classification R417B. Due to its charge gas temperature is considerably
lower R134a content, the volumetric refrig- BITZER compressors are suitable for the lower than with R22 which has a positive
erating capacity as well as the pressure lev- described refrigerants. effect at high compression ratios.
els are higher than with R417A. This results An individual selection is possible upon
in different performance parameters and demand.
emphasis in the application range.
The same applies to a further blend with the
same main components, but R600a as hy-
drocarbon additive. It is offered under trade
name ISCEON MO29 (DuPont) and listed as
R422D in the ASHRAE nomenclature.

22
HFC R32

It must be taken into account that this is R32 as substitute for R22 also be used as a refrigerant in factory pro-
also a zeotropic blend with a distinct tem- duced systems (A/C units and heat pumps)
perature glide. Therefore the criteria as As described earlier R32 belongs to the HFC with low refrigerant charges. Concerning safe-
described in context with R407C are valid refrigerants group but initially was mainly used ty requirements the regulations (e.g. accord-
here as well. as a component of refrigerant blends only. An ing to EN 378) for A2 refrigerants are still valid
essential barrier for the application as a pure although it was proven in flammability tests
BITZER compressors are suitable for that the necessary ignition energy is very high
substance so far is the flammability classifica-
R427A. An individual selection is pos- and the flame speed is low. Based on these
tion in safety group A2L. This requires adequate
sible upon demand. properties R32 (like R1234yf and R1234ze)
charge limitations and/or additional safety
measures, especially with installations inside has been put into the new safety group A2L
Supplementary information concerning according to ISO 817.
buildings. In addition there are very high pres-
the use of HFC blends
sure levels and discharge gas temperatures To what extent the safety demands for A2L
(see also http://www.bitzer.de)
(compression index higher than with R22 and refrigerants (as opposed to A2) can be re-
Technical information KT-651 R410A). lieved in future can not finally be judged to-
Retrofitting R22 systems to day. Therefore, individual risk analyses are re-
On the other hand R32 has favorable thermo-
alternative refrigerants quired.
dynamic properties, e.g. very high evaporating
enthalpy and volumetric refrigerating capacity,
low vapor density (low pressure drop in pipe- BITZER scroll compressors of series
lines), low mass flow and favorable power in- GSD6/GSD8 can be delivered for labora-
put for compression. Besides that the global tory tests with R32. A customized
warming potential is low (GWP100 = 675). design is available upon request.

Looking at these favorable properties and


taking into account the additional and strived
for emission reductions, R32 will increasingly

120
Q o Refrigerating capacity to 5C
COP Coefficient of performance tc 50C
110 p c Condensing pressure t oh 10 K
q m Refrigerant mass flow
100 120
Relative comparison [%]

90
Discharge gas temperature [C]
R410A

80 100

70

60 80

50
R410A

R32

R32

40 60
Qo COP pc qm
Abb. 24 R32/R410A comparison of performance and operating data
of a scroll compressor

23
HFO/HFC blends

HFO/HFC blends as However, due to the properties of the HFC For quite some time a blend has been test-
refrigerants suitable as blend components, ed on a large scale in real systems this
alternatives to HFCs flammability and GWP are related diametri- was developed by DuPont, and is called
cally to one another. In other words: Opteon XP-10. Results available today
Due to the decision with the use of the Blends as alternatives to R22/R407C of are promising.
"Low GWP" refrigerant HFO-1234yf (see GWP < approx. 900 to 1000 are flamma-
pages 11/12) in automotive air-conditioning ble. This is also true with alternatives for This is also true for an R134a alternative
systems, the development of alternatives R404A/R507A and R410A in blends of designated Solstice N-13 and offered by
for other mobile applications and stationary GWP < approx. 1300 to 1400. The reason Honeywell which, however, differs regard-
systems has meanwhile also been initiated. for this is the high GWP of each of the re- ing the blend composition.

The primary goals are the formulation of quired non-flammable components. Meanwhile the refrigerants are listed in the
blends with significantly reduced GWP For R134a alternatives, the situation is ASHRAE nomenclature under R513A
while maintaining similar thermodynamic more favorable. Due to the already relative- (DuPont) and R450A (Honeywell).
properties to those of the HFCs used pre- ly low GWP of R134a, a blend with R1234yf
and/or R1234ze(E) enables a formulation of The same category also includes the refrig-
dominantly today. erant blends ARM-42 (ARKEMA) as well as
non-flammable refrigerants with a GWP of
The base components are the refrigerants approx. 600. AC5X (Mexichem).
R1234yf and R1234ze(E), which belong to All options have refrigerating capacity, power
Currently there are two directions of devel-
the group of hydro fluoro olefins (HFO) with input, and pressure levels similar to R134a.
opment:
a chemical double bond. Due to their com- As a result components and system tech-
Non-flammable HFC alternatives
bination of properties, they are characteri- nology can be taken over. Just minor
(blends) with GWP values according to
zed as preferred candidates. However, both changes like e.g. superheat adjustment of
the above mentioned limits safety
refrigerants are flammable (safety group the expansion valves is necessary.
group A1. Regarding safety require-
A2L). Moreover, their volumetric refrigerat-
ments these refrigerants can then be Polyolester oils are suitable lubricants
ing capacity is low. That of R1234yf is
utilized the same way as currently used which must meet special requirements,
approximately at the level of R134a and
HFCs e.g. for the utilization of additives.
that of R1234ze(E) is even more than 20%
Flammable HFC alternatives (blends)
lower. Very favorable perspectives arise in super-
with GWP values below the above men-
The list of additional potential refrigerants tioned possible limits according to market applications in the medium tem-
from the HFO group is relatively long. How- safety group A2L (for refrigerants of low perature range in a cascade with CO2 for
ever, there are only few substances that flammability). See also explanations on low temperature, just as in liquid chillers
meet the requirements in terms of thermo- page 11. with higher refrigerant charges where the
dynamic properties, flammability, toxicity, use of flammable or toxic refrigerants would
chemical stability, compatibility with materi- Among others this group of refrigerants is require comprehensive safety measures.
als and lubricants. They include, for exam- then subject to charge limitations accord-
ple, low-pressure refrigerants such as ing to today's requirements for A2 refriger- Alternatives for R22/R407C,
R1336mzzZ (DuPont DR-2) and R1233zd(E) ants. R404A/R507A and R410A
which, however, are primarily an option for Since the available HFO molecules
To what extent the safety requirements for
chillers with large centrifugal compressors (R1234yf und R1234ze) show a consider-
A2L refrigerants (compared to A2) can be
or can be used with positive displacement ably smaller volumetric refrigerating capaci-
relieved, can only be assessed by individ-
compressors in high temperature applica- ty compared to the above mentioned HFC
ual risk analyses.
tions. Furthermore, R1233zd(E) has a (very) refrigerants, for the particular alternatives
low ozone depleting potential (ODP), which relatively large HFC proportions with high
Non-flammable R134a alternatives
may lead to restrictions in its use. volumetric refrigerating capacity must be
As mentioned before, the most favorable added. The potential list of candidates is
On the other hand, currently there are no starting situation for developing non-flam- rather limited. R32 with relatively low GWP
suitable candidates of similar volumetric mable blends exists for R134a alternatives. is one option. However, a negative aspect
refrigerating capacity as R22/R407C, is its flammability (A2L), resulting also in a
For them, GWP values of approx. 600 can
R404A/R507A and R410A with prospects flammable blend upon adding fairly large
be achieved. This is less than half com-
for commercial application. Direct alterna- proportions in order to increase the volu-
pared with R134a (GWP100 = 1430). In
tives for these refrigerants of significantly metric refrigerating capacity while maintai-
addition to that, this type of blend versions
lower GWP must therefore be "formulated" ning a favorable GWP.
can have azeotropic properties, which is
as a blend of R1234yf and/or R1234ze(E)
why they can be used like pure refrigerants.
with HFC refrigerants, and possible small
proportions of hydrocarbons.

