Symposiums Bethesda Refrigerants Now and in The Future 9 17 12

Refrigerants: Now and in the Future 9/17/2012
Bill Walter
Manager Industry Relations
UTC Climate Controls and Security
© 2012 Carrier Corporation
EDUCATION AND CREDENTIAL CREDITS

In order to receive a certificate for this course you must both:
1. Sign the workshop attendance sheet which demonstrates that you have attended
the workshop
This will be passed around the room at the start of each workshop.
Print legibly so that information can be easily verified.
2. Complete the in-class exercise sheet. Questions are self graded.
Each workshop requires the completion of an in-class exercise with questions
that will be addressed during the workshop.
As questions are addressed during the presentation, record your answers on the answer
sheet.
At the end of the workshop, you must also complete the workshop evaluation.
Turn in both the completed exercise sheet and evaluation to the moderator.
The moderator will verify that you signed in and completed the written activities before
issuing your certificate. Certificates will be delivered to you after the workshop.
For participants who wish to claim continuing education credit in Florida, New York or
North Carolina you must also sign the additional attendance sheet and include your
PE registration number.
If you would like to have an Adobe PDF copy of any of the presentations, go to
www.carrieruniversity.com and look under Sustainability Symposiums.
2
© 2012 Carrier Corp. 1

SESSION OBJECTIVES
At the end you should be able to:
1. Explain the primary chemical differences between the
refrigerant
g designations;
g ; CFC,, HCFC,, HFC and HFO
2. Describe for each of the four refrigerant groups the
environmental impact on ozone depletion and global
warming
3. Name the safety classifications listed in ASHRAE
Standard 34 with the appropriate letter and number
designations
4. List the key differences in requirements of the Montreal
Protocol to those of the Kyoto Protocol
5. Explain in a sentence the importance of energy
efficiency and how it impacts global warming
3
REFRIGERANTS
Today’s Topics:
• Historical Perspective
p
• Refrigerants and the Environment
• ASHRAE Standard 34
• ASHRAE Standard 15
• International Mechanical Code

REFRIGERANTS
Early Refrigerants
Refrigerant Comments
Ammonia Toxic and Flammable
Methyl Chloride Toxic and Flammable
Sulfur Dioxide Toxic
"...the
the refrigeration industry needs a new refrigerant
if it is ever to get anywhere.”
Thomas Midgley began search for non-toxic,

non-flammable and cheap refrigerant
BASIC ELEMENTS AND REFRIGERANT COMPOUNDS
C N O F
S Cl
H H He
Br
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Ar
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Ti Pb Bl Po At Rn
Fr Ra As
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Th Pg U Np Pu AmCm Bk Ct Es Fm Md No Lw
6

REFRIGERANTS
1930:Thomas Midgley announced
the development of a new refrigerant
that
a would
ou d later
a e beco
become
e known
o as R-12
CCl2F2
dichlorodifluoromethane
REFRIGERANTS
CFC chlorine, fluorine, carbon
HCFC hydrogen, chlorine, fluorine, carbon
HFC hydrogen, fluorine, carbon
CFC-11 CCl3F trichlorofluoromethane
CFC-12 CCl2F2 dichlorodifluoromethane
HCFC-22 CHClF2 chlorodifluoromethane
R-500 CFC-12/HFC-152a (73.8/26.2)

REFRIGERANTS
Timeline
1970: James Lovelock discovers R-11 in the air over western Ireland
1972: Atomic Energy Commission sponsors meeting of chemists
and meteorologists
1973: Rowland and Molina discover that CFCs can destroy
ozone in the stratosphere
1977: United Nations holds the first international meeting to
discuss ozone depletion
1978: Use of CFCs in aerosols banned in U.S. & Canada
1984: British research group detects a 40% ozone loss over Antarctica
during the austral spring
1987: The Montreal Protocol is signed, calling for eventual
worldwide CFC reductions of 50%
9
REFRIGERANTS
Montreal Protocol Updates
1988: 50% reduction of CFC production
1990: Complete CFC phase-out by 2000
1992: Complete CFC phase-out by 1996
HCFC CAP in 1996 with phase-out by 2030
1995: HCFC CAP reduced from 3.1% to 2.8%
From 2020 to 2030, HCFC use for service only
HCFC controls for developing countries
2007: Meeting of the Parties in Montreal
Accelerated phase-out of HCFCs
Agreed to review need for service tail in 2015
10

