HFO-1234yf Low GWP Refrigerant Information for Manufacturing and Service Facilities

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HFO-1234yf Low GWP Refrigerant Information for Manufacturing and Service Facilities 10 November, 2010 Mary E. Koban Sr. Automotive Engineer DuPont Fluoroproducts

Agenda 2 HFO-1234yf Properties Flammability of HFO-1234yf Automotive OEM Plant Implementation Automotive Service Implementation Summary

HFO-1234yf Properties 3 Same operating conditions as 134a (similar P/T curve) 3.5 Vapor Pressure Thermally stable under extreme use conditions in a MAC system Pressure (MPa) 3 2.5 2 1.5 1 0.5 REFPROP Equation Of State available HFC-134a HFO-1234yf Cooling capacity equivalent to 134a Energy efficiency better or equivalent to 134a Only modest design changes required in MAC Temperature, o C 0-40 -20 0 20 40 60 80 100 HFO-1234yf has vapor pressure, toxicity class A, similar to R-134a, but has mild flammability

HFO-1234yf Flammability Properties 4 High MIE indicates HFO-1234yf is very difficult to ignite Burning velocity of HFO-1234yf is only 1.5 cm/sec weak flame not easily propagated Minimum Ignition Energy (mj) 10000 1000 100 10 1 0.1 0.01 HFO-1234yf Ammonia HFC-152a Methane Propane 0 10 20 30 40 50 Burning Velocity (cm/s)

HFO-1234yf Automotive OEM Plant Implementation 5 Customer Driven HFO-1234yf Product Implementation Supplier Driven Dual input process for successful product implementation. Customer/Supplier giving input into process is needed to make this a success!

HFO-1234yf Automotive OEM Plant Implementation 6 Product Plant Site Implementation Customer Driven Process Specific to each customer plant site (country, local regulations, etc.) Key Aspects Regulations (ATEX, Serveso, ADR, etc.) Site constraints (available land, etc.) Volumes (types of storage) Supplier Driven Process-Product Stewardship Can customer safely handle the product? Does customer have the correct information to make implementation a success?

HFO-1234yf Automotive OEM Plant Implementation 7 POSSIBLE STRATEGIES Leak Detection Ventilation Mitigation Area Classification Based Strategy employed will depend on location, volume, potential amount of refrigerant in area, potential leak scenarios, etc.

HFO-1234yf Automotive OEM Plant Implementation Potential Implementation Strategies 8 Various HFO-1234yf plant implementation strategies can be employed. It is important to consult with appropriate regulatory agencies regarding strategies and limitations

HFO-1234yf Automotive OEM Plant Implementation 9 Comparison of Some Appropriate Regulations for Germany HFO-1234yf vs HFC-134a Regulations are similar for both products. HFO-1234yf has some additional regulations that need to be considered due to mild flammability

HFO-1234yf Automotive Service Implementation- Potential Leakage Scenarios 10 CFD-Computational Fluid Dynamics DuPont conducted CFD modeling to understand potential flammable region of a leak from a severed AC line under various leakage scenarios Three Scenarios evaluated 1. Leak from a point in open space (simulating vehicle with potential leak sitting outdoors) 2. Leak from a point in bounded space (simulating potential leak in garage or mfr plant) 3. Leak from a point under an open car hood and impinging on a surface (in a service garage) CFD Model Output Refrigerant concentration at several distances (x,y and z directions) from the leak point during leak event. Size of refrigerant plume above lower flammability limit (LFL) Results useful as input for risk assessments

CFD MODEL DEVELOPMENT 11 Approach Used Several CFD Models Designed 1 st CFD Model - Release was initially modeled with no bounding 2 nd & 3 rd CFD Model -Release modeled as bounded vapor release using methodology in Venetsanos paper Information presented at the American Institute of Chemical Engineers 2010 Spring National Meeting 6th Global Congress on Process Safety 44th Annual Loss Prevention Symposium, San Antonio, Texas Ref-Koban, Herrmann-AIChE Loss Prevention 2010

