co2 safety
TRANSCRIPT
Welcome to BOCWelcome to BOCCarbon Dioxide SafetyCarbon Dioxide Safety
Training ProgramTraining Program
Presented byBOC
NATIONAL TRAINING CENTER
...this seminar is designed to give participants abetter understanding of the properties,
characteristics, hazards, and installationprocedures associated with carbon dioxide.
Our mission is for you to leave this session withnot only an increased skill level but, with an
added confidence in your ability to work safely.
QUESTION:QUESTION:
WHAT DO WE INTEND TOWHAT DO WE INTEND TOACCOMPLISH IN THIS SEMINAR?ACCOMPLISH IN THIS SEMINAR?
ANSWER:ANSWER:
ELIMINATE PREVENTABLEELIMINATE PREVENTABLEACCIDENTS THROUGHACCIDENTS THROUGH
EDUCATION!!!EDUCATION!!!
WHY?WHY?
BECAUSE INFORMEDBECAUSE INFORMEDEMPLOYEES CREATE A SAFEREMPLOYEES CREATE A SAFER
WORKPLACE!!!WORKPLACE!!!
HowHow will this be accomplished? will this be accomplished?
LEARNING OBJECTIVESExplore what you knowSee where you need to expand yourknowledgeObtain a general knowledge about the CO2industryHave some fun while you learn
1929: Air Reduction gained controlling interest of thePure Carbonic Company.1930: Pure Carbonic Company acquired assets andbusiness of National Carbonic Gas Company of NewJersey.1934: Pure Carbonic Company & its subsidiary Dry IceInc., purchased American Dry Ice Corporation.1935: Air Reduction acquired remaining shares ofPure Carbonic company.1936: Pure Carbonic Company becomes PureCarbonic, Inc.
BRIEF BOC/CO HISTORY
1967: Pure Carbonic consolidated into the AIRCOIndustrial Gases Division.1979: BOC Gases acquires AIRCO.1986: AIRCO Carbon Dioxide split from AIRCOIndustrial Gases.1987: AIRCO Carbon Dioxide division is formed.1989: AIRCO acquires Americas CO2 division.1995: AIRCO switches name to BOC Gases.1995 BOC acquires ADM CO2 product.
BRIEF BOC/CO HISTORY
It is a compound formed by the combination of carbonand oxygen atoms in a 1:2 ratio . Proportioned byweight of about 27.3% carbon to 72.7% oxygenIt is expressed by the chemical symbols CO2
It is present in the atmosphere at a concentration of0.03 percent by volumeIt is a normal product of human metabolismIt is a gas at normal atmospheric temperature andpressureA slightly acidic gasRelatively non reactive and non toxic
WHAT IS CARBON DIOXIDE?
Synonym: Carbon anhydrideDOT Classification: Non flammable gasDOT Label: Non flammable gasTransport Canada Classification: 2.2UN Number: UN 1013 (compressed gas)
UN 2187 (refrigerated liquid) UN 1845 (solid)
WHAT IS CARBON DIOXIDE?
PHYSICAL STATES OF CO2SolidLiquidGas
CARBON DIOXIDEChemical symbol: CO2
Molecular weight: 44.01Color: vapor-none, solid-translucent whiteOdor: slightly pungent odortaste: bitingSpecific gravity: 1.5289 @ 1 atm @ 70 °F
CARBON DIOXIDE Density, lbs/ft3:
solid: -109.25 °F = 97.6 lb/cu. ft.liquid: +1.7 °F, 300 psig = 63.36 lb/cu. ft.liquid: 70 °F, 830 psig = 47.35 lb/cu. ft.liquid: -69.8 °F = 73.5 lb/cu. ft.