MONTREAL PROTOCOL
HCFC Phase-out Schedule
*100% = 2.8% of CFCs plus 100% of HCFCs in 1989

** Service only
2015 review "the need for the 0.5% for servicing” 11
REFRIGERANTS
Comparison of the Montreal Protocol and the U.S. HCFC Phase-out Schedules
Montreal Protocol United States
% Reduction in
Year Consumption Year Clean Air Act Regulation
and Production
2004 35% 2003 No production and no importing of HCFC 141b
No production and no importing of HCFC-142b and

HCFC-22, except for use in equipment manufactured
2010 75%( 65%) 2010
before 1/1/2010 (so no production or importing for NEW
equipment that uses these refrigerants.)
No production and no importing of any HCFCs,

2015 90% 2015 except for use as refrigerants in equipment
manufactured before 1/1/2020
No production an no importing of HCFC-142b and
2020 99.5%* 2020
HCFC-22
2030 100% 2030 No production and no importing of any HCFCs
Added September 2007

* The Parties agreed to review in 2015 the need for the 0.5% production or import
for servicing during the period 2020-2030.
12

REFRIGERANTS
Ozone Protection Policies  U.S. Clean Air Act
2010: Montreal Protocol cap

p reduced to 25%
U.S. phase-out of R-22 in new equipment
2015: Montreal Protocol cap reduced to 10%

U.S. forecast R-22 shortage for service
2020: Montreal Protocol cap reduced to 0

0.5%
5%
U.S. no HCFC in new equipment
13
REFRIGERANTS
Composition Designating Technical Prefixes
Prefixes R-12
CFC-12 Refrigerant 12
HCFC-22
HFC-134a
CFC-12 HCFC-22 HFC-134a

ODP = 1.00 ODP = 0.05 ODP = 0.0
Lifetime = 102 Lifetime = 13.3 Lifetime = 14
Designation
14

REFRIGERANT TRANSITION
CFCs HCFCs HFCs

1930s – 1990s 1950s – 2010s 1990s+
Very Stable Less Stable Less Stable
Contains Chlorine Contains Chlorine No Chlorine
Strong Ozone Depletion Lower Ozone Depletion Zero Ozone Depletion
Strong Global Warming Lower Global Warming Lower Global Warming
15
ENVIRONMENTAL PROPERTIES OF REFRIGERANTS

Ozone Global Atmospheric
ASHRAE
Formula Depletion Warming Lifetime
Number
Potential Potential (Years)
CFC
11 CCl3F 1.00 4,750 45
12 CCl2F2 1.00 10,890 100
113 CCl2FCClF2 1.00 6,130 85
114 CClF2CClF2 1.00 10,400 300
115 CClF2CF3 0.44 7,370 1700
HCFC
22 CHClF2 0.05 1,810 12.0
123 CHCl2CF3 0.02 77 1.3
124 CHClFCF3 0.02 609 5.8
142b CH3CClF2 0.07 2,310 17.9
HFC
32 CH2F2 0 675 4.9
125 CHF2CF3 0 3,500 29
134a CF3CH2F 0 1,430 14
152a CH3CHF2 0 124 1.4
143a CH3CF3 0 4,470 52
245fa CHF2CF2CHF3 0 1,030 7.6
16


ASHRAE
Number
CFC
11 CCl3F 1.00 4,750 45
12 CCl2F2 1.00 10,890 100
113 CCl2FCClF2 1.00 6,130 85
114 CClF2CClF2 1.00 10,400 300
115 CClF2CF3 0.44 7,370 1700
HCFC
22 CHClF2 0.05 1,810 12.0
123 CHCl2CF3 0.02 77 1.3
124 CHClFCF3 0.02 609 5.8
142b CH3CClF2 0.07 2,310 17.9
HFC
32 CH2F2 0 675 4.9
125 CHF2CF3 0 3,500 29
134a CF3CH2F 0 1,430 14
152a CH3CHF2 0 124 1.4
143a CH3CF3 0 4,470 52
245fa CHF2CF2CHF3 0 1,030 7.6
17

