Refrigerants

and their
Application

Presented by

Thomas E. Watson, P.E.

Fellow ASHRAE
McQuay International
Staunton, Virginia USA

What is a Refrigerant?

• In a refrigerating system, the medium of heat transfer

which picks up heat by evaporating at a low
temperature and pressure, and gives up heat on
condensing at a higher temperature & pressure.

• (Refrigerating fluid) fluid used for heat transfer in a

refrigerating system which absorbs heat at a low
temperature and low pressure of the fluid and
transfers heat at a higher temperature and higher
pressure of the fluid, usually involving changes of state
of the fluid.

Ref: ASHRAE Terminology of Heating, Ventilation, Air Conditioning, & Refrigeration

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Agenda / Topics

• Introduction • Refrigerants In The

• History of Refrigerants Future?
• Basic Refrigerant • Alternative Refrigerants
Chemistry • Ozone Depletion &
• Refrigerant Properties Montreal Protocol
• Refrigerant Applications • Global Warming
• Summary

History of Refrigerants

• 1830s - Jacob Perkins - Vapor Compression (ether)

• 1851 - John Gorrie - Patent for Air Cycle
• 1859 - R-717 / R-718 (Ammonia / Water)
• 1866 - CO2 - Marine Applications
• 1873 - R-717 (Ammonia) Commercial Refrigeration -
Carl Linde
• 1875 - R-764 (Sulfur dioxide)
• 1920s -R-600a (Isobutane) & R-290 (Propane)
• 1922 - Willis Carrier - R-1130 (Dielene)
• 1926 - R-30 (Methylene Chloride)

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Toxicity - Best Minds Tried to Solve

Solving Problem of Toxicity

was a Large Problem to
Development of Refrigeration

1927 Leo Szilard &

Albert Einstein
Improved on von Platen /
Munters Absorption Design
Electromagnetic Pumping
Patent

Challenged to Find Refrigerant:

• Non-flammable

• Good Stability

• Low Toxicity

• Atmospheric Boiling Point between -40oC & 0oC

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Common Refrigerants in 1920s

Ammonia (R-717) NH3

Carbon Dioxide CO2
Sulfur Dioxide SO2
Hydrocarbons CnHm
Methyl Choride CH3Cl
Water H2O

History of Refrigerants

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History of Refrigerants

Midgley Selections

H
C N O F
S Cl
Br
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Refrigerant Chemistry

Hydrocarbon Formula NBP

Methane CH4 -260 F -162 ̊C
Ethane C2H6 -127 F -88 ̊C
Propane C3H8 -44 F ̊
-42 C

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Refrigerant Chemistry

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Refrigerant Chemistry

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Refrigerant Chemistry

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Refrigerant Chemistry

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 Refrigerant Chemistry

Fluorocarbons
• CFCs, HCFCs, HFCs & HFOs HYDROGEN

• Limited Combinations Flammable

– Adding Chlorine Or Bromine

Increases ODP
– Adding Fluorine Increases Toxic
GWP
– Adding Hydrogen Increases
Flammability And Lowers
Atmospheric Lifetime CHLORINE FLUORINE
Long Atmospheric Lifetime
(fully halogenated)

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Refrigerant Chemistry

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Refrigerant Chemistry

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Refrigerant Chemistry

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Refrigerant Chemistry

• Refrigerant Blends
– Two or More Refrigerants to Achieve Required Properties
• Flammability
• Volumetric Capacity
• Limit Discharge Superheating for Lower Disch Temp
• etc

• Two Basic Types

– Zeotropes
– Azeotropes

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Refrigerant Chemistry

Zeotropes

ZEOTROPIC BEHAVIOR (32/134a)

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T vap
T liq
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Temperature, °F

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P= 64 PSIA
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15

-5
0 20 40 60 80 100
% R-32

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Refrigerant Chemistry

Zeotropic Behavior
• Fractionalization - Can be Separated by
Distillation
• Service Procedures

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Refrigerant Chemistry

Azeotropes
AZEOTROPIC BEHAVIOR (R-125/R-143a)
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T vap
38 T liq
Temperature, °F

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P=100 PSIA
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R-507 = AZEOTROPIC MIXTURE R-125/R-143a (50/50)

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0 10 20 30 40 50 60 70 80 90 100

% R-125

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ASHRAE Standard 34

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ASHRAE Standard 34

• Nomenclature
• Toxicity Classification
• Flammability Classification

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ASHRAE Standard 34
Nomenclature