Specific volume, lbs/ft3 :8.57 @ 1 atm @ 60 °F8.74 @ 1 atm @ 70 °F
Normal boiling point: -109.35 °F
Carbon dioxide is stable and relatively inertSpecific heat-gas-varies (at constant pressureof 1 atmosphere):
70 °F.........................................0.20 BTU/lb(at constant volume)...............0.15 BTU/lb
CHEMICAL PROPERTIES
CHEMICAL PROPERTIES Viscosity-gas at atmospheric pressure
& 70 °F temperature.............0.015 centipoise liquid at 0 °F..........................0.14 centipoise
Dissolved in water, carbon dioxide formscarbonic acid (H2CO3)
Becomes chemically active in moisture or highheat
HEAT OF VAPORIZATIONSolid: -109.25 °F = 246.6 BTU/lbLiquid: +1.7 °F, 300 psig = 119.2 BTU/lbLiquid: +70 °F, 839 psig = 63.9 BTU/lb
TRIPLE POINTTemperature/pressure combination at whichcarbon dioxide can exist simultaneously as asolid, liquid, or gas:
-69.83 °F 60.4 psig
CRITICAL POINTHighest temperature & pressure at which carbon
dioxide can remain a liquidCRITICAL TEMPERATURE
87.82 °FCRITICAL PRESSURE
In lbs per sq. in. abs.: 1071.6
SOLUBILITY OF CARBON DIOXIDEReadily dissolves in most liquidsAmount is affected by temperature and pressureUnder normal conditions water dissolves its ownvolume of carbon dioxideThe greater the pressure, the more CO2 a liquid canholdOnce the pressure is released, CO2 escapes in theeffervescent characteristic of uncapped soft drinksThe colder the liquid, the more CO2 it can holdCarbon dioxide flows downhill, settles in the bottom,and displaces air
CO IN HIGH TEMP CONDITIONS+1200 °F CO2 dissociates into carbonmonoxide and free O2
Degree of dissociation:0.000025% at 1340 °F2.1% at 3134 °F
The reaction readily reverses as thetemperature dropsAt these levels, the gas reacts with carbon andcertain metals
Carbon Dioxide is obtained as a by-product from one ofseveral sources:
Ammonia PlantsFermentation ethanol plantsHydrogen Plants within refineriesEthylene oxideNatural gas process plantsExtractions from flue gases from the burning ofnatural gas or fuelsIn some parts of the South and Southwest, CO2 isobtained from CO2 wells at extremely highconcentrations and pressures
PRODUCTION
Feed gas collectionCO2 compressionPurification and liquefactionRefrigeration for the liquefier unitStorage of product liquid carbon dioxideRecompression of flash carbon dioxideReactivation of dryers and adsorber dryersCarbon filterShipment of product liquid carbon dioxide
PRODUCTION PROCESS
LIQUEFYING CARBON DIOXIDEAll impurities and foreign odors are removedfrom the gasGas is compressed and condensed usually at240 psi with ammonia refrigerationPurified liquid CO2 is shipped to customers inbulk form or converted into solid dry ice orpellets
I. REFINERY AND AMMONIA PLANTS - (REFORMERS)
CH4 + 2H20 CO2 + 4H2METHANE + STEAM CO2 + HYDROGEN
METHANE (CH4)STEAM
NATURALGAS
STEAMREFORMER
ADSO
RB
ER
H2
STR
IPP
ER
STEAM
SO
LVE
NT
CO2 TOBOC
CO2 AND SOLVENT
TYPICAL SOLVENTS - CATACARBMEARECTISOLSELEXOLPOTASSIUM CARBONATE
II. ETHANOL PLANTS - FERMENTATION
C6H12O6 + YEAST 2C2H5OH + 2CO2DEXTROSE ETHANOL
CO2 TOBOC
ETHANOL &DDGS
FERMENTERS
CORN MASH& YEAST
BATCH OR CONTINUOUSFERMENTERS
III. ACID NEUTRALIZATION
CaCO3 + H2SO4 CO2 + CaSO4 + H20ARAGONITE LIMESTONE + SULFURIC ACID CO2 + GYPSUM + WATER
CO2 TO BOC
SULFURIC ACIDH2SO4
ARAGONITELIMESTONECaCO3
WASTE ACIDNEUTRALIZATION TANK
GYPSUM
IV. COMBUSTION/COGENERATION
AIR(02 + N2)
CH4 + 2 (O2 + N2) CO2 + 2 H20 + 2N2FUEL + AIR CO2 + WATER + N2
H20
FUEL(NATURAL GASOIL OR COAL)
CO2 TO BOC
N2
ADSORBER STRIPPER
SO
LVE
NTFLUE GAS CO2 +H20+N2
