Insights into the Next Generation of Refrigerants
Steve KujakDirector, Next Generation Refrigerant Research
2016 ASHRAE Houston Chapter
Houston, TexasNovember 15, 2016
Outline/Agenda
• Refrigerants: History and Where Used
• Refrigerant Impacts on Global Warming
• Regulatory Actions
• Designing Refrigerants
• Next Gen Refrigerants Offerings, Challenges and Opportunities
• Flammability Considerations & Optimization
• Insights Into The Refrigerant Future
Refrigerant History
Houston, TexasNovember 15, 2016
2016 ASHRAE Houston Chapter
A thing is right when it tends to preserve the integrity, stability and beauty of the biotic community.
It is wrong when it tends otherwise.
Aldo LeopoldR290 (propane)
N
H
HH
R717 (ammonia)
C
OO
R744 (CO2)
OHH
R718 (water)
S
OO
R764 (SO2)
Examples of the First Refrigerants
What is a Refrigerant?
• A refrigerant is a substance or mixture of
substances usually as a liquid, used for
either providing cooling (usually, air
conditioning or refrigeration) or heating
(heat pumps).
• Refrigerants are all around you
– Sometimes referred to “natural” refrigerants.
– Most refrigerants are engineered to provide
the right safety, right efficiency for the right
application at the right cost.
• A specific refrigerant is used by your body
to keep you cool and you drink it
everyday. R718 or water. R1234yf
History of HVAC&R Refrigerants
Societal Demands Continue To Drive Refrigerant Innovations
1st Generation“What Ever Worked”
2nd Generation“Safety and Stability”
3rd Generation“Ozone Protection”
Ozone
Depletion
4th Generation“Global Warming”
Global
Warming
1830’s – 1930’s 1930’s – 1990’s 1990’s – 2010’s 2010 - ??
• Limited applications mainly industrial
• “Poor safety & cost”
• Innovation enabled exponential societal improvements
Preserved 2nd gen. innovations, safety, stability and efficiency
• Fewer optimal choices• Safety and design
challenges
• NH3
• CO2
• Various Hydrocarbons• H2O• Sulfur Dioxide
• Methyl Chloride (R40)
• NH3
• CFCs and HCFCso R11o R12o R22o R502
• NH3
• HCFCs & HFCso R123o R134ao R410Ao R404Ao Many Blends
• NH3
• Low GWP HFCs & HFOso R1233zd (E)o R1234yf & R1234ze(E)o HFC/HFO blends
• Renewed “Natural” interesto CO2
o Hydrocarbons
How Important Are Refrigerants?
R134a for refrigeratorsR245fa in the insulation foam
R404A for Refrigeration Blend of R125/R143a/R134a
R410ABlend of R32 &
R125R134a
R410A for A/CAmmonia for RefrigeratorR134a or R245fa for foams
R134a, R245fa, water, or hydrocarbons in Foam
Insulation
Refrigerants are Critical to Societies Improved Standard of Living;
Enabling a Global Food Chain,Improving Health &
Allowing Population Mobility to Hot Climates
Refrigerants Impacts on Global Warming
Houston, TexasNovember 15, 2016
2016 ASHRAE Houston Chapter
R1233zd(E)
Environmental pollution is an incurable disease. It can only be prevented.
Barry Commoner
Global Climate Change: Good or Bad?
Climate Change Impacts - Depends On Your Perspective
Impact of Indirect CO2 or Direct CO2eq Pollution
US 2014 – 6,870 Million Metric Tons621,000,000 Dump Truck Loads Annually
What does 1 million metric tons of CO2 physically look like as dry ice?
~90,000 Dump Trucks Loads of Dry Ice - Yearly
F-gases Smallest GWP Contributor – Fastest Growing Segment
Global Warming Impacts In Perspective• GWP Direct Effects
− 16% of total
− Inclds: F-Gas, NO and Methane
− F-Gases 2% of totalo Leaks or direct emmisions
o Minimize by: Smaller refrigerant charges,
reduced leak technologies & lower GWP
refrigerants
*US EPAU.S. Greenhouse Gas Emissions in 2010Total Emissions in 2010 = 6,822 Million Metric Tons of CO2 Equivalent
Indirect GWP Effects
• GWP Indirect Effects− 84% of total
− Burning of fossil fuels
− inclds: industrial
processes, like cemento Minimize by: higher
efficiency equipment,
systems, process, low
carbon energy
Direct GWP Effects
Indirect Effects
Direct Effects
Refrigerant (Direct) GWP Contributions
*US EPA2010
• Refrigerants (HFC‘s and HCFC‘s) account for ~90% of the 2%− Not all gases have equal global warming potential
− GWP based on CO2 = 1
− For example below: Methane has GWP of 21 or 1 molecule of methane
released can do the global warming of 21 CO2 molecules
• GWPs Current IR Refrigerants R123 = 79
R134a = 1300
R410A = 1945
R404A = 3943
R245fa = 858
HFCs Largest Direct GWP Contributors
HFCs
Why Go After HFC’s First?
