throbber
«JMHII
`
`the miracles ofsdencr
`
`Honeywell
`
`HFO-1234yf Low GWP Refrigerant:
`A Global Sustainable Solution for Mobile
`
`Air Conditioning
`
`Honeywell I DuPont Joint Collaboration
`
`Mark Spatz
`
`Barbara Minor
`
`SAE 2008 Alternate Refrigerant Systems Symposium,
`
`June 10-12, 2008, Scottsdale, AZ
`
`Arkema Exhibit 1083
`
`

`
`The miracles of science‘
`
`Honeywell
`
`Agenda
`
`- Performance Optimization Tests
`
`- HFO-1234yf Properties
`
`— Toxicity
`
`— Environmental
`
`— Water solubility/Electrical
`
`— Desiccant compatibility
`
`- HFO-1234yf Handling/Supply Chain
`
`- Path Forward
`
`2
`2 of 26
`
`2008 SAE Alternative Refrigerant System Symposium
`
`

`
`The miracles of science‘
`
`HFO-1234yf Overview
`
`Honeywell
`
`- Excellent environmental properties
`— Very low GWP of 4, Zero ODP, Favorable LCCP
`
`— Atmospheric chemistry determined and published
`
`- Low toxicity, similar to R-134a
`— Low acute and chronic toxicity
`
`— Significant testing completed
`
`- System performance very similar to R-134a
`— Excellent COP and Capacity, no glide
`- From both internal tests and OEM tests
`
`— Thermally stable and compatible with R-134a components
`
`— Potential for direct substitution of R-134a
`
`- Mild flammability (manageable)
`— Flammability properties significantly better than 152a; (MIE, burning velocity, etc)
`
`— Potential for “A2L” ISO 817 classification versus
`
`for 152a based on AIST data
`
`— Potential to use in a direct expansion A/C system
`
`- Global Solution
`
`— Lowest total cost of transition than any alternative
`
`— good performance in all climates, and car sizes
`
`3
`3 of 26
`
`2008 SAE Alternative Refrigerant System Symposium
`
`

`
`‘ System Bench Test Results H0|1e)’We||
`
`The miracles alsciencr
`
`120%
`
`110%
`
`100%
`
`RelativeTo134a
`
`- No changes were made to system including TXV; Industry standard test conditions
`
`- Both Capacity and COP are generally within 5% of 134a performance.
`— This was recently confirmed at two outside labs-
`- Lower compression ratio, low discharge temperature
`(12°C lower at peak conditions)
`- Further improvements likely with minor system optimization, for example:
`— Lower AP suction line and I or TXV optimization to maintain a more optimum superheat.
`HFO-1234yf performance is comparable to 134a; further improvement
`possible with minor optimization
`2008 SAE Alternative Refrigerant System Symposium
`
`4
`4 of 26
`
`

`
`Superheat Study — Capacity and COP Honeywell
`The miracles of science‘
`
`2.5
`5.000
`
`II-
`IIIIIFIIIIII
`I
`
`0
`
`‘
`
`kW
`
`
`
`CoolingCapacity,
`
`4_5oo
`4.000
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`
`2.500
`
`2 000
`
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`
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`
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`
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`
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`
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`
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`
`Superheat, K
`
`Significant COP Improvement with Optimized SH
`
`2008 SAE Alternative Refrigerant System Symposium
`
`
`
`COP,kWIkW
`
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`
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`
`5
`5 of 26
`
`

`
`‘flflmi
`
`we miracles ofsciencr
`
`$lL35'2KSu>eme¢l
`
`Superheat Study — PH Diagram
`
`Honeywell
`
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`5
`6 of 26
`
`2008 SAE Alternative Refiigerant System Symposium
`
`
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`
`The miracles olscience‘
`
`Superheat Study — Mass Flow and
`Discharge T
`
`|-|oneywe||
`
`100
`
`9 95
`2. 90
`3
`
`Q.
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`
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`
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`
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`
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`
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`
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`
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`
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`
`Optimized Superheat Return Parameters to R-134a Levels
`
`7
`7 of 26
`
`2008 SAE Alternative Refrigerant System Symposium
`
`