CO2 AND SOLVENT
TYPICAL SOLVENTS - CATACARBMEARECTISOLSELEXOLPOTASSIUM CARBONATE
V. CO2 NATURAL WELLS
HIGH PRESSURECO2 PIPELINE TO BOC PLANT
EARTH
HIGH PRESSURECO2 DOME
500’ TO 10,000’
THE PROCESSEach CO2 plant is built specifically to handlethe type of impurities found in the particularfeed gas
The standard grade purity for bulk liquid is defined as:Maximum Impurities Parts per Million by Volume
Minimum % Purity 99.9 Carbon Monoxide 10Inerts 1000 Hydrocarbons (non-volatile) 10Hydrocarbons (Volatile) 50 NOx 5Water 32 Sulfur Dioxide 5Oxygen 30 Carbonyl Sulfide 0.5Ammonia 25 Hydrogen Sulfide 0.5
PURIFICATION METHODSZinc Oxide BedsDryersAdsorbersNoble Catalyst BedsCarbon BedsMolecular Sieve BedsWater Wash ColumnsPotassium Permanganate Beds
MAIN PROCESS COMPONENTSPurificationCompressionChilling (either by ammonia or freon)Removal of inertsLiquefaction
BASIC PROCESS FLOWSHEET
Water
CO2
Feedgas
WaterSolubles
KMnO4Column
SulfurCompounds
OrganicsandHydrocarbons
Catalytic Combuster
CompressorZincOxideBed
H2SRemoval
OrganicRemoval
CarbonBeds
Driers
Removal of TraceQuantities of all impurities
Ammonia
CO2Condenser
DistillationColumn
Noncondensibles
Pure CO2 (L) Guard Carbonor 13x Bed
CO2 Tank
Trailer or RailCar Fill
WaterWash Column
GRADES AND PURITYCylinder Gas: industrial grade @ 70 °F
CO2 99.5% minimumWater 25 °F dew point or drier (130 ppm by weight)
Cylinder gas: welding gradeCO2 99.5%Water -40 °F dew point (97 ppm by weight)
Bulk liquid: standard gradeCO2 99.98% minimumWater 60 °F dew point or drier (34 ppm by volume)Oil 1 ppm by weight maximumDry ice may have up to 25 white oil or propylene glycol
CO GRADE 4.5 RESEARCHMAXIMUM IMPURITIES--PARTS PER MILLION BY VOLUME
Maximum % Purity 99.995Argon 5Carbon Monoxide 1Helium 4Hydrogen 4Krypton 0Neon 0Nitrogen 20Oxygen 4Nitrous Oxide 4THC 5Dew Point °F -86Total hydrocarbons expressed as methane.
CARBON DIOXIDE HAZARDSHeavier than air-accumulates in low or confined areasAsphyxiant− Even in normal concentrations of oxygen carbon
dioxide can paralyze the respiratory system− Concentrations of 10% CO2 or more can cause
unconsciousness or deathThe seriousness of the symptoms of asphyxiationexperienced depends on the concentration levels andlength of exposureCarbon dioxide should only be used in areas with goodventilation
POTENTIAL HAZARDSSafety relief valvesBall valvesLines anchored firmlyExpansion & shrinkage of linesUnauthorized personnelStatic electricityFlexible hosesConfined spaceAsphyxiation
SYMPTOMS OF ASPHYXIATIONHeadachesSweatingRapid breathingIncreased heart beatShortness of breathDizzinessBlurred visionShakingMake it difficult to leave the area
Group Classification Numberof
Fatalities
Toxic Atmospheres in confined work spaces 82
Asphyxiating atmospheres in confined work spaces 67
Other hazards present in confined work spaces 24
TOTAL FATALITIES 173
(not all due to nitrogen/argon)
FATALITIES DUE TO ASPHYXIATION
PREVENTATIVE MEASURESExercise caution when entering areas toensure proper oxygen/ CO2 levelsMonitor levels in all such areasAn alarm should be sounded if either theoxygen level drops or CO2 levels risesDuring down time and maintenance use:− Entry permits− Lock out procedures− Confined space entry standards
PREVENTATIVE MEASURES All equipment using CO2 must be equippedwith a properly designed exhaust system System design must ensure that CO2concentrations in work areas never exceedsthe allowable exposure limits Monitors may be set up to not only sound analarm but turn on ventilation if needed (doneby customer only).