CFD MODEL DEVELOPMENT 12 Assumptions for all three scenarios 600 g total refrigerant leaked 12.4 g/s of HFO-1234yf total time of leak 48.4 secs Air exchange rate was zero, or low wind field (<0.5 m/sec) for unbounded leak Release Details HFO-1234yf will create a two phase leak when released under a severed line situation. The release plume was modeled as vapor phase, since initial modeling did not show large differences in shape of jet plume

HFO-1234yf Plume Release Diagrams 13 Two Phase Jet Two Phase Jet All Vapor Jet All Free Vapor Jet Jet February 2008 Process Safety and Fire Protection 24 Liquid and vapor combined release will have the shape above. HFO-1234yf will create a two phase release under a severed line situation. February 2008 Process Safety and Fire Protection 23 An all vapor release will have the shape above Plume is fully formed within 1/2 second of the start of the release. Modeled in both horizontal and parallel directions of the air flow Outcome -similarities in plume shape/length

Diagram of Scenario - Unbounded leak 14 Leak source pointsevered A/C line Refrigerant plume formed when refrigerant escapes from leakpoint Assumptions: Leak is not bounded by room/structure. (imagine severed line AC line outside, not bound/hitting any object) Leak assumed to be in low wind field, so no dissipation of refrigerant by wind.

Plume Concentration Profile Unbounded Leak Results can vary based on hole size/shape and release direction versus air currents. HFO-1234yf Conc. 15 Above 6.2 vol% 6.2 vol% 5.5vol% 5.0 vol% 4.5 vol% 4.0 vol% 3.5 vol% meters 3.0 vol% 2.5 vol% Length of plume above LFL is very small (about 15 cm) 2.0 vol%

Diagram of Scenario - Bounded leak 16 Dimensions of a single bay garage (7 x 4 x 3 m). Leak source pointsevered A/C line Refrigerant plume Small holes at bottom of box keep pressure from building up - Assumed 600 g charge released in 48 seconds and zero air flow

Plume Profile Bounded Leak HFO-1234yf Conc. >10 vol% 10 vol% 6.3 vol% 4.0 vol% 2.5 vol% 1.6 vol% 17 Air Velocity >100 m/sec 100 m/sec 10 m/sec 1.0 m/sec 0.1 m/sec meters Below 0.1 m/s Plume above LFL is very small (10 cm in x direction, 2 cm in z)

Diagram of Surface Impinging Scenario 18 Dimensions of a single bay garage (7 x 4 x 3 m) Surface that leak impinges upon Leak source severed A/C line Small holes at bottom of box keep pressure from building up Modeled three different distances of leak to impinging surface (0.1 m, 0.22 m and 0.85 m)

19 Plume Profile Bounded Leak Impinged on a Surface (0.1m) Distance to surface = 0.1m HFO-1234yf Concentration 10 vol% 6.3 vol% 4.0 vol% 2.5 vol% 1.6 vol% Below 1.0 vol% Plume is continually dispersed by surface, almost no flammable zone available

Plume Profile Bounded Leak Impinged on a Surface Side View HFO-1234yf Conc. 20 >10 vol% 10 vol% 6.3 vol% 4.0 vol% 2.5 vol% 1.6 vol% meter Below 1.0 vol% Air Velocity >100 m/s 100 m/s 10 m/s 1.0 m/s 0.1 m/s meter Below 0.1 m/s Plume is continually dispersed by surface with almost no flammable zone formed (~ 2-4 cm around impact point)

Summary 21 HFO-1234yf is very similar to HFC-134a, except for mild flammability. HFO-1234yf has low burning velocity, high minimum ignition energy and is difficult to ignite. HFO-1234yf is less flammable than other commonly used substances. Potential automotive OEM plant implementation strategies have been investigated. Potential automotive service leak scenarios have been investigated for use in service implementation (risk assessments.) As with any substance, customers will need to follow appropriate regulations and best practices for product implementation.

22 More Information www.refrigerants.dupont.com www.smartautoac.com Please feel free to contact the author at Mary.e.Koban@usa.dupont.com for any additional information.

Thank You!