Welcome to BOC Carbon Dioxide Safety Training Program

Presented by BOC NATIONAL TRAINING CENTER

...this seminar is designed to give participants a better understanding of the properties, characteristics, hazards, and installation procedures associated with carbon dioxide.

Our mission is for you to leave this session with not only an increased skill level but, with an added confidence in your ability to work safely.

QUESTION:
WHAT DO WE INTEND TO ACCOMPLISH IN THIS SEMINAR?

ANSWER:
ELIMINATE PREVENTABLE ACCIDENTS THROUGH EDUCATION!!!

WHY?
BECAUSE INFORMED EMPLOYEES CREATE A SAFER WORKPLACE!!!

How will this be accomplished?

LEARNING OBJECTIVES
Explore what you know See where you need to expand your knowledge Obtain a general knowledge about the CO2 industry Have some fun while you learn

BRIEF BOC/CO HISTORY

1929: Air Reduction gained controlling interest of the Pure Carbonic Company. 1930: Pure Carbonic Company acquired assets and business of National Carbonic Gas Company of New Jersey. 1934: Pure Carbonic Company & its subsidiary Dry Ice Inc., purchased American Dry Ice Corporation. 1935: Air Reduction acquired remaining shares of Pure Carbonic company. 1936: Pure Carbonic Company becomes Pure Carbonic, Inc.

BRIEF BOC/CO HISTORY

1967: Pure Carbonic consolidated into the AIRCO Industrial Gases Division. 1979: BOC Gases acquires AIRCO. 1986: AIRCO Carbon Dioxide split from AIRCO Industrial 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.

WHAT IS CARBON DIOXIDE?

It is a compound formed by the combination of carbon and oxygen atoms in a 1:2 ratio . Proportioned by weight of about 27.3% carbon to 72.7% oxygen It is expressed by the chemical symbols CO2 It is present in the atmosphere at a concentration of 0.03 percent by volume It is a normal product of human metabolism It is a gas at normal atmospheric temperature and pressure A slightly acidic gas Relatively non reactive and non toxic

WHAT IS CARBON DIOXIDE?

Synonym: Carbon anhydride DOT Classification: Non flammable gas DOT Label: Non flammable gas Transport Canada Classification: 2.2 UN Number: UN 1013 (compressed gas) UN 2187 (refrigerated liquid) UN 1845 (solid)

PHYSICAL STATES OF CO2

Solid Liquid Gas

CARBON DIOXIDE
Chemical symbol: CO2 Molecular weight: 44.01 Color: vapor-none, solid-translucent white Odor: slightly pungent odor taste: biting Specific 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 F 8.74 @ 1 atm @ 70 F Normal boiling point: -109.35 F

CHEMICAL PROPERTIES
Carbon dioxide is stable and relatively inert Specific heat-gas-varies (at constant pressure of 1 atmosphere): 70 F.........................................0.20 BTU/lb (at constant volume)...............0.15 BTU/lb

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 forms carbonic acid (H2CO3) Becomes chemically active in moisture or high heat

HEAT OF VAPORIZATION
Solid: -109.25 F = 246.6 BTU/lb Liquid: +1.7 F, 300 psig = 119.2 BTU/lb Liquid: +70 F, 839 psig = 63.9 BTU/lb

TRIPLE POINT
Temperature/pressure combination at which carbon dioxide can exist simultaneously as a solid, liquid, or gas: -69.83 F 60.4 psig

CRITICAL POINT
Highest temperature & pressure at which carbon dioxide can remain a liquid CRITICAL TEMPERATURE 87.82 F CRITICAL PRESSURE In lbs per sq. in. abs.: 1071.6

SOLUBILITY OF CARBON DIOXIDE

Readily dissolves in most liquids Amount is affected by temperature and pressure Under normal conditions water dissolves its own volume of carbon dioxide The greater the pressure, the more CO2 a liquid can hold Once the pressure is released, CO2 escapes in the effervescent characteristic of uncapped soft drinks The colder the liquid, the more CO2 it can hold Carbon dioxide flows downhill, settles in the bottom, and displaces air

CO IN HIGH TEMP CONDITIONS

+1200 F CO2 dissociates into carbon monoxide and free O2 Degree of dissociation: 0.000025% at 1340 F 2.1% at 3134 F The reaction readily reverses as the temperature drops At these levels, the gas reacts with carbon and certain metals