EXPOSURE TO CARBON DIOXIDEResponse varies from person to personIt is not constant with the same person atdifferent timesSince CO2 is the regulator for the body’sbreathing, a change in levels will cause animmediate responseExertion will burn oxygen content within aperson, thus increasing the body’sconcentrations of CO2
EMPLOYEE EXPOSURE LIMITS FOR CO2
AGENCY MAXIMUM CONCENTRATION(IN AIR)
EXPOSURE TIME LIMIT
Occupational Safety andHealth Administration
1/2% or 5,000 parts per million(ppm)
Per 8 hour work shift/40 hour week
American Conference ofGovernment IndustrialHygienists
3% or 30,000 parts per million(ppm)
5% or 50,000 parts per million(ppm)
15 minute period
immediately dangerous to life andhealth (IDLH)
HANDLING LEAKS & EMERGENCIESVentilate areas to prevent the formation of toxicconcentrations of carbon dioxide.If carbon dioxide content exceeds 3% you must wearan SCBA to enter that area.Avoid contact of the skin or eyes with cold carbondioxide.Evacuate the immediate area if the leak is large.If water spray is used to dissipate leak, a dense fogmay form as well as carbonic acid.Leak will dissipate itself given time if the ambianttemperature is above freezing.
PREPARING FOR AN EMERGENCYPre-arranged emergency plan including:
TransportationMedical attentionFirst aid techniques for CO2
Evacuation planPerimeter security
Personnel should be trained to use approved skinand respiratory protectionPersons required to shut off the CO2 source shouldbe properly trained and adequately protected
COLD CONTACTSolid (dry ice) and liquid CO2 are normallyvery cold. Contact with these may result infrostbiteContact could also result in lesions or moreserious injury from deep freezing of thetissuesContact should also be avoided with gaseousCO2 coming out of a pressurized containersince this gas can also be very cold
FIRST AID FOR COLD CONTACTFrozen tissues are painless and appear waxyyellowRemove restrictive clothing and immerseaffected part in warm water (approximately105°F)Do not rub frozen parts, tissue damage mayresultNever use dry heat
If the exposure has been massive and generalbody temperature is depressed, immerse patientin a warm water bathSupportive treatment for shock should beprovidedMedical assistance should be obtained as soon aspossibleIf the frozen part thaws before medical attention isobtained, cover with loose, dry, sterile dressingAlcoholic beverages or smoking are prohibited.Warm drinks and food may be administered
FIRST AID FOR COLD CONTACT
CARBON DIOXIDE SAFETY APPARELWear clothing resistant totemperatures of -109 °FLoose fitting glovesSteel toed shoesHard hatEar protectionEye protectionLong sleeves (should not berolled up while working )
CARBON DIOXIDE APPLICATIONSDry ice pelletsCarbonationRefrigerationCrude Oil RecoverypH controlDeflashingIndustrial cleaning
ElectronicsPreservingBaked goods manufacturingFumigationInert blanketing and purgingShielding gasSolvent
CARBON DIOXIDE APPLICATIONS
CARBON DIOXIDE APPLICATIONSMetallurgy (steel making)TextilesPressurizationPapermakingPlasticsAgricultureHorticultureChemical
LIQUID LEVEL GAUGESDifferential pressureDensityNPSHDead leg
CARBON DIOXIDE RECEIVERCONFIGURATION
VESSEL
PRESSURE
INSULATION
PIPING
PRESSURE BUILDINGVAPORIZER
COOLING
HORIZONTAL/VERTICAL
CARBON STEEL
350 PSIG (MAX)
FOAMBLOCKSPRAY
SCHEDULE 80 CARBON STEEL
ELECTRICAUXILIARY
MECHANICAL
SPECIFICATIONS ON TOMCO EQUIPMENTStorage unit capacities: from one ton to 100 ton orgreater.Pressure vessel: ASME coded for maximum workingpressure of 350 psig, Code Specifications V1 1 1,Division 1.Piping: schedule 80 seamless pipe, 2,000 lb. forgedsteel fittings, ball type valves.Safeties: ASME approved direct spring loaded or pilotoperated, sized for unconfined outdoors installations.Insulation: 4” polyurethane.Outer jacket: 063” aluminum.
