Heat Transfer

Select Heat-Transfer Fluids

for Low-Temperature Applications

Satish C. Mohapatra,
Advanced Fluid Technologies, Inc.

Ultra-low-temperature HTF Dynalene MV is

being used in a lyophilizer to crystallize
thermally sensitive materials. Photo courtesy
of Hull Corp. (Hatboro, PA).

Consider such factors as thermophysical properties, toxicity,

environmental concerns, and economics when choosing a fluid.

ountless operations in the chemical

process industries (CPI) require the
transfer of heat. One way to obtain
low process temperatures is secondary refrigeration, where a primary refrigerant or a liquified gas is used to cool a
heat-transfer fluid first, then the cold heat-transfer fluid is circulated through the process.
Secondary refrigeration is more efficient than
direct refrigeration using a liquified gas (such as
liquid nitrogen) or mechanical refrigeration
using a fluorocarbon-based refrigerant. The advantages of secondary refrigeration include:

it uses approximately 7580% less primary refrigerant

there are fewer refrigerant leaks since there
is substantially less refrigerant piping
fewer service calls are required
more stable process temperatures can be
maintained.
Secondary refrigerants such as ethylene and
propylene glycols are very popular heat-transfer
fluids (HTFs) in the temperature range of
121C to 40C. Glycols are usually added to
water to control the latters freezing point and
viscosity. Trichloroethylene (TCE) has also

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Heat Transfer

been used extensively in the past because of its low viscosity at low temperatures and nonflammability. Glycols and
TCE are inexpensive, but they have several limitations. The
most important drawback is the environmental concerns associated with their use. Ethylene glycol and TCE are considered toxic, so they cannot be used in many processes.
Propylene glycol, although nontoxic, has very high viscosity at low temperatures, so it is normally used at temperatures above about 23C. Glycols also degrade over time
and form glycolic acid, which can contribute to the corrosion of metals in the system.
This article discusses several other low-temperature
heat-transfer fluids, including aromatics, aliphatics, silicones, fluorocarbons, and naturally derived terpenes.

Requirements for low-temperature HTFs

Low-temperature HTFs must have certain characteristics:
low freezing point and low viscosity at low operating temperatures
high boiling point under normal pressure
good thermophysical properties
good thermal stability and low sensitivity to oxidation
in the applications temperature range
high flash point and autoignition temperature
noncorrosive to materials of construction
no or minimal regulatory constraints
favorable economics.
The best low-temperature HTF is an inexpensive and
nontoxic liquid with excellent low-temperature thermophysical properties and a long service life. A low-temperature HTF must have a low freezing point (at least 20C
lower than the lowest operating temperature) to avoid freezing on the heat-transfer surfaces. It should also have a low
vapor pressure or high boiling point to avoid the need to
pressurize the system at elevated temperatures. High flash
point and autoignition temperature are desired so that the
fluid is less susceptible to ignition. Also, good thermophysical properties are required to obtain high heat-transfer coefficients, while minimizing the pumping power needed to
move the fluid through the pipes at the required flow rate.
To compare two fluids, Ballard and Manning (1) have
developed a parameter called the relative heat-transfer efficiency factor (RHTEF):
RHTEF =

k
k TCE

0.67

0.52

TCE

TCE

0.57

Cp
C p,TCE

0.33

(1)

This parameter takes into account four thermophysical

properties of a fluid: thermal conductivity (k), viscosity (),
density (), and heat capacity (Cp). It compares these properties of the fluid of interest with those of a reference fluid,
in this case TCE. This article uses the RHTEF to compare
some of the commonly used low-temperature HTFs.
Apart from thermophysical properties, the fluid should

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also exhibit sufficient stability toward oxidative degradation. Most organic fluids oxidize at high temperatures in
the presence of air and can form acidic and polymerization
products in the system that can initiate corrosion and fouling. This can severely affect the heat-transfer efficiency of
the system.
A very important characteristics of a good HTF is that it
should be nontoxic and environmentally friendly. The ideal
candidate is the one that can be classified as food grade and
also satisfy the U.S. Food and Drug Administration (FDA)
and U.S. Dept. of Agriculture (USDA) criteria for incidental food contact. Additionally, its vapor should neither
contribute to the greenhouse effect nor to the depletion of
the ozone layer.
None of the currently used HTFs satisfy all of these requirements. A few liquids satisfy most of the criteria, but
those that do are very expensive. Some of the currently
used low-temperature HTFs can satisfy the needs of many
applications, as discussed below.