Long Atmospheric Lives Magnify GWP Contributions
GWP = 10900
GWP = 4750
GWP = 1300
GWP = 1760
GWP = 6130
GWP = 7390
GWP = 110
Old Installation
• 8,250 tons Capacity
• 1.103 kw/ton Efficiency
• R22 Refrigerant
NGR Chiller Impacts
Environmental Impact: 372,000 MT of CO2eqSaving Entire Electrical Emissions for Island of Aruba
New Installation
• 8,250 tons Capacity
• 0.608 kw/ton Efficiency
• R1233zd Refrigerant
HFO Chillers to Cool Channel Tunnel
Indirect Effects
Direct Effects
Regulatory Actions
Houston, TexasNovember 15, 2016
Houston, TexasNovember 15, 2016
2016 ASHRAE Houston Chapter
R1336mzz(Z)
We will need a new substantially new way of thinking if humanity is to survive
Albert Einstein
R1336mzz(E)
October 15, 2016
Nations, Fighting Powerful Refrigerant That Warms Planet, Reach Landmark Deal
KIGALI, Rwanda — Negotiators from more than 170 countries on Saturday reached
a legally binding accord to counter climate change by cutting the worldwide use of a
powerful planet-warming chemical used in air-conditioners and refrigerators.
Montreal Protocol HFC Amendment Agreement Kigali Amendment – Dubai Pathway on HFCs – Global Transitions Based on GWP
October 15, 2016
Montreal Protocol HFC Phase Down Timing Kigali Amendment - Global Transitions Based on GWP
20442040 204220322028 203020262022 202420202016 2018 20382034 2036 20482046
90%
70%
60%
50%
40%
30%
20%
10%
80%
93
63
45
31
2421
90
60
40
20
15
90
70
50
20
European Union
A2 Countries (Developed)
A5 Countries (Group 2)Established Baseline Quantity
A5 Countries (Group 1)
90
80
70
15
2
1
Summary of NAR Current and Pending Regulations
2017 2018 2019 2020 2021 2022 2023 2024 2025 20262016
X
Aerosols & Propellants
R-134a, R-227ea & Blends
ALL HFCs – Com/Res
Any HFC with a GWP > 750
AC – Chillers (ALL)
Any HFC with a GWP > 700
California EPA
Environment andClimate Change Canada
Proposed RegulationsFinal Rulings
20
21
Mo
del
Yea
r
AC & Refrig – Motor Vehicles
R-134a
AC & Refrig – Retail Food
R-404A, R-134a, R-507A…
AC – Chillers (ALL)
R-134a, R-407C, R-410A…
Significant NewAlternatives Policy
Ban on shipment of new equipment with HFCs
Regulatory Actions Will Drive Refrigerant Changes
US EPA to Tighten HFC RegulationsChanges to Section 608 Refrigerant Management Regulations of the Federal Clean Air Act
Overview of Changes Current Requirement EPA Final Ruling (changes indicated in red)
Refrigerants Covered CFCs and HCFCsCFCs, HCFCs, HFCs and all other replacement refrigerants (HFOs,
HFO blends, etc.)