TOMCO STORAGE VESSELSVaporizers (optional): Steam or electriccapacities to 6,000 lb./hr and greaterLiquid level gauges: Differential pressureindicators. Usually Barton gauges.Pressure gauges: 0-600 psig with 6” dialStyle: Vertical or horizontalMinimum design temperature: -40 °FElectrical: 208, 230/460 three-phase 60 cyclesUL listed components
MAINTAINING PRESSURE IN LIQUID CO2RECEIVERS - HORIZONTAL CONFIGURATION
CARBON DIOXIDE DELIVERY PIPING
PB SIDEARM VAPORIZER
STEAM VAPORIZER
DIRECT TO PROCESS VAPORIZER
FIGURE 2
GENERAL SITE REQUIREMENTSAtmospheric conditionsClearance from exposuresUnderground interferenceOverhead interferenceTrailer access
UTILITIESElectricalPhoneLighting
REGS GOVERNING INSTALLATIONSFederal LawsState and Local LawsBoiler Pressure Vessel LawsIndustry GuidelinesInsurance CompaniesOther Experience
GUIDELINES & AGENCIESBOCA: Building Officials Code AssociationCGA: Compressed Gas AssociationNFPA: National Fire Protection AssociationOSHA: Occupational Safety Health
AdministrationUFC: Uniform Fire CodeNEC: National Electric CodeSFPC: Standard Fire Prevention Code
SBCCI: Southern Building Code Congress International
UBPVL:Uniform Boiler and Pressure Vessel Laws
ASME: American Society of Mechanical Engineers
ANSI: American National Standards InstituteFDA: Food & Drug AdministrationBOC Gases Installation StandardsBOC Gases National Training Center
GUIDELINES & AGENCIES
CGA REGS FOR COCGA G-6 “Carbon Dioxide”CGA G-6.1 “Standard for Low Pressure Carbon DioxideSystems at Customer Sites”CGA G-6.2 “Commodity Specifications for CarbonDioxide”CGA G-6.3 “Carbon Dioxide Cylinder Filling andHandling Procedures”CGA G-6.4 “Safe Transfer of Low Pressure Liquefied Carbon Dioxide in Cargo Tanks, Tank Cars, and Portable Containers”CGA G-6.5 “Standard for Small Stationary LowPressure Carbon Dioxide Systems”
CGA HB-3 “Handbook of Compressed Gases”CGA P-1 “Safe Handling of Compressed Gases in
Containers”CGA P-14 “Accident Prevention in Oxygen-Rich and
Oxygen-Deficient Atmospheres”CGA S-1.1 “Pressure Relief Device Standards
(Cylinders for Compressed Gases)”CGA S-1.2 “Pressure Relief Device Standards (Cargo
and Portable Tanks for Compressed Gases)”CGA S-1.3 “Pressure Relief Device Standards
(Compressed Gas Storage Containers)”
CGA REGS FOR CO
EQUIPMENT AND COMPONENTSSuitable for temperatureSuitable for pressureCompression fittingsStainless steelMaterial constructionLeak rate
SUITABLE MATERIALS FOR COSchedule 80 threaded steel pipeForged steel fittings rated at 3000 psfSeamless schedule 40 steel pipe, welded jointsStainless steelCopperBrass
LABELING AND MARKINGSThe Corporate Identification LogoProduct IdentificationCAS NumberUNC NumberSafety Venting DecalsProduct Hazard Warning
Pipeline LabelingAuthorized PersonnelPressure Vessel IdentificationCorporate Identification NumberEmergency Information Valve and ComponentIdentificationAnnual Safety Inspection
LABELING AND MARKINGS
Carbon dioxideCauses severe burnsLiberates a gas which may cause suffocationAvoid contact with skin and eyes-- do not tasteDo not put in stopped or closed containersUse and store only in well ventilated areasLiquid under pressureEmergency phone numbers
SIGN INFORMATION
EQUIPMENT INSPECTION POLICYEquipment must be inspected yearlySafeties must be changed out and re-testedevery five years
CUSTOMER TRAININGMSDS (Material Safety Data Sheet)General site reviewEmergency contact information
REFRIGERATION LAWSREFRIGERATION LAWS
To remove refrigerant in any condition from asystem and store it in an external container
without necessarily testing or processing it inany way.