24
HFO/HFC blends

Actual Alternatives Components / Mixture components "Low GWP" alternatives


HFC Refrigerants
2 2
Safety GWP R1234yf R1234ze(E) R32 R152a R134a R125 CO2 R290
Group A2L A2L A2L A2 A1 A1 A1 A3
GWP 4 7 675 124 1430 3500 1 3


A1 ~ 600
R134a
A2L < 150
(GWP 1430)
A2L < 10
A1 < 2500 1
A1 < 1400
R404A/R507A
A2L < 250
(GWP 3922/3985)
A2L 3 < 150
A2 < 150
A1 900..1400
R22/R407C A2L < 250
(GWP 1810/1774) A2L 3 < 150
A2 < 150
R410A A2L < 750
(GWP 2088) A2L < 500

1 Refrigerating capacity, mass flow, discharge gas temperature similar to R404A


2 Only low percentage due to temperature glide (CO2) and flammability (R290)
3 Significantly lower refrigerating capacity than reference refrigerant
Abb. 25/1 Potential mixture components for "Low GWP" alternatives (Examples)

Current "Low GWP" Alternatives for HFC refrigerants 3

HFC refrigerant

ASHRAE Trade Name Composition GWP 4 Safety Group


Number (with blends) (AR4)
R513A Opteon XP10 DuPont R1234yf/134a 631 A1
R450A Solstice N-13 Honeywell R1234ze(E)/134a 601 A1
R134a AC5X Mexichem R32/1234ze(E)/134a 620 A1
1
(GWP 1430) R1234yf various 4 A2L
2
R1234ze(E) various 7 A2L
ARM-42 Arkema R1234yf/152a/134a < 150 A2L
R449A Opteon XP40 DuPont R32/125/1234yf/134a 1397 A1
R448A Solstice N-40 Honeywell R32/125/1234yf/1234ze(E)/134a 1386 A1
ARM-32b Arkema not disclosed ~ 1400 A1
LTR4X Mexichem R32/125/1234ze(E)/134a 1295 A1
R404A/R507A R452A Opteon XP44 DuPont R32/125/1234yf 2140 A1
(GWP 3922/3985) ARM-35 Arkema not disclosed ~ 2150 A1
Opteon XL40 DuPont R32/1234yf 246 A2L
Solstice L4F Honeywell not disclosed 145 A2L
ARM-20a/20b Arkema not disclosed < 150 / ~ 250 A2L
ARM-25 Arkema not disclosed < 150 A2
DR-91 DuPont not disclosed 949 A1
Solstice N-20 Honeywell R32/125/1234yf/1234ze(E)/134a 975 A1
R22/R407C
ARM-32c Arkema not disclosed ~ 1350 A1
(GWP 1810/1774)
DR-3 DuPont R32/1234yf 148 A2L
R444B Solstice L-20 Honeywell R32/152a/1234ze(E) 294 A2L
R32 various 675 A2L
Opteon XL41 DuPont R32/1234yf 466 A2L
R410A
R447A Solstice L-41 Honeywell R32/125/1234ze(E) 582 A2L
(GWP 2088)
ARM-71a Arkema not disclosed < 500 A2L
HPR1D Mexichem R32/R1234ze(E)/CO2 407 A2L
1 The relatively low GWP allows the use of R134a also longer term
2 Significantly lower refrigerating capacity than reference refrigerant
3 A number of refrigerants listed above are declared by the manufacturer as development products. This is subject for possible changes in composition and product name
4 AR4: according to IPCC IV
Abb. 25/2 "Low GWP" Alternatives for HFC refrigerants
25
HFO/HFC blends

On the other hand, when formulating as a In transport applications or in low tempera- investigate and evaluate a series of the
non-flammable blend a relatively large pro- ture systems with smaller condensing units, products including halogen-free refrige-
portion of refrigerants with high fluoric con- the compressors used can often not meet rants. A part of them is also listed in Fig.
tent (e.g. R125) must be added which the required operating ranges, due to the 25/2. The first phase of the project has
allows the flammability to be suppressed. high discharge gas temperatures. This is been completed, and further investigations
A drawback here is the relatively high GWP why refrigerant blends on basis of R32 and including those in special applications have
of these chemicals. This results in GWP HFO with a relatively high proportion of already been initiated.
values of more than approx. 900 for non- R125 have also been developed. The GWP
flammable R22/R407C alternatives and is slightly above 2000, but below the limit From a compressor manufacturers point
more than approx. 1300 with options for of 2500 set in the EU F-Gas Regulation of view there should be an aim for limiting
R404A/R507A. Compared to R404A/ from 2020. The main advantage of such the product variety currently becoming
R507A, however, this means a reduction blends is their moderate discharge gas apparent and to reduce the future offer to
down to a third. temperature, which allows the operation a few "standard refrigerants". It will not be
within the typical application limits of R404A. possible for component and equipment
The future drastic phase-down of F-Gases,
manufacturers nor for installers and servi-
e.g. as part of the EU F-Gas Regulation, Fig. 25/1 shows an overview of the poten-
ce companies to deal in practice with a
leads already today to a demand for R404A/ tial blend components for the alternatives
larger range of alternatives.
R507A substitutes with GWP values clearly described above. With some refrigerants
below 500. Although this is possible with the mixture components for R22/R407C
BITZER is strongly involved in various
an adequate composition of the blend and R404A/R507A substitutes are identical
projects dealing with HFO/HFC blends
(high proportions of HFO, R152a, possibly but their distribution in percent is different.
and has already gained important know-
also hydrocarbons), the disadvantage will
Meanwhile suitable blend versions for labo- ledge in the use of these refrigerants.
be its flammability (safety groups A2L or
ratory tests, some of them also for field Semi-hermetic reciprocating compres-
A2). In this case, the application will have
tests or real applications are being offered sors of the ECOLINE series and CS. and
higher safety requirements and the need of
primarily by DuPont, Honeywell, Arkema HS. Screw compressors can be used
an adequately adjusted system technology.
and Mexichem. A series of refrigerants are with the new refrigerant generation in
For R410A there is no non-flammable alter- still to be considered development pro- laboratory and field tests. Scroll com-
native on the horizon. Either R32 (see page ducts, which for various reasons are not pressors of series GSD6/GSD8 have
23) as pure substance or blends of R32 yet distributed commercially. Until now been released for laboratory tests with
and HFO can be used for this. Due to its trade names are mainly used although R32 or R32/HFO blends.
high volumetric refrigerating capacity this some HFO/HFC blends are already listed in An individual compressor selection is
requires a very high proportion of R32, the ASHRAE nomenclature. possible on demand.
which is why only GWP values in the range For further information see brochure
from approx. 400 to 600 can be achieved. Fig. 25/2 lists a range of currently available A-510, section 6 and brochure
With a higher HFO proportion, the GWP refrigerants or refrigerants declared as No. 378 20 386.
can be reduced even further, but at the cost development products. For some of them
of a clearly reduced refrigerating capacity. the blend components are also given. Due
to the large number of different versions
All blend options described above show a and the potential changes in development
more or less distinct temperature glide due products, BITZER has so far tested only
to significant boiling point differences. The some of the new refrigerants. This is why
same criteria apply as described in context in the tables on pages 38/39 (Fig. 33/34)
with R407C. for the time being only refrigerant proper-
Beyond that the discharge gas temperature ties of non-flammable alternatives for
of most R404A/R507A alternatives is con- R134a and R404A/R507A (GWP < 1500)
siderably higher compared to the corre- are listed which have already received an
sponding HFC blends. ASHRAE number.
In single stage low temperature systems For testing the "Low GWP" refrigerants
this may lead to restrictions in the com- AHRI (USA) has initiated a test program
pressor application range or require special entitled "Alternative Refrigerants Evaluation
measures for additional cooling. Program (AREP)". It was established to