000 Series Methane Based

100 Series Ethane Based
200 Series Propane Based
300 Series Cyclic Organic Compounds
400 Series Zeotropes
500 Series Azeotropes
600 Series Organic Compounds
700 Series Inorganic Compounds
1000 Series Unsaturated Organic Compounds

Code Key

Rule of 90 - Example R-12

R- 1 2

+ 9 0
C H F

= 1 0 2

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ASHRAE Standard 34

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HFO--1234ye Stereoisomers
HFO

Entgegen Zusammen
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ASHRAE Standard 34
• Toxicity Classification based on
Chronic (long term) Measure
- Class A has PEL > 400 PPM
- Class B has PEL < 400 PPM
PEL = Permissible Exposure Limit

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ASHRAE Standard 34

• Flammability Classification based on:

ASTM E 681 with an Electrically

Activated match

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ASHRAE Standard 34

Flammability Classification
• Class 1 - No Flame Propagation
• Class 2 - LFL > 0.10 kg/m^3
and hc < 19 MJ/kg
• Class 2L – Cl 2 w/ flame speed < 10 cm / sec
• Class 3 - LFL < 0.10 kg/m^3
or hc > 19 MJ/kg

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ASHRAE Standard 34

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A2L Refrigerants

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ASHRAE Standard 15

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ASHRAE Standard 15

What is ASHRAE 15?

• An industry standard that specifies safe

design, construction, installation, and
operation of refrigerating systems

• Establishes safeguards for life, limb,

health, and property, and prescribes
safety standards

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ASHRAE Standard 15

Scope
• Design, Construction, Installation,
Operation & Inspection of Mechanical
and Absorption Machines
• Modifications if not Identical in Function
and Capacity
• Refrigerant Substitutions with Different
Designation

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ASHRAE Standard 15

Requirements
Based on 3 Classifications
• Occupancy
• Refrigerating System
• Refrigerant

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ASHRAE Standard 15
Occupancy Classifications
- Ability to Respond to Exposure
• Institutional - Assistance Required
• Public Assembly - Large Numbers
• Residential - Sleeping
• Commercial - Business Transactions
• Large Mercantile - 100 Persons or More
• Industrial & Refrigerated Rooms - Access Controlled
• Mixed - Two or More in Same Building

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ASHRAE Standard 15

Refrigerating System Classification

• High Probability - Leak Can Enter Occupied

Space
• Low Probability - Leak Cannot Enter Occupied
Space

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ASHRAE Standard 15

Restrictions on Refrigerant Use - Section 7

• Standard 15 Gives Rules based on Occupancy,
System, & Refrigerant Classification

• 3 kg or Less of Flammable Refrigerants may be used

in Listed Equipment

• A2L Refrigerant Application Requirements NOT

Included – Presently Under Consideration

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ASHRAE Standard 15

Refrigerant Qty/vol Limits - See Std 34

• Acute Exposure / Ability to Escape
• Direct Systems
• Volume - Space to which Refrigerant Disperses
in Event of Leak

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ASHRAE 15 Users Manual

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 Mechanical Room Safety Check
Location of inlet Location of roof drains ?
vents in relation
to exhaust outlets ?

Rupture disc
outlet locations ? Is there a tight
Purge vents seal on doors ?
to outside ?
Are safety rupture
lines the right size ?
Is access to mechanical
room restricted ?

Are drain valves connected

to evacuation devices ?

Are there any Where do the

pit areas in the floor drains
room ? empty ?

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Mechanical Room Safety Check

Relief discharge shall be located not less
than 20 ft (6 m) from ventilation opening and
not less than 15 ft (4.5 m) above ground level (9.7.8)

All indoor machinery

rooms must be vented
Purge systems and relief devices to the outdoors utilizing
must be vented to outside (8.16) mechanical ventilation
98.13.3 & 4
Access to mechanical
room shall be restricted.
Tight fitting doors opening
outward (self closing if the
open into the building)
adequate in number to
ensure freedom of escape.
No other openings that would
permit passage of escaping
refrigerant (8.13)

Refrigerant sensors are located in areas where The total amount of

refrigerant vapor from a leak will be concentrated refrigerant stored in a
so as to provide warning at concentration not machinery room in all containers not provided
exceeding the refrigerant PEL with relief valves & piped in accordance with
standard shall not exceed 330 lb (150 kg). (11.5)

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 Sample Sensor Locations*

Entrance / Exits

Refrigerant
Storage
Just Above floor
Next to Chillers Drains

Pits

*Examples not part of standard

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Mechanical Room per ASHRAE 15

