1.0 key issue review mb - conglobal gas seminar 05.2012
TRANSCRIPT
C t i ti f R f i t dContamination of Refrigerated Container SystemsContainer Systems
Review of Key Issues
Presented by Mike Baldwinid d C O f C Gl b l d i
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President and CEO of ConGlobal IndustriesMay 1, 2012
Introduction and Background
ConGlobal Industries
• 23 Locations – Three Countries
20 000 G t M / W k• 20,000+ Gate Moves / Week
• 150,000 TEU Storage Capacity
• 800 International Employees
• 3,000+ Reefer Repairs / pretrips / week
• Dealership for all reefer manufacturers in various ConGlobal locations
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Introduction and Background
Container Owners Association (COA)www.containerownersassociation.org www.containerownersassociation.org
• Trade Association with 300 members +/‐
• Coordinating International initiatives with TT Club, CRT, IICL, Reefer M f SS Li L d O h I d E (iManufactures, SS Lines, Lessors and Other Industry Experts (ie: DuPont)
• Hosted four educational sessions
• 2011 ‐ Hamburg and London
• 2012 ‐ Singapore and Antwerp
• Depot division role
• Vetting various testing methods
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• Global testing and contamination survey
Agenda
• History of incidentsHistory of incidents • Understanding the chemistry and theories• Experience of other industriesExperience of other industries
• Global efforts to eliminate counterfeit supplyGlobal efforts to eliminate counterfeit supply• Identify clean and contaminated units• ConGlobal policies and procedures• ConGlobal policies and procedures
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First Cases in Vietnam April 2011
• Two units exploded in two daysdays
• Both units under PTI
• Units had gas service three• Units had gas service three to four weeks before
• Authorities sealed off terminal
• Very little evidence availableavailable
• Conclusion – Possible leak testing with oxygen
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North America Incident
Engineer reports gas burning spontaneously in air – August 2011
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North America Incident
• Opening high pressure valve on compressor – liquid emerging started burning
• Samples taken from the compressor showed:compressor showed:
• R134a – 32%• R40 – 6%• R133a – 11 5%• R133a – 11.5% • TMS – 12%• Neopentane – 13%• Isobutane – 2 6%Isobutane 2.6%• trace quantities of several
other gases
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Gas extraction and testing was done by McCampbell Analytical Labs (www.mccampbell.com)
South America Incident – Fall 2011
• Engineer identifies low gas• Engineer identifies low gas and connects R134a supply during PTI
• Explosion of compressor
• Samples taken for forensic analysis – compressor now at CRT (Cambridge, U.K.)
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South America Incident ‐ Continued
• Compressor filled with• Compressor filled with black sludge
• No aluminum componentsNo aluminum components remaining
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South America Incident ‐ Continued
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Other Units
• Lack of aluminum components remaining
• Most machine types have been affected
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China Incident
• Similar damage to• Similar damage to Vietnam explosion
• White AluminumWhite Aluminum Oxide visible
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China Incident ‐ Continued
Corrosion to stainless steel lining
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Other Industries – Affected
• 2009: Public Transport Company, Southern Bus A/C Unit
Europe• Several injuries (poisoning and explosion)• AC hoses and seals disintegrated • POE oil, belt driven compressors , p
• 2009: Fridges, Germany• Product recall• Hermetic compressors• Hermetic compressors
• 2010: Vehicles • Currently in investigation• PAG oil, belt driven compressors
• 2012: Commercial Refrigeration, Australia• Product recall
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• Product recall
Chemistry – Theory
• Fake gas contains 50% R40 (methyl chloride or chloromethane)
• R40 reacts quickly with aluminum components in compressor
• Chloromethane + aluminum• Chloromethane + aluminum
trimethyl aluminum + aluminum chloride
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TMA – trimethyl aluminum
• Pyrophoric in air and water – burns spontaneously
• Melts at 15ºC, boils at 127ºC
• Powerful reducing agent
• Reacts strongly with :
• Water, oxidizers, alcohols, amines, amides, inorganic hydroxides, carbon dioxide, carbon tetrachloride, halon, halogens and halogenatedhydrocarbons, oxides of nitrogen or sulpher, y , g p ,phenols and many others
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Chemistry Theory Continued
• Chemistry is complex and remains somewhat unclear
• Many variables – Quantity and makeup of counterfeit gas, and make/model of reefer
POE il l l• POE oils play a role
• Low pressure (or vacuum) possible by R40 converting to solid/liquid TMAsolid/liquid TMA
• TMA reacts with R134a further reducing pressure as TMA forms in the systemy
• Idle compressor – TMA may build up when R134a has been ‘used up’
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Coupon Test – Pressure Rise
• Pressure rise from reactions can exceed compressor maximum operating• Pressure rise from reactions can exceed compressor maximum operating pressure and may cause rupture to occur
• Higher temperature = higher pressure rise
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• POE oil contributes to pressure rise
Copyright © 2012 Carrier Transicold, “All Rights Reserved.”