26
Halogen free refrigerants

NH3 (Ammonia) is favourable for large plants makes the These measures significantly increase
control of the refrigerant injection more diffi- the expenditure involved for NH3 plants,
as alternative refrigerant
cult with small capacities. especially in the medium and smaller cap-
acity area.
The refrigerant NH3 has been used for more A further criteria which must be considered
than a century in industrial and larger re- is the corrosive action on copper contain- Efforts are therefore being made world-wide
frigeration plants. It has no ozone depletion ing materials; pipe lines must therefore to develop simpler systems which can also
potential and no direct global warming po- be made in steel. Apart from this the de- be used in the commercial area.
tential. The efficiency is at least as good as velopment of motor windings resistant to A part of the research programs is dealing
with R22, in some areas even more favour- NH3 is also hindered. Another difficulty with part soluble lubricants, with the aim of
able; the contribution to the indirect global arises from the electrical conductivity of improving oil circulation in the system. Sim-
warming effect is therefore small. the refrigerant with higher moisture content. plified methods for automatic return of non-
In addition it is incomparably low in price. soluble oils are also being examined as an
Additional characteristics include toxicity
Summarized, is this then an ideal refrigerant alternative.
and flammability, which require special safe-
and an optimum substitute for R22 or an
ty measures for the construction and oper-
alternative for HFCs!? NH3 has indeed very BITZER is strongly involved in these
ation of such plants.
positive features, which can also be mainly projects and has a large number of
exploited in large refrigeration plants. compressors operating. The experi-
Resulting design and construction
Unfortunately there are also negative as- criteria ences up to now have revealed that
pects, which restrict the wider use in the systems with part soluble oils are diffi-
Based on the present "state of technology", cult to govern. The moisture content in
commercial area or require costly and
industrial NH3 systems demand totally diffe- the system has an important influence
sometimes new technical developments.
rent plant technology, compared to usual on the chemical stability of the circuit
A disadvantage with NH3 is the high isen- commercial systems. and the wear of the compressor. Be-
tropic exponent (NH3 = 1.31 / R22 = 1.19 / sides, high refrigerant solution in the oil
Due to the insolubility with the lubricating
R134a = 1.1), that results in a discharge (wet operation, insufficient oil tempera-
oil and the specific characteristics of the
temperature which is even significantly hig- ture) leads to strong wear on the bear-
refrigerant, high efficiency oil separators
her than that of R22. Single stage compres- ings and other moving parts. This is
and also flooded evaporators with gravity
sion is therefore already subject to certain due to the enormous volume change
or pump circulation are usually employed.
restrictions below an evaporating tempera- when NH3 evaporates in the lubricated
Because of the danger to the public and to
ture of around -10C. areas.
the product to be cooled, the evaporator
The question of suitable lubricants is also not often cannot be installed directly at the cold These developments are being continued.
satisfactorily solved for smaller plants in space. The heat transport must then take The emphasis is also on alternative
some kinds of applications. The oils used place with a secondary refrigerant circuit. solutions for non-soluble lubricants.
previously were not soluble with the refriger-
Two stage compressors or screw compres- Besides to this various equipment manufac-
ant. They must be separated with complex
sors with generously sized oil coolers, must turers have developed special evaporators,
technology and seriously limit the use of
already be used at medium pressure ratios, where the refrigerant charge can be signifi-
"direct expansion evaporators" due to the
due to the unfavorable thermal behaviour. cantly reduced.
deterioration in the heat transfer.
Refrigerant lines, heat exchangers and fit- In addition to this there are also develop-
Special demands are made on the thermal
tings must be made of steel; larger size ments for the "sealing" of NH3 plants. This
stability of the lubricants due to the high
pipe lines are subject to examination by a deals with compact liquid chillers (charge
discharge gas temperatures. This is espe-
certified inspector. below 50 kg), installed in a closed container
cially valid when automatic operation is
considered where the oil should remain for Corresponding safety measures and also and partly with an integrated water reser-
years in the circuit without losing any of its special machine rooms are required de- voir to absorb NH3 in case of a leak. This
stability. pending upon the size of the plant and the type of compact unit can be installed in
refrigerant charge. areas which were previously reserved for
NH3 has an extraordinarily high enthalpy plants with halogen refrigerants due to the
difference and as a result a relatively small The refrigeration compressor is usually of safety requirements.
circulating mass flow (approximately 13 to "open" design, the drive motor is a separ-
15% compared to R22). This feature which ate component.

27
Halogen free refrigerants

An assessment of the use of NH3 compact Conversion of existing plants The result of this research project is a re-
systems in place of systems using HFC The refrigerant NH3 is not suitable for the frigerant blend of NH3 (60%) and dimethyl
refrigerants and conventional technology ether "DME" (40%), developed by the "Insti-
conversion of existing (H)CFC or HFC plants;
is only possible on an individual basis, tut fuer Luft- und Kaeltetechnik, Dresden",
they must be constructed completely new
taking into account the particular applica- Germany (ILK), that has been applied in a
with all components.
tion. From the purely technical view-point series of real systems. As a largely inorgan-
and presupposing an acceptable price ic refrigerant it received the designation
Supplementary BITZER information
level, it is anticipated that a wider range of R723 due to it its average molecular weight
concerning the application of NH3
products will become available. of 23 kg/kmol in accordance to the stan-
(see also http://www.bitzer.de)
dard refrigerant nomenclature.
Technical Information KT-640
The product range from BITZER today Application of Ammonia (NH3) DME was selected as an additional compo-
includes an extensive selection of opti- as an alternative refrigerant nent for its properties of good solubility and
mized NH3 compressors for various high individual stability. It has a boiling point
types of lubricants: of -26C, a relatively low adiabatic expo-
Single stage open reciprocating nent, is non toxic and is available in a high
compressors (displacement 19 to R723 (NH3/DME) as an technical standard of purity.
152 m3/h with 1450 rpm) for air-con- In the given concentration NH3 and DME
ditioning, medium temperature and alternative to NH3 form an azeotropic blend characterised by
Booster applications a slightly rising pressure level in comparison
Open screw compressors (displace- The previously described experiences with to pure NH3. The boiling point lies at
ment 84 to 1015 m3/h with parallel the use of NH3 in commercial refrigeration -36.5C (NH3 -33.4C), 26 bar (abs.) of
operation to 4060 m3/h with 2900 plants with direct evaporation caused fur- condensing pressure corresponds to
rpm) for air-conditioning, medium ther experiments on the basis of NH3 un- 58.2C (NH3 59.7C).
and low temperature cooling. der the addition of an oil soluble refrigerant
Options for low temperature cooling: component. The main goals were an im- The discharge gas temperature in air-con-
Single stage operation provement of the oil transport characteristics ditioning and medium temperature ranges
Economiser operation and the heat transmission with conventional decrease by about 10 to 25 K (Fig. 26/1)
Booster operation lubricants along with a reduced discharge and thereby allows for an extension of the
gas temperature for the extended applica- application range to higher pressure ratios.
tion range with single stage compressors. On the basis of thermodynamic calculations

180 25
R723
NH 3 20
160
tc 40C
t oh 10K 15
140 0.8
Discharge gas temperature [C]

10
Pressure [bar]

120 R22
NH 3
R22
6
100
R134a 4
80
R290

R404A 2
60

40 1
-40 -30 -20 -10 0 10 -40 -20 0 20 40 60
Evaporation [C] Temperature [C]

Fig. 26/1 Comparison of discharge gas temperatures Fig. 26/2 NH3/R22 comparison of pressure levels

