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Contamination of Refrigerated Container Systems UNEP - Joint Meeting of the Regional Ozone Network For South Asia, Southeast Asia and the Pacific Paro , Bhutan, May 2012 Mark Bennett Container Owners Association - COA Triton Container International . Introduction.
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Contamination of Refrigerated Container Systems UNEP - Joint Meeting of the Regional Ozone Network For South Asia, Southeast Asia and the Pacific Paro, Bhutan, May 2012 Mark Bennett Container Owners Association - COA Triton Container International
Introduction • Triton Container International • Private company founded 31 years ago • Triton fleet: • 1.9 million containers (TEU) • 72,000 refrigerated containers (units) • World fleet: • c.30 million containers (TEU) • 1.3 million refrigerated containers (units)
COA – Container Owners Association • Forum to represent the interest of all marine freight container owners • Members include: • Most major shipping lines • Container Leasing Companies • Service Depots • Manufacturers of containers and refrigeration machinery
Agenda • Refrigerated Containers • Fake Refrigerants and Explosions • Shipping Industry response • The Future
1. Refrigerated Containers New Refrigerated Containers at a factory in China
The Emma Maersk can carry 1,000 refrigerated containers and up to 15,000 TEU total containers.Length 400m. Deadweight is 150,000 Tons Modern large container ship
Refrigerated Containers • Mostly 12m/40’ length, 67m3 cube and 30T cargo capacity • Strong rigid structure, insulated with foam blown with HCFC 141b or Cyclopentane • c.5kg of R134a refrigerant (some use R404a) • Operating life of 12 to 15 years • Cost new US$18,000 (c.$8k machine/$10k box)
Refrigerated Containers • Operate in ambient temperatures up to +50C • Cargo temperatures from +15C down to -30C • Wide operating temperatures compared to other sectors – design challenges for efficiency • Manufacturers: • Carrier Transcold (50%+ market share) • MCI Starcool • Daikin • Thermoking
Montreal Protocol - Actions • 1993 – R12 unit production phased out and R134a/R404a models introduced • R134a models – larger compressors, higher power consumption for same cooling capacity • Many continued with R12 until retirement • R409a used to convert some machines from R12 but market resistance due to service issues on ships • Last R12 units retired by 2000
Fake Refrigerants & Explosions • Shipping industry becomes aware of contamination in Q3 2011 after tests to exploded reefers • Demand for R134a and shortage/price of Fluorspar linked to sharp price rises in 2nd half 2010 • Rise in price and supply shortages of R134a may have enabled cheaper fake R134a into the market • Fake refrigerants supplied as “R134a” under main brand names
Explosions in Vietnam April 2011 2 units explode in 2 days Both units under PTI - service Units had gas service 3-4 weeks before
Vietnam incidents… • Authorities sealed off the terminal • Very little evidence available • Initial conclusion:possibleleak testing with Oxygen
US West Coast incident Engineer reports gas burning spontaneously in air – August 2011
US West Coast incident - 2 Opening high pressure valve on compressor – liquid emerging started burning Alkyl metal halide is suspected Samples taken from the compressor show R40 – methyl chloride
Brazil incident • Unit serviced Vietnam then R134a recharged in transit • Unit moved to Brazil • Engineer identifies low gas and connects R134a supply during service • Explosion of compressor similar to Vietnam • No aluminum components remaining
China incident • Similar damage to Vietnam explosions • White Aluminium Oxide visible • Technician moved away from machine to take a phone call
China incident - 2 • Corrosion to stainless steel lining
Other Industries • 2009: public transport companyin Greece • Passengers: several injuries (poisoning) • Workshop staff: several injuries (poisoning/explosion) • AC rubber hoses and seals disintegrated • 2009: fridges, Germany • Product recall • 2010: vehicles • Reports of poisoning from methyl chloride leaks in passenger compartment
Other Industries Bus air-con unit :
DuPont – Fake Gas Tank ORIGINAL DuPont R134a FAKE Dupont R134a Dupont spelled with lower case “p” instead of “P”
Fake Gas Supply • Gas bottles on ships tested found contaminated • Gas bottles found in Philippines, China, Angola, Spain with R40/methyl chloride • Several different mixes of fake gas found with more than one containing R40/methyl chloride • Other gases used include: • R12, R22, R142b, R124, R30 • Easy to order from the internet: http://www.gzzhigao.net/products/977.html
Chemistry – Theory • Fake gas in Vietnam contained c.50% R40 (methyl chloride/chloromethane) and 50% R134a • R40 reacts quickly with alumunium components in compressor • chloromethane + aluminium → trimethylaluminium(TMA) + aluminium chloride 6 CH3Cl + 4 Al → Al2(CH3)6 + 2 AlCl3
Possible Cause of Explosion • New R134a added or circulated on startup may react strongly with TMA in compressor possibly causing a hydrogen fluoride reaction • Air entering the system may react with TMA: Al2(CH3)6 + 24O2 → AL2O3 + 6CO2 + 9H20 Less likely and doesn’t explain stainless steel corrosion • Chemistry is complex • Why no recent explosions?