`
`"'°'"”°"°‘°""°"“‘
`
`Superheat Study - Subcool and
`Pressure Ratio
`
`Honeywefl
`
`12
`
`108
`
`4
`
`2
`
`Subcooling,K
`
`mm
`II¥I-—"’ 5
`
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`
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`
`10
`
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`
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`
`— 3
`
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`
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`
`0.00
`
`5.00
`
`10.00
`
`15.00
`
`20.00
`
`25.00
`
`30.00
`
`Superheat, K
`
`Optimized Superheat Return Parameters to R-134a Levels
`
`2008 SAE Alternative Refrigerant System Symposium
`
`3
`8 of 26
`
`

`
`The miracles of science‘
`
`Honeywell
`
`Sanden HFO-1234yf Optimization
`Bench Tests
`
`- Tests conducted
`
`— R-134a Baseline
`
`— HFO-1234yf drop-in with no changes
`
`— HFO-1234yf with TXV adjustment
`
`— HFO-1234yf with modified TXV by Fujikoki
`
`9
`9 of 26
`
`EsANE21—
`
`Delivering Excellence
`
`

`
`The miracles of science‘
`
`Sanden Test Matrix
`
`Honeywe"
`
`Test Condiitions
`
`[1Imin]
`
`[°C]
`
`[°C]
`
`[kglh]
`
`[kglh]
`
`[% rel.H.]
`
`25
`
`25
`
`25
`
`-bNOU‘!
`
`800
`
`1500
`
`2500
`
`800
`
`1500
`
`2500
`
`800
`
`1500
`
`2500
`
`800
`
`A O
`
`1500
`
`2500
`
`25
`
`25
`
`25
`
`ANNOU1U1
`
`750
`
`1200
`
`2200
`
`750
`
`1200
`
`2200
`
`750
`
`1200
`
`2200
`
`750
`
`1200
`
`2200
`
`175
`
`175
`
`175
`
`350
`
`350
`
`350
`
`175
`
`175
`
`175
`
`350
`
`350
`
`350
`
`50
`
`O
`
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`
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`
`0101O
`
`01O
`
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`
`toL2=8°C
`
`toL2=8°C
`
`to,_2=8°C
`
`to._2=8°C
`
`toL2=8°C
`
`toL2=8°C
`
`toL2=8°C
`
`to._2=8°C
`
`toL2=8°C
`
`max PWM
`
`max PWM
`
`max PWM
`
`4.2
`
`4.3
`
`19
`10 of 26
`
`EsANE21—
`
`Delivering Excellence
`
`£ &
`
`1.2
`
`1.3
`
`2.2
`
`2.3
`
`3.2
`
`3.3
`
`-- -- -- --
`
`

`
`IJIIHIJII
`
`Sanden Test Results - Capacity Honeywell
`
`The mimdes alsciencr
`
`
`
`CoolingCapacity(kW)
`
`
`
`
`
` EH
`IIEIEEII
`
`Cooling capacity similar to R-134a E SAM
`
`11
`11 of 26
`
`Delivering Excellence
`
`

`
`‘s'1mm_ Sanden Test Results - COP
`
`Honeywefl
`
`COP improved versus R-134a
`
`12
`
`Delivering Excellence
`
`
`

`
`«i1I]H[[[[
`vmmdesvrsa-=~=e~
`
`Sanden Bench Test —
`Capacity with modified TXV
`
`H°"°ywe"
`
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`
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`
`Cooling capacity similar to R-134a
`
`13
`13 of 26
`
`Dollvorlng Excellence
`
`

