next generation of refrigerants - ashrae...

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



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



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




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

https://www.epa.gov/section608/revised-section-608-refrigerant-management-regulations

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



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


Global

Warming

Chemistry : Designing Low GWP Impacts


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



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


Most Low GWP (<10)

Flammability• GWP 400-600 nonflammable

• GWP <150 flammable

Good efficiency


• 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


Lowest GWP (460-675)

All candidates flammable

Good efficiency – most higher


• 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



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



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

next generation of refrigerants - ashrae...

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