28
Halogen free refrigerants

a single-digit percent rise in cooling capaci- remains in the safety group B2, but may R290 (Propane) as
ty results when compared to NH3. The receive a different classification in case of a
substitute for R502 and R22
coefficient of performance is similar and is revised assessment.
even more favourable at high pressure
ratios, which experiments have confirmed. Resulting layout criteria R290 (propane) can also be used as a sub-
Due to the lower temperature level during stitute refrigerant. As it is an organic com-
The experiences made with the NH3 com- pound (hydrocarbon) it does not have an
compression an improved volumetric and
pact systems described above can be used ozone depletion potential and a negligible
isentropic efficiency is also to be expected,
in the plant technology. However, adjust- direct global warming effect. To take into
at least with reciprocating compressors in
ments in the component layout are neces- consideration however, is a certain contri-
case of an increasing pressure ratio.
sary under consideration of the higher mass bution to summer smog.
Due to the higher molecular weight of DME, flow. Besides a suitable selection of the
mass flow and vapour density increase with evaporator and the expansion valve a very The pressure levels and the refrigerating
respect to NH3 by nearly 50% which is of stable superheat control must be ensured. capacity are similar to R22 and the tem-
little importance to commercial plants, es- Due to the improved oil solubility wet ope- perature behaviour is as favourable as with
pecially in short circuits. In classical indus- ration can have considerable negative re- R134a.
trial refrigeration plants, however, this is a sults when compared to NH3 systems with There are no particular material issues. In
substantial criterion with regard to pressure non-soluble oil. contrast to NH3 copper materials are also
drops and refrigerant circulation. Also from suitable, so that semi-hermetic and herme-
With regards to safety regulations the same
these considerations it can be clearly seen tic compressors are possible. The mineral
criteria apply to installation and operation
that in commercial applications and especi- oils usually found in a HCFC system can be
as in the case of NH3 plants.
ally in water chillers, R723 has its preferred used here as a lubricant over a wide appli-
utilisation. Suitable compressors are special NH3 ver- cation range.
sions which possibly have to be adapted to
The material compatibility is comparable to Refrigeration plants with R290 have been in
the mass flow conditions and to the con-
that of NH3. Although non-ferrous metals operation world-wide for many years, main-
tinuous oil circulation. An oil separator is
(e.g. CuNi alloys, bronze, hard solders) are ly in the industrial area it is a "proven"
usually not necessary with reciprocating
potentially suitable, provided that the water refrigerant.
compressors.
content in the system is at a minimum
(< 1000 ppm), a system design that cor- Meanwhile R290 is also used in smaller
Bitzer NH3 reciprocating compressors compact systems with low refrigerant char-
responds with typical ammonia practise
are suitable for R723 in principle. An ges like residential A/C units and heat
is recommended nonetheless.
individual selection of specifically pumps. Furthermore, a rising trend can be
As lubricant mineral oils or (preferred) poly- adapted compressors is possible on seen in its use with commercial refrigeration
alpha olefin can be used. As mentioned be- demand. systems and chillers.
fore the portion of DME creates improved
oil solubility and a partial miscibility. Besides Propane is offered also as a mixture with
this the relatively low liquid density and an Isobutane (R600a) or Ethan (R170). This
increased concentration of DME in the oil, should obtain a good performance match
positively influences the oil circulation. PAG with halocarbon refrigerants. Pure Isobu-
oils would be fully or partly miscible with tane is mostly intended as a substitute for
R723 for typical applications but are not R12 in small plants (preferably domestic
recommended for reasons of the chemical refrigerators).
stability and high solubility in the compres- The disadvantage of hydrocarbons is the
sor crankcase (strong vapour development high flammability, and therefore been classi-
in the bearings). fied as refrigerants of "Safety Group A3".
Tests have shown that the heat transfer co- With the normal refrigerant charge found in
efficient at evaporation and high heat flux is commercial plants this means that the sys-
improved in systems with R723 and mineral tem must be designed according to flame-
oil than when using NH3 with mineral oil. proof regulations.

Further characteristics are toxicity and flam- The use of semi-hermetic compressors in
mability. By means of the DME content, the so called "hermetically sealed" systems is in
ignition point in air diminishes from 15 to this case subject to the regulations for haz-
6% but. Despite of this, the azeotrope still ardous zone 2 (only seldom and short term
risk). The demands for the safety technology

29
Halogen free refrigerants

include special devices to protect against On the thermodynamic side an internal heat order does include an individual agree-
excess pressures and special arrangements exchanger between the suction and liquid ment between the contract partners.
for the electrical system. In addition meas- line is recommended as this will improve Open reciprocating compressors are
ures are required to ensure hazard free ven- the refrigerating capacity and COP. also available for R290, together with a
tilation to effectively prevent a flammable comprehensive program of flame-proof
Owing to the particularly high solubility of
gas mixture occurring in case of refrigerant accessories which may be required.
R290 (and R1270) in common lubricants,
leakage.
BITZER R290/R1270 compressors are
Conversion of existing plants with R22
The design requirements are defined by charged with a special oil of a high viscosity
or HFC
standards (e.g. EN378) and may vary in dif- index and particularly good tribological
ferent countries. For systems applied within properties. Due to the flame-proof protection measures
the EU an assessment according to the required for an R290 plant, it would appear
In connection to this, an internal heat
EC Directive 94/9/EC (ATEX) may become that a conversion of existing plants is only
exchanger is also an advantage as it leads
necessary as well. possible in exceptional cases.
to higher oil temperatures thus to lower
With open compressors this will possibly solubility with the result of an improved They are limited to systems, which can be
lead to a classification in zone 1. Zone 1 viscosity. modified to meet the corresponding safety
demands, however, electrical equipment in regulations with an acceptable effort.
Due to the very favourable temperature
special flame-proof design.
behaviour (Fig. 26/1), single stage com-
Supplementary BITZER information
pressors can be used down to approxi-
Resulting design criteria concerning the use of R290
mately -40C evaporation temperature.
Apart from the measures mentioned above, R290 could then also be considered as an Technical Information KT-660
propane plants require practically no special alternative for some of the HFC blends. Application of Propane and Propy-
features in the medium and low tempera- lene with semi-hermetic compressors
ture ranges compared with a usual (H)CFC A range of semi-hermetic reciprocating
and HFC system. When sizing components compressors and CS. compact screws is
consideration should however be given to available for R290. Due to the individual
the relatively low mass flow (approximately requirements a specifically equipped
55 to 60% compared to R22). An advan- compressor version is offered.
tage in connection with this is the possibili- Inquires and orders need a distinstive
ty to greatly reduce the refrigerant charge. indication to R290. The handling of the

120
25

20
Q o (R1270) R1270
110 15
Relation R290 and R1270 to R22 (=100%)

COP (R290)
Pressure [bar]

10
COP (R1270) R22
100 R290

4
90
Q o (R290)
2
tc 40C
toh 20C
80 1
-40 -30 -20 -10 0 10 -40 -20 0 20 40 60
Evaporation [C] Temperature [C]

Fig. 27 R290/R1270/R22 comparison of performance data of a Fig. 28 R290/R1270/R22 comparison of pressure levels
semi-hermetic compressor