Coupon Test – Gas Sample
19 Copyright © 2012 Carrier Transicold, “All Rights Reserved.”
Possible Causes of Explosion
• New R134a added may react strongly with TMA in compressor probably causing an HF reaction (hydrogencompressor probably causing an HF reaction (hydrogen fluoride)
• Air in the system may start a chain reaction with TMA leading to an explosion:
• Moisture enters the system leading to explosion
• Ultra high temperatures / pressures possible when operating a contaminated unit
• Other ignition source (i.e. internal spark)
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Signs to Watch For
• Slight Gas – Dark and Cloudy or “Foamy”• Unusual noise from compressor – knocking and buzzing
• Unusually high compressor temperature
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Fake Gas Supply
• In other industries, supply of fake R134a found in Asia, Middle East and Southern Europe
• In our industry, fake R134a found in Africa, China, Philippines, Spain and Vietnam
l d h d d l f d b d d/• Gas cylinders on ships tested and also found to be contaminated and/or counterfeited
• Gas manufacturers confiscated fake product and are working to prosecute counterfeits
• Russian authority confiscated 1150 cylinders totaling 19 tonnes of counterfeit R134a gascounterfeit R134a gas
• At least three different types of fake gas found with only one containing R40
• Other gases used: R12, R22, R30, R142b
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g , , ,
Fake Refrigerant
Note: DuPont spelled with lower case “p Dupont”
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DuPont – Fake Gas Tank
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DuPont – Fake Gas Tank
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Testing for R40 and Chloride in Gas
• VOC Detectors (volatile organic compounds) d ’ k i h R40most don’t work with R40
• Infra Red Analyzers – difficulty in distinguishing between R134a and R40
• Halide Flame Test – sensitive to 300 PPMHalide Flame Test sensitive to 300 PPM• Dangerous gas emitted
G S iff T b iti t 10 PPM• Gas Sniffer Tubes – sensitive to 10 PPM
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Testing for R40 – Gas Chromatography
b O l i i d• Laboratory Only – Requires trained VOC Chemist to competently operate
• Test cost of $250.ºº / $350.ºº (Lab costs)
• Perform GC after positive chloride test
• Use MS – Mass Spectrometry –Use MS Mass Spectrometry Open Scan
• http://www.mccampbell.com/
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McCampbell GC‐MS Lab Summary
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COA Global Test Survey – Sample Size
• Period – December 2011 – May 2012
• Sample size 744• Sample size ‐ 744
• Location – seven cities in four regions (Europe, M i N Z l d d U it d St t )Mexico, New Zealand, and United States)
• Container Owners – 17 Shipping Lines/Lessors
• If a unit failed the field test, a GCMS test was performed
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COA Global Test Survey – Test Results
Flame TestUnits Not Serviced Vietnam
% of Units Not Serviced in Vietnam
Units Serviced in Vietnam
% of Units Serviced in Vietnam
Failed * 42 13% 49 12%
Passed 287 87% 366 88%
Grand Total 329 415
* Positive chloride contamination** no TMA identified in GCMS tests (to date)( )** 1 TMS contamination identified in GCMS test
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COA Global Test Survey – Test Results
– HCC40 – R152a
In addition to R134a, samples also contained:– HCC40
– R11
– R12
– R14
– R152a
– Bromomethane
– 1‐Nitro‐propane
– 5 6‐dimethyl‐5 6‐dicarbadecaborane– R14
– R22
– R112
R113
– 5.6‐dimethyl‐5,6‐dicarbadecaborane
– FC1131
– FC1122
FC133a– R113
– R122
– R123
R124
– FC133a
– Isobutane
– Neopentane
Tetramethysilane– R124
– R132a
– R134b
R142b
– Tetramethysilane
– Methylbutane
– 1,1‐Dichlorethane
Trichlororthene
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– R142b
– R143a
– Trichlororthene
Summary – “What Have We Learned?”
• All Counterfeit gas found to date have chloride containing component gasses
• Chlorinated gas will reduce the performance and useful life of reefers (particularly aluminum components)
• Some chlorinated gas (i.e. R40) is very aggressive and can create extremely dangerous conditions (TMA‐TMS – other?)
Chl i t d (i l di R40) h b f d i Vi t• Chlorinated gas (including R40) has been found in non Vietnam serviced reefers
• Chlorinated gas can be safely and reliably screened for by typical field applications
• Exact chemistry and causes of past explosions (or potential future explosions) is not 100% clear or certain
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explosions) is not 100% clear or certain
ConGlobal Policies Developed To:
• Ensure worker safety
• Mitigate the introduction and proliferation of counterfeit g pgas or contaminated gas
• Safeguard customer equipment
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R134a Refrigerated Container Technicians Handbook
• New R134a bottle testing procedures
• Other operating safety policies and procedures
• Start up protocolp p
• Schrader valve protocol
• Safe Gas Extraction and Field testing of R134a (C‐GEARS)Safe Gas Extraction and Field testing of R134a (C GEARS)
• Code of conduct for reefer gas handling – All ConGlobal Technicians – Mitigate the introduction and spread of contamination
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Th k YThank YouQuestions?Questions?
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