`
`v~mi~«=s«rs««~=e~
`
`6
`
`Sanden Bench Test —
`cop with modified TXV
`
`H
`
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`
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`
`54
`
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`
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`
`
`Additional cop improvement with modified TXV E flim-
`
`Dclivorlng Excolbnoc
`
`14 of 26
`
`

`
`The miracles of sciente‘
`
`Honeywell
`
`Significant Toxicity Information Available
`
`Test
`
`H FO-1234yf
`
`134a
`
`- Acute Lethality
`
`No deaths 400,000 ppm No deaths 359,700 ppm
`
`- Cardiac sensitization
`
`NOEL > 120,000 ppm
`
`NOEL 50,000 ppm
`LOEL 75,000 ppm
`
`- 13 week inhalation
`
`NOEL 50,000 ppm
`
`NOEL 50,000 ppm
`
`- Developmental
`
`NOAEL 50,000 ppm
`
`NOAEL 50,000 ppm
`
`- Genetic Toxicity
`
`Not Mutagenic
`
`Not Mutagenic
`
`- 13 week genomic
`(carcinogenicity)
`
`Not active (50,000 ppm) Baseline (50,000 ppm)
`
`\/
`
`\/
`
`J
`
`\/
`
`\/
`
`\/
`
`- Environmental Tox
`
`NOEL > 100 mg/L (Pass) NOEL > 100 mg/L (Pass) J
`
`15
`15 of 26
`
`HFO-1234yf Has Low Toxicity
`
`2008 SAE Alternative Refrigerant System Symposium
`
`

`
`The miracles of science‘
`
`Honeywell
`
`Based on the toxicity results due end of August, 2008,
`Honeywell and DuPont will be in a position to commit to
`production of HFO-1234yf
`
`- Second Species Developmental Preliminary Results
`
`— Based on what we know today, we believe HFO-1234yf will have a no
`effect level (NOEL) of 4000 ppm. Therefore, we believe HFO-1234yf
`will not be classified as a developmental toxin in Europe and will be
`classified as ASHRAE Class A (low toxicity)
`
`— Final report due end of August, 2008
`
`- Reproductive study is in progress
`
`— Preliminary Interim results 1—Gen end of August 2008
`
`— 2-Gen is being conducted to satisfy possible future requests of data
`
`,5
`16 of 26
`
`2008 SAE Alternative Refrigerant System Symposium
`
`

`
`The miracles of science‘
`
`Honeywell
`
`Acute Toxicity Exposure Limit
`
`Refrigerant
`
`ATEL (ppm)
`
`-
`
`It provides an estimate of the maximum
`exposure limit for a short time period (530
`
`minutes) with no adverse health effects.
`
`- HFO-1234yf developmental test results
`
`have no impact on ATEL value.
`
`101,000
`
`18,000
`5°»°°°
`
`50,000
`
`40,000
`
`R-152a
`
`CO2
`
`HFO-1234yf
`
`HFO-1234yf Has a Favorable ATEL Value - Short Term Tox
`Exposure Not an Issue for Collisions, Accidental Releases
`
`The Acute Toxicity Exposure Limit (ATEL) is a value used by Standards organizations (e.g., ASHRAE 34, ISO 817) to establish the maximum refrigerant
`concentration limit for a refrigerant in air.
`It is calculated from the acute toxicity data using methods determined in accordance with the Standards.
`
`,7
`17 of 26
`
`2008 SAE Alternative Refrigerant System Symposium
`
`