Shipping Industry Response • October 17 – news of Qingdao explosion • All 5 units serviced at Cat Lai terminal, Ho Chi Minh and the US West Coast incident • Shipping lines quarantine units serviced at Cat Lai • November – COA conference at European Intermodal • Saigon Newport circulate c.1200 serial numbers • ILWU trade union injunction on handling Vietnam serviced refrigerated containers.
Testing Options • Search for suitable test methods • Methyl chloride/R40 difficult to test for • Flame Halide Lamp Test detects chloride contamination • Industry resistance to Flame Halide Test • Other methods inaccurate or too costly • 3 conferences held to review and demonstrate test methods – London, Singapore, Antwerp
Current Test Programme • Testing gas bottles on ships and in depots • Focus on high risk units serviced in Vietnam • 15,000 refrigerated containers serviced per day • Big terminals can service 100+ units per day • Samples extracted with care and tested with flame halide lamp • Where positive, sample sent for Gas Chromatograph testing using Mass Spectrometry method.
Test Programme – Issues/Challenges • Training depots – resistance and time: risk of testing versus risk of not testing • Time, availability and cost of GC MS testing • Contamination with CFC/HCFC also gives flame test fail • Still no safe way to neutralize methyl chloride contaminated units • Repair is uneconomic due to system damage • c.100 main service depots and c.500 independent service companies worldwide.
Flame Halide Lamp Normal Flame – blue color Chloride contamination
Environmental Issues • Presentation has primarily focused on the issue of safety and operational impact • A delegate in Antwerp challenged if our testing considered environmental issues • Estimated that 10-20 mg of gas are needed for flame halide test • For GC analysis, only 1 – 2 cm3 of gas required • Licensed engineers in Europe, concerned about local regulation and losing their license
Action Summary • Eliminate contaminated supplies of gas from service network – this is critical. • Identify clean and contaminated refrigeration units • Remove CFC/HCFC contamination • Find cost effective solutions for neutralising methyl chloride contamination
The Future 4. • Controlling or eliminating global supply • Find cost effective and quick test methods to enable check at every service event for all units Challenges – Fake Refrigerants
FutureChallenges – System Design • Cyclopentane blown insulation has 10% more heat leakage than R141b foam • Existing machinery will use more power to hold the same temperature • Exceptional demands for refrigerated containers in ambient temperature ranges and cargo requirements • System efficiency and power consumption
Future Design Options & Requirements • Improved insulation efficiency – new blowing agents? • Hydocarbons – Propane • Dismissed due to flammability issue on ships • CO2 systems: • complete system change • can it meet range of performance requirements? • can power consumption match R134a performance?
Future Design Options & Requirements • HFOs – 1234yf • use similar system design • retrofit to R134a systems? • higher cost than R134a will encourage use of fakes • future legislative issues?
Conclusion • Fake/contaminated refrigerants caught the industry by surprise. • Risk of injury or death to staff • Ongoing big cost and service disruption implications • Shipping is a highly competitive and cyclical business • Many players globally
Conclusion • COA’s challenge is to provide coordination on this project with the support of other organizations • Ships are isolated at sea and restricted access in port • Relatively small global service network • We have some confidence that the inadvertent use of contaminated and banned refrigerants in the shipping industry can be brought under control Thank you