Allowable Leak Rates (50+ lbs. of refrigerant)
Industrial Process RefrigerationCommercial Refrigeration
Comfort Cooling Equipment
35%35%15%
30%20%10%
Leak Inspections None RequiredIf allowable leak rate is exceeded, then:
50-500 lbs.: annual inspections500+ lbs.: quarterly inspections
Recordkeeping Requirement 50+ lbs.5+ lbs. for disposal
50+ lbs. for service/repair
Chronic LeaksNone Required
(“should be repaired”)If leaks ≥ 125% of charge in a calendar year, must submit detailed
reports of efforts to identify leaks and repair equipment
https://www.epa.gov/section608/revised-section-608-refrigerant-management-regulations
Section 608 Changes - Increasing Leak Tightness Requirements to Reduce HFC Impacts
US & Canada Regulating HFCs Anticipating Global Agreement
Other Regulatory Details
• USA has to use SNAP Process of Listing and Delisting
• Canada has regulatory ability to cap and phasedown
• Recent additional USEPA proposals -• US –Hydrocarbons unacceptable for;
• Residential splits, light commercial, centrifugal chillers and positive displacement compressors
• Done because of safety reasons
Designing Refrigerants
2016 ASHRAE Houston Chapter
Houston, TexasNovember 15, 2016
The Earth does not belong to us; We belong to the Earth
Marlee Matlin
R1234ze(E)
Chemistry : Designing Refrigerants
What Ever Came From New Industrial Processes“Before Understanding of the Atom”
1st Generation“What Ever Worked”
R290 (propane)“hydrocarbons”
N
H
HH
R717 (ammonia)
O
HH
R718 (water)
C
OO
R744 (CO2)
S
OO
R764 (SO2)
Chemistry : Designing Safer Refrigerants
Understanding of Atoms Leads to“Designer Refrigerants”
• You start with a basic
hydrocarbon
• Exchange hydrogens for
– Fluorine
– Chlorine
– Bromine
– Iodine
2nd Generation“Safety and
Stability”
Thomas Midgley
Chemistry : Designing Safer Refrigerants
Nonflammable Low Toxicity Refrigerants Led to Exponential Expansion of HVACR Applications and Products
R50ASHRAE Class A3
(methane)
C
H
HH
H
C
H
HH
HF
Cl
Cl
Cl
R11A1
C
H
HH
H
F
F
Cl
Cl
R12A1
C
H
HH
H
FF
ClR22A1
C
H
HH
H
Br
FF
FR13B1A1
Chemistry : Designing Environmentally Safer
Increased Environmental Understanding Leads to“Environmental Designer Refrigerants”
• Ozone depletion caused by
chlorine and bromine reaction
with ozone in combination
with long atmospheric life
• Eliminate chlorine and
bromine or decrease
atmospheric life
– Short atmospheric life impact
not fully understood at the time.
3rd Generation“Ozone Protection”
Ozone
Depletion
Chemistry : Designing Low Ozone Impacts
First R400 “zeotropic” Series Blends AdoptedSafety Preserved – Ozone Protections – Start of Low GWP
Hydrocarbon (Multi-carbons)
ClF Br
R410A – A1 R404A – A1
R407C – A1
Chemistry : Designing Low GWP Impacts
Designing Molecules with Short Atmospheric Life
4th Generation“Global Warming”
Global
Warming
Chemistry : Designing Low GWP Impacts
4th Generation“Global Warming”
Global
Warming
• Add Substitutes that React with
Common Atmospheric Species
• Couple of Chemistry Approaches
– Increase the number of Hydrogens
– Include oxygen or others
– Reduce chemical stability – add
bromine or Iodine
– Unsaturation's (double or triple bonds)
• Sometimes called Olefins
ClF Br IOut Come : Adding Unsaturation's and Hydrogen Additions Best Approach
Problem : Flammability Increases
New Low GWP Refrigerants
Commonly Referred to as HFO’s (Hydrofluoroolefins)Flammability Introduced – Ozone Protected– Low GWP
• Add an unsaturation (double bond)
• Sometimes referred to as Olefins
• Many types
– HFO’s
– HCFO’s
– HCO’s
– HBFO’s
R1233zd(E) A1 GWP 1
R1234yfA2L GWP <1
R1130(E)B2L GWP <1
R1336mzz(Z)A1 GWP <2
Next Generation Refrigerant Alternatives
2016 ASHRAE Houston Chapter
Houston, TexasNovember 15, 2016
Conservation is a state of harmony between men and land
Aldo Leopold
R1130(E)
Balancing Key Factors for;
Direct Refrigerant GWP
Efficiency (Indirect GWP)
Safety
Transition Costs
Intellectual Property
Product Sustainability
Refrigerant Replacement Challenge
Minimal
Environmental
Impacts
(TFA)
Low
Emissions
(leaks)