`
`Excellent Environmental Properties Honeywell
`
`The miracles of science‘
`
`-0DP=0
`
`- 100 Year GWP = 4
`
`(owpma = 1430)
`
`I-I.-'
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`
`— Measurements completed & published:
`
`“Atmospheric Chemistry of CF3CF=CH2”
`
`Chemical Physics Letters 439 (2007) pp 18-22
`
`- Atmospheric lifetime = 11 days
`
`- Atmospheric chemistry measured
`
`— Atmospheric breakdown products are the
`same as for 134a
`
`— No high GWP breakdown products (e.g.
`NO HFC-23 breakdown product)
`
`— Results published in 2008
`
`- Good LCCP
`
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`
`HFO-1234yf Environmental Properties Have Been Confirmed in an
`Independent, Peer Reviewed and Published Scientific Paper
`
`18
`
`18 of 26
`
`2008 SAE Alternative Refrigerant System Symposium
`
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`"'°"""°<'*-'50/w‘°'~=*-"
`
`Breakdown Product Discussion —
`Trifluoroacetic Acid (TFA)
`
`Honeywell
`
`- R-134a breakdown product trifluoroacetic acid (TFA) does not pose
`a threat to the environment, based on thorough industry
`evaluations in 1990s
`
`— HFO-1234yf will also breakdown to form TFA
`
`- There is a very large quantity of TFA in the sea (Ref: 1, 2, 3); The
`amount suggests that TFA is a natural component of seawater (3).
`— 1. Scott B.F., et al., Haloacetic Acids in the Freshwater and Marine
`Environment, First International Symposium on Atmospheric Reactive
`Substances, 14-16 April 1999, Bayreuth, Germany.
`— 2.Von Sydow L., A. Grimvall, H. Boren, K. Laniewski, A. Nielsen, Natural
`background levels of trifluoroacetate in rain and snow, Environ. Sci. Technol.,
`34, 3115-3118, 2000.
`
`— 3. Frank H., E.H. Christoph, 0. Holm-Hansen and J.L. Bullister,
`Trifluoroacetate in Ocean Waters, Environ. Sci. Technol., 36, 12-15, 2002.
`
`- “Based on available data, one can conclude that the environmental
`levels of TFA, resulting from the breakdown of alternative
`fluorocarbons do not pose a threat to the environment”.
`— Boutonnet et al., Environmental Risk Assessment of Trifluoroacetic Acid,
`Human and Ecological Risk Assessment, 5(1), 59-124, 1999.
`
`19
`19 of 26
`
`2008 SAE Alternative Refrigerant System Symposium
`
`

`
`The miracles of science‘
`
`Honeywell
`
`Water Solubility Results
`
`Water in
`
`Water in
`
`Refrigerant at
`25°C (ppm)
`
`Refrigerant at
`50°C (ppm)
`
`HFO-1234yf
`
`AR|—700, SAE—J2776 Refrigerant Standard for Moisture: 20 ppm max
`
`No water solubility issues expected for HFO-1234yf
`
`20
`20 of 26
`
`2008 SAE Alternative Refrigerant System Symposium
`
`

`
`The miracles of sciente‘
`
`Honeywell
`
`HFO-1234yf Desiccant Selection
`
`- Required Desiccant Amount/type Depends on:
`
`— Refrigerant solubility and reactivity with water
`
`— Rate of water permeation into a system
`
`— OEM desired level of system dryness
`
`- R—134a Desiccant
`
`— Currently use XH-7 or XH-9
`
`— 40-60 grams typical usage for average R-134a system
`
`- HFO-1234yf Desiccant Testing
`
`— XH7 and XH9 performed well in HFO-1234yf testing.
`
`— HFO-1234yf is less reactive with the adsorbent than R134a.
`
`— Tests were run for 14 days at 82°C with R134a as a baseline.
`
`— UOP would recommend starting with the same amount used in today’s
`R134a systems
`
`HFO-1234yf is usable with the same desiccants and
`amount as R-134a
`
`21
`21 of 26
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`
`

`
`The miracles of science‘
`
`Honeywell
`
`Electrical Properties
`
`‘T “F°-1234“
`
`
`
`Liquid Dielectric
`Constant @ 21 .3°C
`Resistivity, MOhms.m
`
`9.8 (1), 9.0 (2), 9.2 (3)
`
`7.7 (1)
`
`9.6(1) 7.3 (2)
`
`Data References:
`
`1. Honeywell measurements
`2. A. Sekiya & S. Misaki, Journal of Fluorine Chemistry; 101 (2000) pp
`215-221
`
`3. C. Meurer, G. Pietsch & M. Haacke, International Journal of
`
`Refrigeration, 24 (2001) pp 171-175
`
`HFO-1234yf electrical properties similar to R-134a
`
`22
`22 of 26
`
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`
`