30
Halogen free refrigerants

Propylene (R1270) as an that there is a danger of polymerization at As with R290 the use of an internal heat
high pressure and temperature levels. Tests exchanger between suction and liquid lines is
alternative to Propane
carried out by hydrocarbon manufacturers of advantage. However, due to R1270s high-
and stability tests in real applications show er discharge gas temperature restrictions are
For some time there has also been in- that reactivity in refrigeration systems is partly necessary.
creasing interest in using propylene practically non-existent. Doubts have occa-
(propene) as a substitute for R22 or HFC. sionally been mentioned in some literature A range of semi-hermetic reciprocating
Due to its higher volumetric refrigerating regarding propylenes possible carcinogenic compressors and CS. compact screws is
capacity and lower boiling temperature effects. These assumptions have been dis- available for R1270. Due to the individual
(compared to R290) applications in medium proved by appropriate studies. requirements a specifically equipped com-
and low temperature systems, e.g. liquid pressor version is offered.
chillers for supermarkets, are of particular Resulting design criteria Inquires and orders need a distinstive indi-
interest. On the other hand, higher pressure cation to R1270. The handling of the order
levels (> 20%) and discharge gas tempera- With regard to system technology, experi-
does include an individual agreement
tures have to be taken into consideration, ence gained from the use of propane can
between the contract partners. Open
thus restricting the possible application widely be applied to propylene. However,
reciprocating compressors are also avail-
range. component dimensions have to be altered
able for R1270, together with a compre-
due to higher volumetric refrigerating cap-
Material compatibility is comparable with hensive program of flame-proof acces-
acity (Fig. 27). The compressor displace-
propane, as is the choice of lubricants. sories which may be required.
ment is correspondingly lower and therefore
also the suction and high pressure volume
Propylene is also easily inflammable and Supplementary BITZER information con-
flows. Because of higher vapour density the
belongs to the A3 group of refrigerants. The cerning the use of R1270
mass flow is almost the same as for R290.
same safety regulations are therefore to be
As liquid density is nearly identical the same Technical Information KT-660
observed as with propane (page 30).
applies for the liquid volume in circulation. Application of Propane and Propylene
Due to the chemical double bond propylene with semi-hermetic compressors
is relatively reaction friendly, which means

31
Halogen free refrigerants

Carbon Dioxide R744 (CO2) Safety Refrigerants", CO2 became less pop- temperature differences in evaporators,
ular and since the 1950s had nearly disap- condensers, and gas coolers. Moreover,
as an alternative refrigerant
peared. the necessary pipe dimensions are very
and secondary fluid small, and the influence of the pressure
The main reasons for that are its relatively
drop is comparably low. In addition, when
unfavourable thermodynamic characteristics
CO2 has had a long tradition in the refri- used as a secondary fluid, the energy de-
for usual applications in refrigeration and
geration technology reaching far into the mand for circulation pumps is extremely low.
air-conditioning.The discharge pressure
19th century. It has no ozone depleting
with CO2 is extremely high and the critical In the following section, a few examples of
potential, a negligible direct global warming
temperature at 31C (74 bar) is very low. subcritical systems and the resulting design
potential (GWP = 1), is chemically inactive,
Depending on the heat source temperature criteria are described. An additional section
non-flammable and not toxic in the classi-
at the high pressure side transcritical oper- provides details on transcritical applications.
cal sense. That is why CO2 is not subject-
ations with pressures beyond 100 bar are
ed to the stringent demands regarding
required. Under these conditions, the ener-
containment as apply for HFCs (F-Gas Subcritical applications
gy efficiency is often lower compared to the
Regulation), and flammable or toxic re-
classic vapour compression process (with From energy and pressure level points of
frigerants. However, compared to HFCs
condensation), and therefore the indirect view, very beneficial applications can be
the lower practical limit in air has to be
global warming effect is suitably higher. seen for industrial and larger commercial
considered. For closed rooms this may
require special safety and detection systems. refrigeration plants. For this, CO2 can be
Nonetheless, there is a range of applica-
used as a secondary fluid in a cascade sys-
tions in which CO2 can be used very eco-
CO2 is also low in cost and there is no nec- tem and if required, in combination with a
nomically and with favourable Eco-Efficien-
essity for recovery and disposal. In ad- further booster stage for lower evaporating
cy. For example, these include subcritically
dition, it has a very high volumetric refriger- temperatures (Fig. 30/1).
operated cascade plants, but also transcrit-
ating capacity, which depending on oper-
ical systems, in which the temperature glide The operating conditions are always sub-
ating conditions equates to approx. 5 8
on the high pressure side can be used ad- critical which guarantees good efficiency
times more than R22 and NH3.
vantageously, or the system conditions levels. In the most favourable application
Above all, the safety relevant characteristics permit subcritical operation for long periods. range (approx. -10 to -50C), pressures
were an essential reason for the initial wide- In this connection it must also be noted are still on a level where already available
spread use. The main focus for applications that the heat transfer coefficients of CO2 components or items in development, e.g.
were marine refrigeration systems, for ex- are considerably higher than of other re- for R410A, can be matched with accept-
ample. With the introduction of the "(H)CFC frigerants with the potential of very low able effort.

160 80
Critical temperature 31.06 C
140 R744 (CO 2)2 70
Transcritical process

120 Subcritical process 60


CO 2

100 50
Pressure [bar]

Pressure [bar]

40
80 31.06C

30
60
R404A
20
40
R22
10
20
0
0 -60 -40 -20 0 20 40 60 80
100 200 300 400 500 600
Enthalpy [kJ/kg] Temperature [C]

Fig. 29/1 R744(CO2) pressure/enthalpy diagram Fig. 29/2 R744(CO2)/R22/R404A comparison of pressure levels

32
Halogen free refrigerants

Resulting design criteria For the combination with a further compres- Supermarket plants with their usually widely
sion stage, e.g. for low temperatures, there branched pipe work offer an especially
For the high temperature side of such a are different solutions. good potential in this regard. The medium
cascade system, a compact cooling unit temperature system is then carried out in a
can be used, whose evaporator serves on Fig. 30/1 shows a variation with an addition-
conventional design or with a secondary
the secondary side as the condenser for al receiver where one or more Booster com-
circuit and for low temperature application
CO2. Chlorine-free refrigerants are suitable pressors will pull down to the necessary
combined with a CO2 cascade system (for
such as NH3, HCs or HFCs, HFO and evaporation pressure. Likewise, the discharge
subcritical operation). A system example is
HFO/HFC blends. gas is fed into the cascade cooler, condens-
shown in Fig. 30/2.
es and then carried over to the receiver (MT).
With NH3 the cascade heat exchanger The feeding of the low pressure receiver (LT) For a general application, however, not all
should be designed so that the dreaded is achieved by a level control device. requirements can be met at the moment. It
build-up of ammonium carbonate is pre- Instead of classical pump circulation the is worth considering that system technolo-
vented in the case of leakage. This tech- booster stage can also be built as a so- gy changes in many respects and specially
nology has been applied in breweries for called LPR system. adjusted components are necessary to
a long time. The circulation pump is thus not necessary meet the demands.
A secondary circuit for larger plants with but the number of evaporators is then limit-
The compressors, for example, must be
CO2 could be constructed utilising, to a ed with a view to an even distribution of the
properly designed because of the high
wide extent, the same principles for a low injected CO2.
vapour density and pressure levels (par-
pressure pump circulating system, as is In the case of a system breakdown where a ticularly on the suction side). There are
often used with NH3 plants. The essential high rise in pressure could occur, safety also specific requirements with regard to
difference exists therein, that the condens- valves can vent the CO2 to the atmosphere materials. Furthermore only highly dehy-
ing of the CO2 results in the cascade cool- with the necessary precautions. drated CO2 must be used.
er, and the receiver tank (accumulator) only As an alternative to this, additional cooling High demands are made on lubricants as
serves as a supply vessel. units for CO2 condensation are also used well. Conventional oils are mostly not misci-
where longer shut-off periods can be ble and therefore require costly measures
The extremely high volumetric refrigerating
bridged without a critical pressure increase. to return the oil from the system. On the
capacity of CO2 (latent heat through the
changing of phases) leads to very low mass For systems in commercial applications a other hand, a strong viscosity reduction
flow rates and makes it possible to use direct expansion version is possible as well. with the use of a miscible and highly soluble
small cross sectional pipe and minimal en- POE must be considered.
ergy needs for the circulating pumps.