ASHRAE
Number
CFC
11 CCl3F 1.00 4,750 45
12 CCl2F2 1.00 10,890 100
113 CCl2FCClF2 1.00 6,130 85
114 CClF2CClF2 1.00 10,400 300
115 CClF2CF3 0.44 7,370 1700
HCFC
22 CHClF2 0.05 1,810 12.0
123 CHCl2CF3 0.02 77 1.3
124 CHClFCF3 0.02 609 5.8
142b CH3CClF2 0.07 2,310 17.9
HFC
32 CH2F2 0 675 4.9
125 CHF2CF3 0 3,500 29
134a CF3CH2F 0 1,430 14
152a CH3CHF2 0 124 1.4
143a CH3CF3 0 4,470 52
245fa CHF2CF2CHF3 0 1,030 7.6
18


ASHRAE
Number
CFC
11 CCl3F 1.00 4,750 45
12 CCl2F2 1.00 10,890 100
113 CCl2FCClF2 1.00 6,130 85
114 CClF2CClF2 1.00 10,400 300
115 CClF2CF3 0.44 7,370 1700
HCFC
22 CHClF2 0.05 1,810 12.0
123 CHCl2CF3 0.02 77 1.3
124 CHClFCF3 0.02 609 5.8
142b CH3CClF2 0.07 2,310 17.9
HFC
32 CH2F2 0 675 4.9
125 CHF2CF3 0 3,500 29
134a CF3CH2F 0 1,430 14
152a CH3CHF2 0 124 1.4
143a CH3CF3 0 4,470 52
245fa CHF2CF2CHF3 0 1,030 7.6
19
ALTERNATIVE REFRIGERANTS
Original Replacement
CFC-11 HCFC-123 CHCl2CF3 [2020 phase out]
HFC-134a (equipment redesign)
CFC-12 HFC-134a CH2FCF3
HCFC-22 R-410A, R-407C
R-500 R-404A R-507

R-404A,
20

QUESTION #1
A. Which of the following refrigerant groups have the longest
atmospheric lifetime?
CFC
HCFC
HFC
HFO
B. Which of the groups contain chlorine?
CFC
HCFC
HFC
HFO
21
GLOBAL
CLIMATE CHANGE
HFCs are listed as a Green House Gas
in the Kyoto Protocol
22

REFRIGERANTS
Definitions
Webster’s New World Dictionary of the American Language
Second College
g Edition
weather - The general condition of the atmosphere

at a particular time and place, with
regard to the temperature, moisture,
cloudiness, etc.
climate - The prevailing
pre ailing or a
average
erage weather
eather
conditions of a place, as determined by
the temperature and meteorological
changes over a period of years.
23
REFRIGERANTS
Intergovernmental Panel on Climate Change (IPCC)
• Established in 1988 by WMO and UNEP to

Ӎ Assess available scientific information
Ӎ Assess the impacts of climate change
Ӎ Formulate response strategies
• Comprised of 3 working groups

Ӎ WG I: Climate System
Ӎ WG II: Impacts and response options
Ӎ WG III: Economic and Social dimensions
24

REFRIGERANTS
1990 - IPCC Scientific Assessment of Climate Change
1992 - Framework Convention on Climate Change
Reduce GHG levels to 1990 levels by 2000
1995 - IPCC Second Assessment Report (SAR)
“the balance of evidence suggests a discernible human influence
on global climate.”
1995 - COP-1; Berlin Mandate
“...enable governments to take appropriate action
for the period beyond 2000...”
1996 - COP-2; Geneva Declaration
...endorsed the IPCC conclusions and calls for legally binding
objectives and significant reductions in GHG emissions
1997 - COP-3; Kyoto Protocol, December 1-10
25
REFRIGERANTS
Kyoto Protocol
• Worldwide differentiated target of
5.2% reduction between 2008 - 2012
• Six gases included in reduction %
Ӎ CO2, CH4, N2O - 1990 baseline
Ӎ HFC, PFC, SF6 - 1995 baseline option
• “Sinks” (forests, soil and land use) included
26