`
`The miracles of science‘
`
`Honeywell
`
`HFO—1234yf Will Be Handled Similar to R-134a
`
`- Distribution of HFO—1234yf from manufacturer to auto OEM
`plants and after sales service markets will be similar to R-134a
`
`- Minor changes to plant charging equipment and procedures
`
`- HFO—1234yf can be recovered, recycled and reused on site at
`service shops
`
`- HFO—1234yf leaks can be detected with same equipment as R-
`134a
`
`- Unique fittings will be used ensure no cross contamination with
`R-134a
`
`23
`23 of 26
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`
`

`
`The mlmdes alsciencr
`
`Supply Chain Analysis
`
`H0|1e)’We||
`
`TUV Study Description Details
`
`Description of Supply chain
`
`Substance will be imported in bulk: 15 — 20 MT ISO tanks-
`Storage of Substance in bulk in Port Area
`
`Substance is shipped from Port to OEM for delivery in Bulk Storage tank (capaci-
`ty up to 50 MT
`OEM has dedicated filling lines to manufacturing operations, where AC system is
`charged
`Car is supplied to Distributor, Dealer and customer
`
`Step 2:
`Substance is transferred from Port to Re—packaging site
`—
`Substance is filled in cylinders
`-
`- Cylinders are supplied to OEM, then optionl
`
`Step 3:
`
`Step 4:
`-
`—
`-
`
`Substance is transferred from Port to Re-packaging site
`Substance is filled in cylinders
`Substance is supplied to distributor
`Distributor supplies to service centre
`Service centre charges product to Car AC
`
`Substance is recovered at service point
`Substance is treated in recovery unit or
`Substance must be returned to distributor or waste treatment
`
`,4
`24 of 26
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`
`

`
`The miracles of science‘
`
`Path Forward
`
`Honeywell
`
`- Plant Process Design & Planning
`
`In progress
`
`/Second Species Development test — Preliminary results
`
`Mar 2008
`
`- Development Test - final report
`
`Aug 2008
`
`- Regulatory: SNAP/ASHRAE filed; REACH to be filed
`
`Jul 2008
`
`- 1-Gen Reproductive test results
`
`Aug 2008
`
`- Obtain Industry convergence/multiple OEM commitments
`
`Sept 2008
`
`-Industry adoption of HFO—1234yf
`
`-Firm volumes projections to finalize facility plans (June 2008)
`
`- Obtain Honeywell/DuPont Capital Commitment/Funding
`
`Oct 2008
`
`- Plant Construction end & plant start-up
`
`Nov 2010
`
`25
`25 of 26
`
`2008 SAE Alternative Refrigerant System Symposium
`
`

`
`-u
`
`-
`
`The miracles of science‘
`
`Honeywell
`
`For further information on HFO-1234yf please visit:
`
`www.genetr0n.c0m ,
`
`wwwrefrigerants.dupont.c0m , and
`
`WWW.SmartAut0Ac.c0m
`
`Thank you!
`
`DISCLAIMER
`
`Although all statements and information contained herein are believed to be accurate and reliable, they are presented without guarantee or
`warranty of any kind, expressed or implied. Information provided herein does not relieve the user from the responsibility of carrying out its own
`tests and experiments, and the user assumes all risks and liability for use of the information and results obtained. Statements or suggestions
`concerning the use of materials and processes are made without representation or warranty that any such use is free of patent infringement and
`are not recommendations to infringe on any patents. The user should not assume that all toxicity data and safety measures are indicated herein or
`that other measures may not be required.
`
`2.;
`26 of 26
`
`2008 SAE Alternative Refrigerant System Symposium

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