Simplified Simplified
sketch sketch
CO 2 Cascade
HFC (NH 3 / HC)*

CO 2 NH 3 / HC /
HFC

MT LT PC

CPR

LC

LT MT

* only with secondary system

Fig. 30/1 Casacde system with CO2 for industrial applications Fig. 30/2 Conventional refrigeration system combined with CO2 low
temperature cascade
33
Halogen free refrigerants

For subcritical CO2 applications sure" is determined as a function of gas refrigeration plants, for example. Meanwhile
BITZER offers two series of special cooler outlet temperature by means of bal- installations with parallel compounded com-
compressors. ancing between the highest possible en- pressors are in operation to a larger scale.
thalpy difference and simultaneous mini- They are predominantly booster systems
Supplementary BITZER information mum compression work. It must be adapt- where medium and low temperature circuits
concerning compressor selection for ed to the relevant operating conditions are connected together (without heat
subcritical CO2 systems using an intelligent modulating controller exchanger). The operating experience and
Brochure KP-120 (see system example, Fig. 31). the determined energy costs show promis-
Semi-hermetic reciprocating compres- ing results. However, the investment costs
As described above, under purely thermo-
sors for subcritical CO2 application are still considerably higher than for classi-
dynamic aspects, the transcritical operat-
(LP/HP standstill pressures up to cal plants with HFCs and direct expansion.
ing mode appears to be unfavourable in
30/53 bar) terms of energy efficiency. In fact, this is On the one hand, the reasons for the
Brochure KP-122 true for systems with a relatively high tem- favourable energy costs lie in the high
Semi-hermetic reciprocating compres- perature level of the heat sink on the high- degree of optimized components and the
sors for subcritical CO2 application pressure side. However, additional meas- system control, and also in the previously
(LP/HP standstill pressures up to ures can be taken for improving efficiency, described advantages regarding heat trans-
100 bar) such as the use of parallel compression fer and pressure drop. On the other hand,
Additional publications on request (economiser system) and/or ejectors or these installations are preferably used in cli-
expanders for recovering the throttling loss- mate zones permitting very high running
es during expansion of the refrigerant. times in subcritical operation due to the
Apart from that, there are application areas annual ambient temperature profile.
in which a transcritical process is advanta-
Transcritical applications For increasing the efficiency of CO2 super-
geous in energy demand. These include
market systems and for using them in
Transcritical processes are characterized in heat pumps for sanitary water, or drying
warmer climate zones, the technologies
that the heat rejection on the high pressure processes. With the usually very high tem-
described above using parallel compression
side proceeds isobar but not isotherm. perature gradients between the discharge
and/or ejectors are increasingly used.
Contrary to the condensation process dur- temperature at the gas cooler intake and
ing subcritical operation, gas cooling (de- the heat sink intake temperature, a very low Insofar, but also in view of the very de-
superheating) occurs, with corresponding gas temperature outlet is achievable. This is manding technology and the high require-
temperature glide. Therefore, the heat positively influenced by the temperature ments placed on the qualification of plan-
exchanger is described as gas cooler. As glide curve and the relatively high mean ners and service personnel, CO2 technology
long as operation remains above the criti- temperature difference between CO2 vapour cannot be regarded as a general replace-
cal pressure (74 bar), only high-density and secondary fluid. The low gas outlet tem- ment for plants using HFC refrigerants.
vapour will be transported. Condensation perature leads to a particularly high enthalpy
only takes place after expansion to a lower difference, and therefore to a high system
Resulting design criteria
pressure level e.g. by interstage expan- COP.
sion in an intermediate pressure receiver. Detailed information on this topic would go
Low-capacity sanitary water heat pumps
Depending on the temperature curve of the beyond the scope of this publication. In any
are already manufactured and used in large
heat sink, a system designed for transcriti- case, the system and control techniques
quantities. Plants for medium to higher
cal operation can also be operated subcrit- are substantially different from conventional
capacities (e.g. hotels, indoor swimming
ically, whereby the efficiency is better under plants. Already when considering pressure
pools) are still in the development and intro-
these conditions. In this case, the gas levels as well as volume and mass flow
ductory phase.
cooler becomes the condenser. ratios specially developed components,
Apart from these specific applications, there
controls, and safety devices as well as
Another feature of transcritical operation is is also a range of developments for the
suitably dimensioned pipework must be
the necessary control of the high pressure classical areas of refrigeration and air-con-
provided.
to a defined level. This "optimum pres- ditioning. This also covers supermarket

34
Halogen free refrigerants

The compressor technology is particularly Suplementary BITZER information pressure losses have significantly less influ-
demanding. The special requirements result concerning compressor selection ence. Moreover, system efficiency is further
in a completely independent approach. for transcritical CO2-systems improved by the high heat transfer coeffi-
For example, this involves design, materials Brochure KP-130 cients in the heat exchangers.
(bursting resistance), displacement, crank Semi-hermetic reciprocating compres- This is why optimized CO2 air-condition-
gear, working valves, lubrication system, as sors for transcritical CO2 application
ing systems are able to achieve efficiencies
well as compressor and motor cooling. Additional publications upon request
that are comparable to those of R134a.
Hereby, the high thermal load severely limits
Regarding the usual leakage rates of such
the application for single-stage compres-
systems, a more favourable balance is
sion. Low temperature cooling requires CO2 in mobile obtained in terms of TEWI.
2-stage operation, whereby separate high air-conditioning systems
and low pressure compressors are particu- From today's viewpoint, it is not yet pos-
larly advantageous with parallel compound- Within the scope of the long-discussed sible to make a prediction as to whether
ed systems. measures for reducing direct refrigerant the CO2 technology can in the long run
The criteria mentioned above in connection emissions, and the ban on the use of prevail in this application. Certainly, this
with subcritical systems apply to an even R134a in MAC systems* within the EU, also depends on experiences with "Low
higher degree for lubricants. the development of CO2 systems has been GWP" refrigerants (page 11) which in the
pursued intensively since several years. meantime are partially introduced by the
Further development is necessary in many automotive industrie. Hereby, other aspects
areas, and for most applications, transcriti- At the first glance, efficiency and therefore such as operating safety, costs, and global
cal CO2 technology cannot yet be regarded the indirect emissions from CO2 systems logistics will play an important role.
as state-of-the-art. under typical ambient conditions appear to
be relatively unfavourable. But it must be
For transcritical CO2 applications, considered that present R134a systems
BITZER offers a wide range of special are less efficient than stationary plants of
compressors. the same capacity. The reasons for this lie
Their use is aimed at specific applica- in the specific installation conditions and
tions, therefore individual examination the relatively high pressure losses in pipe-
and assessment are required. work and heat exchangers. With CO2, * See page 11 for further information.