TEWI
(Total Equivalent Warming Impact)
• TEWI = DIRECT + INDIRECT

• Calculation
DIRECT = Emission x Equivalent CO2
INDIRECT = Energy Usage x CO2/kW-hr
27
REFRIGERANTS
Ozone depletion Direct global Global warming gas emissions
potential warming potential* (2030)
CFC-11 1.0 3800 Nitrous PFCs,
Oxide SF6,
CFC-12
CFC 12 1.0
10 8100
M th
Methane 3 0%
3.0% HFC 23
HFC-23
HCFC-22 0.05 1500 5.5% 0.6%
HCFC-123 0.02 90
HFC-134a 1300 HFCs
1.8%
HFC-407C 1530
HFC-410A 1730
HFC-404A 3260
HFC-32 650
CO2
HFO 1234 f 1234
HFO-1234yf, 1234ze(E)
(E) 4,7 * = Kyoto Protocol Values 89.1%
Propane 20 except for 1234yf, ze(E)
CO2 1
~95% of an air 48 kg 365 kg 6700 kg

conditioner’s impact CO2/year CO2/year CO2/year
on climate change
is electrical use 10 SEER: 2370 kg CO2/year
13 SEER: 1848 kg CO2/year 28

QUESTION #3
A. Which of the groups are ozone depleting substances?
CFCs and HCFCs because they contain chlorine and
____________________________________________
have long
g atmospheric
p lifetimes
____________________________________________
B. Which of the groups are greenhouse gases?

All of them are greenhouse gases but only HFCs are
____________________________________________
listed identified in the Kyoto Protocol
____________________________________________
29
CLIMATE CHANGE PROPOSALS
EU Directive U.S. EPA SNAP

Covers use of HFCs in mobile air HFO-1234yf SNAP acceptable in
conditioning for passenger cars only mobile air conditioning
January 1, 2011: HFC-134a Propane (R–290) acceptable in

prohibited for air conditioning retail food refrigerators and freezers
systems in new vehicle models (standalone units only).
January 1, 2017: HFC-134a Isobutane (R–600a) and R–441A

prohibited for all new vehicles acceptable in household
refrigerators, freezers,
Currently under review with and
d combination
bi i
revision expected by 4Q2013 refrigerators and freezers.
30

REFRIGERANTS
Next Generation / Low GWP Refrigerants
Hydrocarbons (HCs) Highly Flammable (A3)
Propane (R-290)
Iso-butane (R-600a)
Carbon dioxide (CO2, R-744) Very High Pressure (A1)

Ammonia (NH3, R-717) Toxic & Flammable (B2L)
Low GWP HFCs/HFOs Mildly Flammable (A2L)
HFC-32
HFO-1234yf
HFO-1234ze(E)
HFO = hydrofluoro olefin

Very short atmospheric lifetime
Very low global warming potential
31
QUESTION #2
A. What environmental issues is being addressed by the
Montreal Protocol?
Ozone depletion
_______________
B. W What environmental issue is being addressed by the

Kyoto Protocol?
Global warming
_______________
32

REFRIGERANTS
33
REFRIGERANTS
ASHRAE Standard 34 – Refrigerant Designation
Single Component Refrigerants

IIn most cases number
b derived
d i d ffrom chemical
h i l fformula
l
(e.g. R11, R22, R134a)
Blends (Mixtures of chemical compounds)

Numbers assigned sequentially
(e.g. R404A, R407C, R410A, R507A)
Composition Designating Prefixes

(e.g. CFC-11, HCFC-22, HFC-134a, HC-600a)
34

REFRIGERANTS
ASHRAE Standard 34 – Refrigerant Classification
Toxicity
Class A Occupational Exposure Limit ≥ 400ppm
Class B Occupational Exposure Limit < 400ppm
Flammability
1 No flame propagation (ASTM E681)
2L LFL > 0.1kg/m3 AND
heat of combustion < 19,000 kJ/kg
Burning Velocity <10cm/s
2 LFL > 0.1kg/m3 AND
heat of combustion < 19,000 kJ/kg
3 LFL ≤ 0.1 kg/m3 OR
heat of combustion ≥ 19,000 kJ/kg
35
REFRIGERANTS
Safety Group Classifications – 2010
R-290 propane
Higher
A3 B3
Flammability
Flammability
R-600a isobutane
R-152a
A2 B2
Lower
R-32
Flammability R-1234yf A2L* B2L*
R-143a R-717
R-22 R-404A
No Flame R-134a A1 R-407C B1
Propagation R-410A R-507A R-123
Lower Higher
Toxicity Toxicity
Toxicity
* A2L and B2L are lower flammability refrigerants with a maximum burning velocity of ≤10 cm/s
36