Periodic tests of
detectors, alarms &
ventilation must be Mechanical room should be
performed in dimensioned for easy
accordance with access to all parts and adequate No open flames that use
manufacturers space for service, maintenance, combustion air from the machinery
recommendations and operation. Clear head room room (boilers) can be located
and/or local of not less than 7.25 ft (2.2 m) below within the mechanical as long as
jurisdiction. (11.7.3) equipment situated over the combustion air is ducted from
passageways. (8.12.1 &2,8.13.1) the outside to the boiler or shut
down sensors are installed (8.13.6)

A change in the type of refrigerant in a

system shall not be made without the notification
of the authority having jurisdiction, the user
and due observance of safety requirements. The
refrigerant being considered shall be evaluated for suitability (5.3)

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IIAR 2

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Back to the Future

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Refrigerants in the Future?

Low Direct Global Warming Potential

• CO2

• Ammonia

• Hydrocarbons

• HFOs

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Natural Refrigerants

• Ammonia (NH3) R-717

– Efficient
– B2L Classification
– Industrial Applications
• Water R-718
– Absorption Chillers
– Centrifugal Compressors
– Axial Flow Compressors
• Carbon Dioxide (CO2) R-744
– Low Critical Point

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What about other stuff -HFOs?

Refrigerant Applications

• pV = (m x Ru x T ) / MM

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 Refrigerant Applications

• What is Pressure?
• Pressure = Average Impact of Molecules on a
given area.
• Pressure is dependent on the Kinetic Energy of

the molecules.

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Volumetric Capacity
180.0
R-114
160.0
R-123
140.0
R-245fa R-11

120.0 R-12
Molecular Mass

R-1234yf R-1234ze
100.0 R-500 R-134a

R-22 R-407C
80.0
R-410A
R-152a
60.0
R-32 R-40
R-744 R-290
40.0

20.0 R-718
R-717

0.0
0.1 1.0 10.0 100.0 1000.0
CFM/ton

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 Compressor Types

Compressor
Types

Positive
Dynamic
Displacement

Reciprocating Rotary Orbiting Centrifugal

Singe Shaft Twin Shaft Three Shaft Scroll Axial

Single Screw Twin Screw Tri-Screw Trochoidal

Moving Vane

Fixed Vane
(Rolling Piston)

Compressor Volumetric Capacities

Axial

Centrifugal

Screw

Rotary

Scroll

Recip

0 1 10 100 1,000 10,000 100,000 1,000,000

NOTE: Log Scale

CFM

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 Refrigerant Flow Requirements

1000
R-718

100

R-123
CFM/ton

R-11
R-245fa
10 R-114
R-1234ze
R-1234yf R-134a
R-40 R-12
R-500R-22
R-290
R-407C
1 R-717 R-32 R-410A

R-744

0.1
0.1 1.0 10.0 100.0 1000.0
Suction Pressure, PSIA

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Basic Considerations

• Compressors
– Vapor Pressure
– Temperature Lift
– Tons
• Evaporators
– Glide
• Condensers
– Glide
– Critical Temperature

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R-11 Alternatives
Refrigerant Molecular Mass

CFC-11 137.4

HCFC-123 153.0

HFC-245fa 134.0

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R-12 Alternatives
Refrigerant Molecular Mass

CFC-12 120.9

CFC-500 99.3

HFC-134a 102.0

HFO-1234yf 114.0

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R-22 Alternative
Refrigerant Molecular Mass

HCFC-22 86.5

HFC-407C 86.2

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Global Warming

TEWI - Total Environmental Warming Impact

Consists of
• Direct GWP, from refrigerant discharge +
• Indirect, power plant CO2 discharge dominates
- Over 95% for Well Maintained Equipment
- CO2 from Power Generation depends on IPLV

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Global Warming

GWP

Power
Generation

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Summary - Refrigerant Choice

Ozone saving

Global warming issue - Total Environmental Warming
Impact (TEWI)

Safety

Field availability

Application

Cost

Compressor type

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Questions?

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Information Sources

www.ahri.org

www.ashrae.org

www.epa.gov/docs/ozone/index.html

ASHRAE Handbook – Fundamentals - Refrigerants

ASHRAE Standards 15 & 34

IIR-2 Equipment, Design and Installation of Ammonia Mechanical Refrigerating
Systems

Fluorocarbon Refrigerants Handbook - Ralph C. Downing, Prentice-Hall

Trade-Offs in Refrigerant Selections: Past, Present, and Future - James M. Calm
and David A. Didion - Proceedings of ASHRAE/NIST Refrigerants Conference -
Oct 1997

HFOS – New Low Global Warming Potential Refrigerants – S. F. Brown,
ASHRAE Journal August 2009

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