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Contamination of Refrigerated Container Systems

UNEP - Joint Meeting of the Regional Ozone NetworkFor South Asia, Southeast Asia and the Pacific

Paro, Bhutan, May 2012

Mark Bennett Container Owners Association - COA

Triton Container International

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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)

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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

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Agenda

1. Refrigerated Containers

2. Fake Refrigerants and Explosions

3. Shipping Industry response

4. The Future

New Refrigerated Containers at a factory in China

Refrigerated Containers1.

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 Container being ‘Pre Trip Inspected’

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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)

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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

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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

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Fake Refrigerants & Explosions2.

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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

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Explosions in Vietnam April 2011

• 2 units explode in 2 days

• Both units under PTI - service

• Units had gas service 3-4 weeks before

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Vietnam incidents…

• Authorities sealed off the terminal

• Very little evidence available

• Initial conclusion: possible leak testing with Oxygen

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US West Coast incident

Engineer reports gas burning spontaneously in air – August 2011

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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

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Brazil incident

Unit serviced Vietnam then R134a recharged in transit Unit moved to BrazilEngineer identifies low gas and connects R134a supply during service Explosion of compressor similar to Vietnam No aluminum components remaining

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China incident

• Similar damage to Vietnam explosions

• White Aluminium Oxide visible

• Technician moved away from machine to take a phone call

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China incident - 2

• Corrosion to stainless steel lining

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Other Industries

• 2009: public transport company in 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

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Other Industries

Bus air-con unit :

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Fake Refrigerant

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Fake Refrigerant 2

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DuPont – Fake Gas TankORIGINAL

DuPont R134aFAKE

Dupont R134a

Dupont spelled with lower case “p” instead of “P”

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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

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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 → trimethyl aluminium (TMA) + aluminium chloride

6 CH3Cl + 4 Al → Al2(CH3)6 + 2 AlCl3

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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?

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Shipping Industry Response3.

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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.

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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

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Current Test Programme

1. Testing gas bottles on ships and in depots

2. 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.

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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.

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Flame Halide Lamp

Normal Flame – blue color Chloride contamination

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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

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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

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The Future

• Controlling or eliminating global supply

• Find cost effective and quick test methods to enable check at every service event for all units

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Challenges – Fake Refrigerants

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Future Challenges – 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

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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?

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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?

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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

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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