REFRIGERANTS
Refrigerant Concentration Limit
The refrigerant concentration limit,
in air, determined in accordance with
this standard and intended to reduce
the risks of acute toxicity, asphyxiation,
and flammability hazards in normally
occupied
occup ed e
enclosed
c osed spaces
spaces.
37
REFRIGERANTS
Refrigerant Concentration Limit (RCL)
Criteria:
Mortality
Cardiac sensitization
Anesthetic or central nervous system effects
Other escape impairing symptoms and permanent injury
Oxygen deprivation limit
Flammable concentration limit
38

REFRIGERANTS
Refrigerant Blends in ASHRAE Standard 34
70
59
60
Number of blends in Standard
50
46
40
34
29
30
23
20
11 11 11 11 12
10 7 7
0 1
0
1989 1992 1997 2001 2004 2007 2010
Year Standard Published
Zeotropes Azeotropes
REFRIGERANTS
Flammable Refrigerants in ASHRAE Standard 34
45
40
Number of Flammable Refrigerants
35
30 22
25
12
10
20
10 9
15
10 10
15
10 15 15
10 11
5 5 5
3 3 3 3 3 3 4
0
1989 1992 1997 2001 2004 2007 2010
Year Standard Published
Class 2L Class 2 Class 3

QUESTION #4
A. What are the eight safety group classifications identified
in ASHRAE Standard 34?
A1, A2L, A2, A3, B1, B2L, B2, B3
______________________________________
B. Which safety groups contain refrigerants that are of

lower toxicity?
All class A refrigerants are of lower toxicity
______________________________________
C. Which safety groups contain refrigerants that are mildly

flammable?
All class 2L refrigerants are mildly flammable
_______________________________________
41
ASHRAE STANDARD 15
Safety Standard for Refrigeration Systems
Specifies safe design, construction, installation,
and operation of refrigeration systems.
Refers to ASHRAE Standard 34 for:
Refrigerant Safety Classification
Refrigerant Concentration Limit
Developing requirements for application of

2L refrigerants
42

REFRIGERANTS
Refrigerants Systems
ASHRAE STANDARD 34 and EN378 ASHRAE STANDARD 15 and EN378
High Flammability Direct System - Rooftop
Occupied Space
A3
Propane, Butane
B3 Refrigerant
Flammable
Direct System - VRF
A2 B2 Refrigerant
Occupied Space
R152a, R413a, R439A, R440A R40 Methyl Chloride
Occupied Space
Refrigerant
Lower Flammability Refrigerant Occupied Space
NEW
A2L B2L
R717 (Ammonia)
HFO1234yf, HFO1234ze(E), R32
Indirect System Occupied Space
No Flame Propagation Heat E
Exchanger
changer
Refrigerant Water
A1
R22, R410A, R407C,
B1
R123
R134a R1233zd
Lower Toxicity Higher Toxicity
A2 refrigerants not allowed by building codes;

movement to approve new A2L “lower flammability” category 43
REFRIGERANTS
International Mechanical Code – Chapter 11
Table 1103.1
Refrigerant classification and amount of refrigerant per
occupied space from ASHRAE Standard 34
Application requirements from ASHRAE Standard 15
Updated by ASHRAE during normal code cycles

2012 IMC - Blends up to 438A and R-1234yf
2015 IMC - Blends up to R-442A and R-1234ze(E)
2018 IMC - Add 2L safety classification in addition
to new refrigerants
44