Aromatics
Aromatic hydrocarbons such as diethyl benzene are
very common low-temperature HTFs in the temperature
range of 70C to 260C. Their low-temperature heattransfer characteristics and thermal stability are excellent.
However, these alkylated benzene compounds cannot be
classified as nontoxic. They have a strong odor that can be irritating to the personnel handling them, and very few aromatic compounds have freezing points lower than 80C. Hence,
aromatic HTFs are used above 70C in closed airtight systems in chemical processing and industrial refrigeration.
Aliphatics
Paraffinic and iso-paraffinic aliphatic hydrocarbons are
used in some low-temperature systems. Many petroleumbased aliphatic compounds meet FDA and USDA criteria
for incidental food contact. These fluids do not form hazardous degradation byproducts, and most have a nondiscernible odor and are nontoxic in case of contact with skin
or ingestion.
However, even with all these advantages, these fluids
are not very common in low-temperature applications because of their high viscosity at low temperatures. Also, the
thermal stability of aliphatic compounds is not as good as
aromatic compounds.
Some of the iso-paraffinic fluids (with 12 to 14 carbons)
can be used from 60C up to 150C. These fluids are preferred in food and pharmaceutical applications where toxicity is a major issue.
Silicones
Another class of popular low-temperature HTF is
dimethyl polysiloxane, commonly known as silicone oil.
Since this is a synthetic polymeric compound, the molecular weight and the thermophysical properties can be adjust-

Table. Thermophysical properties of various low-temperature HTFs.

TCE

Aromatic

Aliphatic

Silicone

Freezing Point, C

86

< 84

< 101

< 109

Flash Point, C

None

58

59 60

47

Viscosity,* mPaS

1.206

3.1

7.0

4.8

Density,* kg/m3

1553

915

806

899

Specific Heat,* kJ/kgK

0.887

1.464

1.862

1.644

Thermal Conductivity,
* W/mK

0.138

0.147

0.119

0.123

RHTEF

1.0

0.56

0.32

0.4

Environmental and
Toxicity Concerns

Yes

Yes

No

No

* Viscosity, density, specific heat, and themal conductivity at 40.

RHTEF values are calculated with respect to TCE.

ed by varying the chain length. Silicone fluids can be used

at temperatures as low as 100C and as high as 260C.
These fluids have excellent service life in closed systems in the absence of oxygen. Also, with essentially no
odor and very low toxicity, silicone fluids are known to be
workplace friendly.
However, with low surface tension, these fluids have the
tendency to leak around pipe fittings, although this low surface tension improves wetting. Silicones are usually priced
higher than the aromatic- and aliphatic-based HTFs. Since
silicone fluids are virtually nontoxic, major applications
are seen in the pharmaceutical industry.

Fluorocarbons
Fluorinated compounds such as hydrofluoroethers and
perfluorocarbon ethers have certain unique properties that
allow them to compete in the low-temperature HTF market. First, they are nonflammable and nontoxic. Some fluorinated compounds have an ozone depleting potential of
zero and other favorable environmental properties. Second,
some of these fluids have a low freezing point and low viscosity at low temperatures.
However, these fluids are very expensive. Due to the extremely low surface tension, leaks can develop around fittings. Also, fluorocarbons have a much lower boiling point
than many other HTFs. Therefore, these compounds are
not suitable for applications where both low and high temperatures are desired.
Typical applications of fluorocarbon-based fluids are in
the pharmaceutical and semiconductor industries within
the temperature range of 100C to 150C.
D-limonene
Other low-temperature HTFs are based on naturally
derived terpenes, such as d-limonene. Ref. 2 describes
d-limonene as being particularly preferred among all the

Terpene
Mixture

monocycloterpenes because of its characteristic properties such as low viscosity at

< 109
low temperatures. D-limonene is the major
component in the oil of citrus fruit and
55
present in trace quantities in orange juice.
3.15
It is recovered in commercial quantities by
distilling orange oil obtained from citrus
907
peels. Because it is derived from citrus
1.59
fruit, d-limonene is considered a safe and
environmentally friendly HTF, and hence
it is preferred in many food and pharma0.138
ceutical processes.
0.54
However, the melting point of dlimonene is about 78C; below this temperature, it becomes a thick white gel-like subNo
stance that is impossible to pump. Therefore,
the use of d-limonene is limited to above
about 60C. In addition, at temperatures
above 50C, d-limonene oxidizes rapidly in
the presence of air, which triggers the acidification and
polymerization of the molecules. Because of this, dlimonene is not recommended for use above 50C.