Simplified
sketch
CO 2 Booster System

MT LT

Fig. 31 Example of a transcritical CO2 Booster System

35
Special applications

R124 and R142b as Chlorine free substitutes The "Low GWP" refrigerant R1234ze(E) can
also be regarded as a potential candidate
substitutes for for special applications
for extra high temperature applications.
R114 and R12B1 Compared to R124, its cooling capacity is
Due to the limited markets for systems with higher by 10 to 20% and its pressure level
Instead of the refrigerants R114 and extra high and low temperature applica- by about 25%. At an identical refrigerating
R12B1 predominately found in the past in tions, the requirements for the development capacity, the mass flow differs only slightly.
high temperature heat pumps and crane of alternative refrigerants and system com- Its critical temperature is 107C, which
cabin A/C installations, the HCFC R124 ponents for these areas has not been so would enable an economical operation up
and R142b can be used as alternatives in great. to a condensing temperature of about
new installations. In the meantime a group of alternatives for 90C. However, like R1234yf, R1234ze(E) is
With these gases it is also possible to use the CFC R114 and Halon R12B1 (high tem- mildly flammable and therefore classified in
long proven lubricants, preferably mineral perature), R13B1, R13 and R503 (extra low the new safety group A2L. The correspon-
oils and alkyl benzenes with high viscosity. temperature) were offered as the replace- ding safety regulations must be observed.
Because of the Ozone Depleting Potential, ments. With closer observations it has been However, until now no sufficient operating
the use of these refrigerants must only be found that the thermodynamic properties of experience is available, which is why an
regarded as an interim solution. In the EU the alternatives differ considerably from the assessment of the suitability of this refriger-
member states, the application of HCFCs previously used substances. This can cause ant for long-term use is not yet possible.
is no longer allowed. For R124 and R142b costly changes especially with the conver-
sion of existing systems. For high temperature heat pumps in the
the same restrictions are valid as for R22
process technologie and special applica-
(page 8). The flammability of R142b should
tions in the field of high temperatures
also be considered with the resulting safety
DuPont has presented an HFO based
implications (safety group A2).
Alternatives for R114 refrigerant called DR-2.
Resulting design criteria/ and R12B1 The critical temperature is at 171C, the
Converting existing plants boiling temperature at 33.4C. This enables
R227ea and R236fa are considered suitable an operation at condensing temperatures
In comparison to R114 the boiling tempera-
substitutes even though they may no longer far above 100C for which only purpose-
tures of the alternatives are lower (approx.
be used in new installations in the EU from built compressors and system components
-10C) which results in larger differences in
2020, due to their relatively high GWP. can be used.
the pressure levels and volumetric refriger-
ating capacities. This leads to stronger limi- R227ea cannot be seen as a full replace- DR-2 has a GWP < 10 but is not flammable
tations in the application range concerning ment. Recent research and field tests have according to tests carried out so far. There-
high evaporation and condensing tempera- shown favourable results, but with normal fore a classification in safety group A1 can
tures. system technology the critical temperature be expected.
A conversion of an existing installation will of 102C limits the condensing temperatu-
A more detailed evaluation is not yet possi-
in most cases necessitate the exchanging res to about 85..90C.
ble with respect to the chemical stability of
of the compressor and regulating devices.
R236fa provides the more favourable con- the refrigerant and of the lubricants at the
Owing to the lower volume flow (higher vol-
ditions at least in this regard the critical very high temperatures and the usually very
umetric refrigerating capacity), possible
temperature is above 120C. A disadvan- long operating cycles of such systems.
adjustments to the evaporator and the suc-
tage, however, is the smaller volumetric The special applications also include sys-
tion line will be required.
refrigerating capacity. This is similar to R114 tems for power-heat coupling the so-
and with that 40% below the performance of called "Organic Rankine Cycle" (ORC),
Over the previous years BITZER com-
R124 which is widely used for extra high which become increasingly important. In
pressors have been found to be well
temperature applications today. addition to DR-2 as a potentially suitable
suited with R124 and R142b in actual
operating fluid, a series of other substances
installations. Depending on perform- Refrigerant R600a (Isobutane) will be an
are also possible, depending on the tem-
ance data and compressor type modifi- interesting alternative where the safety reg-
perature level of the heat source and the
cations are necessary, however. Per- ulations allow the use of hydrocarbons
heat sink.
formance data including further design (safety group A3). With a critical tempera-
They include R245ca (GWP100 = 1030) hav-
instructions are available on request. ture of 135C, condensing temperatures of
ing a critical temperature of 154C, which
100C and more are within reach.
like DR-2 is also suitable as refrigerant for
The volumetric refrigerating capacity is chillers with large centrifugal compressors.
almost identical to R124. In addition Solvay offers suitable refriger-

36
Special applications

ants containing the base component A comprehensive description of ORC than R13B1 at evaporating temperatures
R365mfc for ORC applications. A product systems would go beyond the scope of below -60C.
with the trade name Solkatherm SES36 this Refrigerant Report. Further informa- In addition to this, the steep fall of pressure
already presented several years ago con- tion is available upon request limits the application at very low tempera-
tains perfluoropolyether as a blend compo- tures and may require a change to a cas-
nent. It is an azeotrope having a critical cade system with for example R23 in the
temperature of 178C. Meanwhile two low temperature stage.
zeotropic blends containing R365mfc and Alternatives for R13B1
Lubrication and material compatibility are
R227ea have been developed whose criti-
assessed as being similar to the other HFC
cal temperatures are 177C and 182C, Besides R410A, ISCEON MO89 (DuPont)
blends.
due to different mixing ratios. They are can be regarded as potential R13B1 sub-
available under the trade names Solkatherm stitute. With R410A a substantially higher
SES24 and SES30. discharge gas temperature is to be con-
In ORC systems zeotropic behavior may be sidered when compared to R13B1 which
advantageous. In the case of single-phase restricts the application range even in Alternatives for R13
heat sources and heat sinks the tempera- 2-stage compression systems to a greater and R503
ture difference at the so-called "pitch point" extent.
can be raised by the gliding evaporation
ISCEON MO89 is a mixture of R125 and The situation is more favourable with these
and condensation. This leads to improved
R218 with a small proportion of R290. Due substances as R23 and R508A/R508B can
heat transmission due to the higher driving
to the properties of the two main compo- already replace R13 and R503. Refrigerant
average temperature difference.
nents, density and mass flow are relatively R170 (Ethane) is also suitable when the
high and discharge gas temperature is very safety regulations allow the use of hydro-
As an expander for ORC systems screw
low. Liquid subcooling is of particular ad- carbons (safety group A3).
and scroll compressors can be adapted
vantage.
in their construction accordingly. For Due to the partly steeper pressure curve of
several years BITZER has been involved Both of the mentioned refigerants have rel- the alternative refrigerants and the higher
in various projects and has already atively high pressure levels and are there- discharge gas temperature of R23 com-
gained important knowledge with this fore limited to 40 through 45C condensing pared with R13, differences in performance
technology and experience in design temperature with the usually applied 2-stage and application ranges for the compres-
and application. compressors. They also show less capacity sors must be considered. Individual adap-
tation of the heat exchangers and controls
is also necessary.
As lubricants for R23 and R508A/B, polyol
ester oils are suitable, but these must be
40 matched for the special requirements at
extreme low temperatures.
t o -70C
Discharge gas temperature relative difference to R13B1 [K]

30 tc 40C R170 has also good solubility with conven-


t oh 20 K tional oils, however an adaptation to the
temperature conditions will be necessary.
20
BITZER has carried out investigations
10 and also collected experiences with
several of the substitutes mentioned,
R410A

performance data and instructions are


0 available on request.
Basis R13B1
Due to the individual system technolo-
ISCEON MO89

gy for these special installations, con-


-10
sultation with BITZER is necessary.

-20

-30
Fig. 32 R13B1/HFC alternatives comparison of discharge gas temperatures
of a 2-stage compressor

37
Refrigerant Properties

09.14
5 6
Refrigerant Composition Substitute / Application ODP GWP(100a) Safety Practical
type (Formula) Alternative range group 4 limit
for [R11=1,0] [CO2=1,0] [kg/m3] 5