SESSION OBJECTIVES
You should now be able to:
1. Explain the primary chemical differences between the
refrigerant
g designations;
g ; CFC,, HCFC,, HFC and HFO
2. Describe for each of the four refrigerant groups the
environmental impact on ozone depletion and global
warming
3. Name the safety classifications listed in ASHRAE
Standard 34 with the appropriate letter and number
designations
4. List the key differences in requirements of the Montreal
Protocol to those of the Kyoto Protocol
5. Explain in a sentence the importance of energy
efficiency and how it impacts global warming
45
REFRIGERANTS
CARRIER POSITION
Carrier will have the right refrigerant solution
for every application
application, but not every application
will have the same refrigerant solution.
Any choice of refrigerant must factor:

a. Energy efficiency
b. Commercial availability
c. Compliance with safety codes
d. Environmental effectiveness
46

REFRIGERANTS
Natural Refrigerants
CO2 can be an effective natural refrigerant for commercial
refrigeration. Carrier offers CO2 technology for this market
segment.
CO2 can be an effective refrigerant for transport refrigeration.

Carrier has announced breakthrough CO2 technology for
marine container refrigeration.
Propane can be an effective natural refrigerant for systems

with small refrigerant charge size
size. Carrier offers propane
technology for stand alone small food retail display cases.
More research is needed for stationary air conditioning. In

the meantime, HFCs offer energy efficient solutions.
47
THANK YOU!
48


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Refrigerants: Now and in the Future 9/17/2012

© 2012 Carrier Corporation

EDUCATION AND CREDENTIAL CREDITS

© 2012 Carrier Corp. 1

© 2012 Carrier Corp. 2

Methyl Chloride Toxic and Flammable

Sulfur Dioxide Toxic

Thomas Midgley began search for non-toxic,

BASIC ELEMENTS AND REFRIGERANT COMPOUNDS

© 2012 Carrier Corp. 3

CFC-12 CCl2F2 dichlorodifluoromethane

HCFC-22 CHClF2 chlorodifluoromethane

R-500 CFC-12/HFC-152a (73.8/26.2)

© 2012 Carrier Corp. 4

© 2012 Carrier Corp. 5

*100% = 2.8% of CFCs plus 100% of HCFCs in 1989

2004 35% 2003 No production and no importing of HCFC 141b

No production and no importing of HCFC-142b and

No production and no importing of any HCFCs,

2030 100% 2030 No production and no importing of any HCFCs

Added September 2007

© 2012 Carrier Corp. 6

2010: Montreal Protocol cap

2015: Montreal Protocol cap reduced to 10%

2020: Montreal Protocol cap reduced to 0

CFC-12 HCFC-22 HFC-134a

© 2012 Carrier Corp. 7

CFCs HCFCs HFCs

Very Stable Less Stable Less Stable

Contains Chlorine Contains Chlorine No Chlorine

Strong Ozone Depletion Lower Ozone Depletion Zero Ozone Depletion

Strong Global Warming Lower Global Warming Lower Global Warming

ENVIRONMENTAL PROPERTIES OF REFRIGERANTS

© 2012 Carrier Corp. 8

ENVIRONMENTAL PROPERTIES OF REFRIGERANTS

ENVIRONMENTAL PROPERTIES OF REFRIGERANTS

© 2012 Carrier Corp. 9

ENVIRONMENTAL PROPERTIES OF REFRIGERANTS

CFC-12 HFC-134a CH2FCF3

HCFC-22 R-410A, R-407C

R-500 R-404A R-507

© 2012 Carrier Corp. 10

© 2012 Carrier Corp. 11

weather - The general condition of the atmosphere

• Established in 1988 by WMO and UNEP to

• Comprised of 3 working groups

© 2012 Carrier Corp. 12

• “Sinks” (forests, soil and land use) included

© 2012 Carrier Corp. 13

• TEWI = DIRECT + INDIRECT

~95% of an air 48 kg 365 kg 6700 kg

© 2012 Carrier Corp. 14

B. Which of the groups are greenhouse gases?

CLIMATE CHANGE PROPOSALS

EU Directive U.S. EPA SNAP

January 1, 2011: HFC-134a Propane (R–290) acceptable in

January 1, 2017: HFC-134a Isobutane (R–600a) and R–441A

© 2012 Carrier Corp. 15

Carbon dioxide (CO2, R-744) Very High Pressure (A1)

HFO = hydrofluoro olefin

B. W What environmental issue is being addressed by the

© 2012 Carrier Corp. 16

Single Component Refrigerants