Terpene mixtures
The use of eutectic mixtures of monocycloterpenes in
low-temperature applications is discussed in Ref. 3. These
new environmentally friendly HTFs have melting points
below 110C and thermophysical properties comparable
to many other HTFs. Because these new HTFs are biologically based and obtained from renewable sources, they require less energy for production than other synthetic HTFs.
With the addition of proper antioxidants and using an inert
gas such as N2, these fluids can be used from 100C to
150C in a variety of applications.
Comparing fluids
The table lists some of the properties and RHTEFs
of commonly used low-temperature HTFs. At 40C,
TCE has the highest RHTEF, followed by aromatics
and terpenes. However, TCEs environmental properties
are no more favorable than those of the other fluids.
Aromatics have some degree of toxicity, so many applications in the food and pharmaceutical industry do not
prefer these fluids. Thus, terpenes, silicone oil, and
aliphatic-hydrocarbon-based HTFs are the first choices
in these industries.
The figure compares the viscosities of several of the
HTFs. This property accounts for the differences in the
RHTEFs of various fluids at ultra-low temperatures. The
HTFs based on aliphatic hydrocarbons have much higher
viscosity than other fluids at low temperatures. Thus,
these fluids cannot be used effectively in applications
below 60C.
In applications below 70C, the user must choose between terpene and silicone based on price and fluid service

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Heat Transfer

1,000

Viscosity, mPas

Aliphatic Hydrocarbon
100
Silicone Fluid

10
Terpene
Mixture
Aromatic
1
-100

-80

-60

-40

-20

20

Temperature, C

Figure. Comparison of low-temperature viscosities

for various heat-transfer fluids.

life. Silicone fluids are usually more expensive than terpenes, but they may have a longer life. The service life of
the HTF depends on such factors as temperature, exposure
to oxygen (in the air) and moisture, the presence of impurities, and catalytic degradation on the metal surfaces. Terpenes have double bonds, which make them susceptible to
oxidation and polymerization, whereas silicones have a stable structure and are normally stable up to 250C. At typical operating conditions of 70C to 150C, silicone may
last two to three times longer than a terpene. However,
with proper antioxidants, the life of terpenes can be extended to match that of the silicones. Therefore, when
choosing between terpenes and silicone, the following parameters should be considered:
process temperature
inert gas blanketing in the liquid expansion tank
fluid life determined by the manufacturer (temperature, inert gas blanketing, and antioxidant concentration
play a major role in determining this)
fluid cost.
These parameters ultimately affect the economics of the
fluid in the long run, and the purchaser must be aware of
the long-term effects.

Literature Cited
1. Ballard, D., and W. P. Manning, Boost Heat-Transfer System
Performance, Chem. Eng. Progress, 86 (11), pp. 5159, (Nov.
1990).
2. Hsu, H., Heat Transfer Processes, U.S. Patent No. 3,597,355
(1971).
3. Hsu, J. T., and D. J. Loikits, Fluid Heat Transfer Medium and
Heat Transfer Process, U.S. Patent No. 5,847,246 (1998).

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Switching HTFs in existing equipment

Changing HTFs is becoming a common practice in CPI
plants because of the trend toward replacing toxic fluids
with environmentally friendly and safer fluids. Sometimes,
switching to another fluid can provide better heat-transfer
efficiency and/or require less pumping power. When
switching HTFs in existing equipment, the following factors should be taken into consideration:
Whether a substantial change in the system is necessary. The change may be in the pump size, heat exchanger
size, piping configuration, or any other ancillary equipments. This will depend on the thermophysical properties
of the fluids.
System cleaning. All fluid manufacturers recommend
a thorough system cleaning when changing an HTF. In
certain cases, the new fluid may not be compatible or miscible with the old fluid. For example, when switching
from aqueous fluids such as glycol/water or calcium chloride brine solution to a hydrocarbon or silicone-based
fluid, or vice versa, the system must be cleaned according
to the fluid manufacturers instructions before the new
fluid is charged.
Quality control. After switching to a new fluid, representative samples should be analyzed every few months.
For nonpolar fluids, such as hydrocarbons or silicones, the
moisture level should be measured from time to time. If the
moisture content exceeds the solubility of water in the
HTF, then water forms a separate phase that can be detrimental to a system, since it can freeze at low temperatures.
In summary
Whether choosing a low-temperature HTF for a new
system or as a replacement fluid in an existing system,
proper selection based on the factors discussed here can reCEP
duce the overall cost of a process in the long run.

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SATISH C. MOHAPATRA is the vice president of engineering at Advanced

Fluid Technologies, Inc., Whitehall, PA (Phone: (610) 262-3681; Fax:
(610) 262-5256; E-mail:satishm@dynalene.com), which manufactures
and distributes Dynalene heat-transfer fluids. He has been involved in
all the Dynalene technological advances since 1993. He is currently
working on the development of fluids for fuel cells, solar heating, and
supermarket secondary-refrigeration applications. He received a BTech
in chemical engineering from the Indian Institute of Technology,
Kharagpur, an MTech in biochemical engineering from the Indian
Institute of Technology, New Delhi, and a PhD in chemical engineering
from Lehigh Univ. He has authored or coauthored several publications
and patents. He is a member of AIChE and ACS.