HCFC-Refrigerants 5

R22 CHClF2 R502 (R12 1 ) see 0.055 1810 A1 0.3


R124 CHClFCF3 1 page 40 0.022 609 A1 0.11
R114 , R12B1
R142b CCIF2CH3 0.065 2310 A2 0.066
HFC Single-component Refrigerants
R134a CF3CH2F R12 (R22 1 ) 1430 A1 0.25
R152a CHF2CH3 124 A2 0.027
R125 CF3CHF2 mainly used as 3500 A1 0.39
R143a CF3CH3 part components see 4470 A2 0.056
R32 CH2F2 for blends page 40 0 675 A2L 0.061
1
R227ea CF3-CHF-CF3 R12B1, R114 3220 A1 0.59
R236fa CF3-CH2-CF3 R114 9810 A1 0.59
R23 CHF3 R13 (R503) 14800 A1 0.68
HFC Blends
R404A R143a/125/134a 3922 A1 0.52
R507A R143a/125 3985 A1 0.53
R407A R32/125/134a R22 (R502) 2107 A1 0.33
R407F R32/125/134a 1825 A1 0.29
R422A R125/134a/600a 3143 A1 0.29
R437A R125/134a/600/601 R12 (R500) 1805 A1 0.08
R407C R32/125/134a 1774 A1 0.31
R417A R125/134a/600 see 2346 A1 0.15
R417B R125/134a/600 page 40 0 2920 A1 0.07
R422D R125/134a/600a R22 2729 A1 0.26
R427A R32/125/143a/134a 2138 A1 0.28
R438A R32/125/134a/600/601a 2264 A1 0.08
R410A R32/125 R22 1 (R13B1 2
) 2088 A1 0.44
ISCEON MO89 R125/218/290 R13B1 2 3805 N/A N/A
R508A R23/116 13214 A1 0.23
R503 A1
R508B R23/116 13396 0.2
HFO and HFO/HFCBlends
R1234yf CF3CF=CH2 4 A2L 0.058
R1234ze(E) CF3CH=CHF 7 A2L N/A
R513A (XP10) R1234yf/134a R134a 631 A1 0.35
see
R450A (N-13) R1234ze(E)/134a page 40 0 601 A1 N/A
R448A (N-40) R32/125/1234yf/1234ze(E)/134a R404A, 1386 A1 N/A
R449A (XP40) R32/125/1234yf/134a R507A 1397 A1 N/A
Halogen free Refrigerants
R717 NH3 R404A (R22) 0 B2 0.00035
R723 NH3/R-E170 R404A (R22) 8 B2 N/A
R600a C4H10 R134a 1 3 A3 0.011
R290 C 3H 8 R404A (R22) see 3 A3 0.008
R1270 C 3H 6 R404A (R22) page 41 0 3 A3 0.008
3
R170 C 2H 6 R23 3 A3 0.008
R744 CO2 various 1 A1 0.07
Fig. 33 Refrigerant properties (continued on Fig. 34)
These statements are valid subject to reservations; they are based on information published by various refrigerant manufacturers.
1 Alternative refrigerant has larger deviation in 3 Also proposed as a component in R290/ 6 AR4: according to IPCC IV time horizon 100 years
refrigerating capacity and pressure 600a-Blends (direct alternative to R12) also basis for EU F-Gas Regulation 517/2014
2 Alternative refrigerant has larger deviation 4 Classification according to EN378-1 N/A Data not yet published.
below -60C evaporating temperature and ASHRAE 34
5 According to EN 378-1: 2008 + A2: 2012,
Annex E

38
Refrigerant Properties

09.14
Refrigerant Boiling Temperature Critical Cond. temp. Refr. Discharge Schmierstoff
type temperature glide temperature at 26 bar capacity gas temp. (Verdichter)
[C] 1 [K] 2 [C] 1 (abs) [C] 1 [%] 3 [K] 3

HCFC-Refrigerants
R22 -41 0 96 63 80 (L) 4 +35 4

R124 -11 0 122 105 5 5


R142b -10 0 137 110
HFC Single-component Refrigerants
R134a -26 0 101 80 97 (M) -8
R152a -24 0 113 85 N/A N/A
R125 -48 0 66 51 N/A N/A
R143a -48 0 73 56 N/A N/A
R32 -52 0 78 42 N/A N/A
R227ea -16 0 102 96
5 5
R236fa -1 0 >120 117
R23 -82 0 26 1 5 5

HFC Blends
R404A -47 0.7 73 55 105 (M) -34
R507A -47 0 71 54 107 (M) -34
R407A -46 6.6 83 56 98 (M) -19
R407F -46 6.4 83 57 104 (M) -11
R422A -49 2.5 72 56 100 (M) -39
R437A -33 3.6 95 75 108 (M) -7
R407C -44 7.4 87 58 100 (H) -8
R417A -39 5.6 87 68 97 (H) -25
R417B -45 3.4 75 58 95 (M) -37 see
R422D -45 4.5 81 62 90 (M) -36 page 41
R427A -43 7.1 87 64 90 (M) -20
R438A -42 6.6 80 63 88 (M) -27
R410A -51 <0.2 72 43 140 (H) -4
ISCEON MO89 -55 4.0 70 50 5 5

R508A -86 0 13 -3 5 5
R508B -88 0 14 -3
HFO and HFO/HFC Blends
R1234yf -30 0 95 82 99 (M) -14
R1234ze(E) -18 0 110 92 5 5

R513A (XP10) -29 0 98 78 102 (M) -7


R450A (N-13) -24 0.4 106 85 88 (M) -6
R448A (N-40) -45 6.1 84 60 94 (M) +12
R449A (XP40) -46 5 82 58 97 (M) +12
Halogen free Refrigerants
R717 -33 0 133 60 100 (M) +60
R723 3 -37 0 131 58 105 (M) +35
R600a -12 0 135 114 N/A N/A
R290 -42 0 97 70 89 (M) -25
R1270 -48 0 92 61 112 (M) -20
R170 -89 0 32 3 5 5

R744 -57 6 0 31 -11 5 5

Fig. 34 Refrigerant properties

1 Rounded values 3 Reference refrigerant for these values 4 Valid for single stage compressors
is stated in Fig. 33 under the nomina-
2 Total glide from bubble to dew line tion Substitute for (column 3)
5 Data on request (operating conditions
based on 1 bar (abs.) pressure. Letter within brackets indicates must be given)
Real glide dependent on operating operating conditions
conditions. 6 Triple point at 5,27 bar
H High temp (+5/50C)
Approx. values in evaporator: M Medium temp (-10/45C) Stated performance data are average values
H/M 70%; L 60% of total glide L Low temp (-35/40C) based on calorimeter tests.

39
Application ranges

Transitional/Service refrigerants

R401A R409A

R401B

R22
2-stage

R402B

R402A R403B R408A


2-stage

R124 R142b

40 20 0 -20 -40 -60 -80 -100


Application with limitations Evaporation C

Fig. 35 Application ranges for HCFCs and Service Blends

HFC and HFO refrigerants

R134a R513A R450A

R437A

R404A R507A
2-stage

R407A R407F R417B


R422A R422D R427A R438A
R448A R449A

R407C R417A

R410A 1
2 2-stage

R227ea R236fa

2
ISCEON MO89 2 2-stage

R23 R508A R508B CASCADE

40 20 0 -20 -40 -60 -80 -100


Application with 1 Compressors for high pressure 42 bar Evaporation C
limitations 2 Condensing temperature limited

Fig. 36 Application ranges for HFC refrigerants and blends (ODP = O)

40
Application ranges Lubricants

Halogen free refrigerants

2-stage
NH 3
R723*

2-stage

R290 R1270
2-stage

R600a

R170 CASCADE

CO 2 see pages 32...35

40 20 0 -20 -40 -60 -80 -100


Application with limitations * see information on pages 28/29 Evaporation C
Fig. 37 Application ranges for halogen free refrigerants

Lubricants
Traditional oils New lubricants

glycol (PAG)
olefin (PAO)
Poly-alpha-

ester (POE)
Mineral oil

mineral oil
Mineral oil

Polyvinyl-
benzene

benzene

c racked
+ alkyl-

Polyol

H ydro
Alkyl-

(PVE)

Poly-
ether
(MO)

(AB)

(H)CFC +VG

+VG
Service blends with R22

HFC + blends

HFC/HC blends

HFO+HFO/HFC blends AD

Hydrocarbons VG VG VG VG VG

NH 3 R723

Good suitability Suitability dependant on system design Especially critical with moisture AD Possible special
Application with limitations Not suitable VG Possible higher basic viscosity formulation

Further information see pages 10/11 and explanations for the particular refrigerants.

Fig. 38 Lubricants for compressors

41
Notes

42
Notes

43
B itze r Khlmaschinenbau GmbH
Eschenbrnnlestr ae 15 // 71065 Sindelfingen // Germany
Tel +49 (0)70 31 932-0 // Fa x +49 (0)70 31 932-147
bitzer@bitzer.de // w w w.bitzer.de

Subject to change // 80050203 // 09.2014