Lowest
Indirect GWP
(efficiency)
De Minimis
ODP
Lowest
Direct GWP
Safety
Economic
Environmental
Social
Demands
Challenge: Selecting Refrigerants with Balance
Tool Box for Low GWP NGR’s
6 New HFO’s and HCFO’sMany Proposed Blends to Optimize Properties
R32
R152a
R1234yf
R1234ze(E)
R1123
CO2
Ammonia
GWPModerate HFCs(GWP > 150 to 1,000)
Low HFCs,
HFOs
and NaturalsGWP ≤ 150)
Non-fluorinated (Naturals)
R1233zd(E)
R1336mzz(Z)
R1130 (E)
R1224yd(Z)
Hydrocarbons
Water
Glo
ba
l W
arm
ing
(Kyoto
Pro
tocol)
Global
Warming
HFC’s and HFO’s
R245fa GWP
R143aGWP
GWP
GWP
High HFCs(GWP > 1,000)
R134a
R125
R227ea GWP
ODPOzone Depletion
Potential
Acute Toxicity
Cost
Concerns
Global Warming
Potential
GWP
Slightly
Flammability 2L
Flammable
Efficiency
Chemically
Unstable
NGR Alternatives - Flammability
Low Pressure – Low GWP Nonflammables Available Medium Pressure – GWP 600 Nonflammable Limit
High Pressure – No Nonflammable Available
Most Candidates Blends of HFCs with HFOs Balancing Key Factors for;
Flammability
Direct Refrigerant GWP
Efficiency (Indirect GWP)
Capacity
Glide
Intellectual Property
Other Secondary FactorsR1234yf
Refrigerant Safety ClassificationsASHRAE 34
Developing 2L Class Key To Use Low GWP F-Gases
• Toxicity– Chronic exposure safety
limit
– > or = to 400 ppm dividing line
– Class A, most refrigerants, like R-134a
– Class B, R123 and ammonia are examples
• Flammability– Based on flammability characteristics
– Class 1, non-flammable most refrigerants used today, like R-134a, R123
– Class 2L, new class slightly flammable refrigerants <10 cm/sec burning velocity, most new HFO’s, R32
– Class 2, more flammable, R152a
– Class 3, explosive, like propane
• Today, compressor use is generally distributed as shown by capacity
• In general refrigerants used by compressors are;- Centrifugal – low and medium pressure Refrigerants (R123, R134a)
- Screws – medium and some high pressure (R134a, R22-past)
- Scrolls & Recips – high pressure mostly (R22, R410A, R407C)
Refrigerants –Where Used by Compressor Type
3.5 35 350 3500 35,000Cooling Capacity, kw
Centrifugal
Screw
Scroll
Reciprocating
Low Pressure Chillers R123 and R245fa Alternatives
Number of Chiller Products being Offered with NGR’s with R1233zd(E) and R514A
Alternatives Attributes
Most Low GWP (<10)
Flammability• Most nonflammable
Good efficiency
Near design compatible alternatives available
• Candidates with close capacity matches to R123 and R245fa
No Glide
Medium Pressure Chillers R134a Alternatives
Number of Chiller Products being Offered with NGR’s with R513A, R1234ze(E) and R1234yf
Alternatives Attributes
Most Low GWP (<10)
Flammability• GWP 400-600 nonflammable
• GWP <150 flammable
Good efficiency
Near design compatible alternatives available
• Candidates available which are close matches to R134a
Many with no glide - some with low glide
Centrifugal Chiller Performance of Various Alternatives
New Refrigerants Have Similar Efficiencies
High Pressure Chillers R410A Alternatives
Chiller Products being Offered with NGR’s Limited R32 and R452B Leading Candidates
Alternatives Attributes
Lowest GWP (460-675)
All candidates flammable
Good efficiency – most higher
Near design compatible alternatives available
• Candidates available which are close matches to R410A
Many with glide - some with low glide
Summary of Select Next Gen CandidatesBubble Points and Average Dew Points
Glide an Important Consideration
Difference = Temperature Glide
What is the INDUSTRY providing already…
Looking at Air & Water Cooled Chillers using
HFC alternatives…
… Just a few of the screw, scroll
and centrifugal chillers available now with
new HFO or HFO blend refrigerants.
CTV Chillers (R123 & R134a) – R1233zd, R514A, R513A, R1234ze Screw Chillers – R513A, R1234ze(EU only), R1234yf (EU only)
Scroll Chillers – No Products – R32, R452B, R454B Leading Candidates
Ignition EventFlammability Considerations
2016 ASHRAE Houston Chapter
Houston, TexasNovember 15, 2016
We shall need a substantially new way of thinking if humanity is to survive.