RECOVER
To reduce contaminants in used refrigerant byoil separation, non-condensable removal and
single or multiple passes through deviceswhich reduce moisture, acidity and
particulate matter, such as replaceable corefilter-dryers. This term usually applies to
procedures implemented at the field job siteor in a local service shop.
RECYCLE
To reprocess refrigerant to new productspecifications by means which may include
distillation. Chemical analysis of therefrigerant is required to determine that
appropriate product specifications are met.This term usually implies the use of
processor or procedures available only at areprocessing or manufacturing facility.
RECLAIM
FACTORS-RECOVERED REFRIGERANTReason system is being servicedCondition of refrigerant and systemEquipment manufactures' policiesRefrigerant cleaning capability of recyclingequipmentFeasibility and owner's preference
RECOVERED REFRIGERANT OPTIONSOption 1: Put refrigerant back into the system withoutrecycling it.Option 2: Recycle refrigerant and put it back into thesystem from which it was removed or back into asystem with the same owner.Option 3: Recycle the refrigerant, test to verifyconformance to ARI Standard 700 prior to reuse in adifferent owner's equipment provided that therefrigerant remains in the contractor's custody andcontrol at all times from recovery through recycling toreuse.Option 4: Send refrigerant to a certified reclaimer
CONTAMINANT LEVELSBecause there are no means at this time todetermine all contaminant levels (other than bylaboratory testing), assurance that thesecontaminant levels are not exceeded can beaccomplished by:
The proper use and maintenance of refrigerantrecovery/recycling equipment that is capable ofrecycling refrigerants to or below the levels in thetable orLaboratory analysis (the appendix to ARIStandard 700 describes laboratory analysisprocedures).
MAXIMUM CONTAMINANT LEVELS-RECYCLEDREFRIGERANT / SAME OWNER’S EQUIPMENT
CONTAMINANTS LOWPRESSURESYSTEMS
R-12 SYSTEMS ALL OTHERSYSTEMS
Acid Content byWeight
1.0 ppm 1.0 ppm 1.0 ppm
Moisture by Weight 20 ppm 10 ppm 20 ppm
Non Condensable Gas(By Volume)
N/A 2.0 percent 2.0 percent
High Boiling Residues(vol.)
1.0 percent .02 percent .02 percent
Chlorides by SilverNitrate test
No turbidity Visually clean Visually clean
Particulate Visually clean Visually clean Visually cleanOther Refrigerants 2.0 percent 2.0 percent 2.0 percent
SALE OF REFRIGERANTSUsed refrigerants shall not be sold, or used ina different owner's equipment, unless therefrigerant has been analyzed and found tomeet requirements of ARI Standard 700 (latestedition), “Specifications for Fluorocarbon andOther Refrigerants".
NITROGEN vs CARBON DIOXIDEBoth asphyxiants, but CO2 is considered toxicLiquid CO2 is not subject to the same level of refrigerantlosses associated with LN2Vacuum insulated pipe is sometimes considered necessaryfor longer LN2 lines (usually at twice the piping cost)Phase separators sometimes necessary for LN2 lines & forCO2 lines in chilling applicationsLN2 has a greater temperature difference available (-320 °Ffor LN2 vs -109 °FLN2 contains about 12% greater refrigeration capacity perunit weight than CO2For bulk tank installations, LN2 usually requires less capital