Albert Einstein
Fuel-LFL
Ignition Energy
Severity of Event
Defining Flammability Safety a Large Industry Challenge
Fuel-LFL
Ignition Energy
Ignition Event
Severity of Event
Flammability Safety Controlling & Designing for Key Factors
• Fuel —Refrigerant Concentration (LFL)
Higher the better
• Ignition Sources—Restrict or Enclose
—highest minimum ignition energy
• Severity of Event—Design application to handle
pressure rise (venting)—Design refrigerant to minimize
potential secondary issues
—Lowest possible Burning Velocity
Minimizing Burning Velocity Increases LFL (Fuel)Lower BV Better, But <10 cm/sec Maximum LFL Reached
Optimizing Flammability – Fuel/LFL
Minimizing Burning Velocity Increases Minimum Ignition EnergyPoor Flame Propagation & Combustion Results
Optimizing Flammability – Ignition Energy
2L Refrigerants - 5x Lower HOC than HydrocarbonsHOC Not a Good Measure of Severity of Event
Incomplete Combustion in Most Cases with 2L’s as BV Decreases
Optimizing Flammability – Heat of Combustion
Visual Examples of Burning Velocity Differences with 2L Flammable Refrigerants
Not All 2L’s Have The Same Flammability Safety Characteristics
R32
Burning Velocity 6.7 cm/sec
MIE>30 mj
R1234yf
Burning Velocity 1.5 cm/sec
MIE>5000 mj
Insight Into the Refrigerant Future
2016 ASHRAE Houston Chapter
Houston, TexasNovember 15, 2016
Pollution is Pollution no matter the impact or consequences
Steve Kujak
R1224yd(Z)
R1123
• Limited Nonflammable Alternatives - R123: Ultra low GWP nonflammables available (<10 GWP)
- R134a: 400-600 GWP limit for nonflammables
- R404A/R407C: 1200-1400 GWP limit for nonflammable
- R410A: all candidates 2L – possible technology on the way?
• Flammability a Technical & Application Challenge - No History/Experience
- Designing Refrigerants for Lowest Possible Flammability Possible
- Industry Working on Defining Flammability Safety
• Design Compatible Alternatives Identified –But..- More Zeotropic Blends Possible
- New Design Centerlines Likely
- Product Category Fragmentation by Refrigerant Likely
Insights – Refrigerant Future
• R123- Many ultra low GWP nonflammables refrigerants
identified
- R1233zd(E) products introduced by 3 OEMs
- Market fragmentation?: other introductions planned
• R134a- 400-600 GWP limit for nonflammables- Some ultra low GWP refrigerants ID : all 2L
flammable- Market fragmentation occurring:
Refrigerators –hydrocarbons & R1234yf
Cars - R1234yf
Chillers/Refrigeration – R513A, R1234ze, R1234yf(new)
Alternatives
• R404A/R407C- 1200-1400 GWP limit for nonflammable
- Market fragmentation occurring: Transport refrigeration –R452A & CO2 demonstrations
Stationary refrigeration – wide mix: R448/R449s, hydrocarbons –small charge stand alone systems, transcritical CO2, Cascade systems R513A/CO2, Ammonia/CO2, R1234ze/CO2.
• R410A- All candidates 2L
- Market fragmentation occurring: Small charge systems (RAC/PTAC) –hydrocarbons & R32
Splits – R32 and R452B(DR55)
RTU/VRF – No introductions
Alternatives
Developing Nations F-Gas Phase Down
Product Efficiency Standards
Global HVAC&R Demand
Building HVACR & Electrical Loads
2010 2015 2020 20302025
Today
20402035
Future: Continued Focus On Indirect GWP Contribution (Energy Efficiency & Load) To Meet
Increasing Global HVAC&R Demands
Refrigerant Future TimelineHCFC Phase Out
System & Building Efficiency Standards
Some Low Efficiency Refrigerants In
Products Phased Out, i.e. CO2Global
Warming
Indirect
~84%
Tomorrow
Developed Nations F-Gas Phase DownGlobal
Warming
Direct
~16%
Viable F-Gases To Meet 80% Phase Down
For Most Products & Applications
Some Incremental Use of Naturals
Only Where Safety & Efficiency Met
Thanks for ListeningQuestions?
Men Argue… …Nature Acts
VoltaireSunrise in Kauai, Hawaii 2015