PRODUCTION
Carbon Dioxide is obtained as a by-product from one of several sources: Ammonia Plants Fermentation ethanol plants Hydrogen Plants within refineries Ethylene oxide Natural gas process plants Extractions from flue gases from the burning of natural gas or fuels In some parts of the South and Southwest, CO2 is obtained from CO2 wells at extremely high concentrations and pressures

PRODUCTION PROCESS
Feed gas collection CO2 compression Purification and liquefaction Refrigeration for the liquefier unit Storage of product liquid carbon dioxide Recompression of flash carbon dioxide Reactivation of dryers and adsorber dryers Carbon filter Shipment of product liquid carbon dioxide

LIQUEFYING CARBON DIOXIDE

All impurities and foreign odors are removed from the gas Gas is compressed and condensed usually at 240 psi with ammonia refrigeration Purified liquid CO2 is shipped to customers in bulk form or converted into solid dry ice or pellets

I. REFINERY AND AMMONIA PLANTS - (REFORMERS) CH4 + 2H20 METHANE + STEAM STEAM REFORMER METHANE (CH4) STEAM CO2 + 4H2 CO2 + HYDROGEN H2 ADSORBER STRIPPER CO2 TO BOC SOLVENT

STEAM

NATURAL GAS

CO2 AND SOLVENT

TYPICAL SOLVENTS -

CATACARB MEA RECTISOL SELEXOL POTASSIUM CARBONATE

II. ETHANOL PLANTS - FERMENTATION C6H12O6 + DEXTROSE YEAST 2C2H5OH + 2CO2 ETHANOL

CO2 TO BOC

FERMENTERS

CORN MASH & YEAST BATCH OR CONTINUOUS FERMENTERS

ETHANOL & DDGS

III. ACID NEUTRALIZATION

CaCO3 + H2SO4 ARAGONITE LIMESTONE + SULFURIC ACID

CO2 + CaSO4 + H20 CO2 + GYPSUM + WATER

CO2 TO BOC

SULFURIC ACID H2SO4

ARAGONITE LIMESTONE CaCO3

WASTE ACID NEUTRALIZATION TANK

GYPSUM

IV. COMBUSTION/COGENERATION CH4 + 2 (O2 + N2) FUEL + AIR ADSORBER FLUE GAS CO2 +H20+N2 CO2 + 2 H20 + 2N2 CO2 + WATER + N2 N2 STRIPPER SOLVENT CO2 TO BOC

H20 AIR (02 + N2) FUEL (NATURAL GAS OIL OR COAL) CO2 AND SOLVENT

TYPICAL SOLVENTS -

CATACARB MEA RECTISOL SELEXOL POTASSIUM CARBONATE

V. CO2 NATURAL WELLS

HIGH PRESSURE CO2 PIPELINE TO BOC PLANT

EARTH 500 TO 10,000

HIGH PRESSURE CO2 DOME

THE PROCESS
Each CO2 plant is built specifically to handle the type of impurities found in the particular feed gas
The standard grade purity for bulk liquid is defined as: Maximum Impurities Parts per Million by Volume Minimum % Purity Inerts Hydrocarbons (Volatile) Water Oxygen Ammonia 99.9 1000 50 32 30 25 Carbon Monoxide Hydrocarbons (non-volatile) NOx Sulfur Dioxide Carbonyl Sulfide Hydrogen Sulfide 10 10 5 5 0.5 0.5

PURIFICATION METHODS
Zinc Oxide Beds Dryers Adsorbers Noble Catalyst Beds Carbon Beds Molecular Sieve Beds Water Wash Columns Potassium Permanganate Beds

MAIN PROCESS COMPONENTS

Purification Compression Chilling (either by ammonia or freon) Removal of inerts Liquefaction

BASIC PROCESS FLOWSHEET

Water Solubles Water Sulfur Compounds Organics and Hydrocarbons H2S Removal Organic Removal

CO2
Feedgas

Water Wash Column

KMnO4 Column

Catalytic Combuster

Compressor

Driers Ammonia

Zinc Oxide Bed

Carbon Beds

Noncondensibles

Distillation Column

CO2 Tank Trailer or Rail Car Fill

Removal of Trace Quantities of all impurities

CO2 Condenser

Pure CO2 (L)

Guard Carbon or 13x Bed

GRADES AND PURITY

Cylinder Gas: industrial grade @ 70 F
CO2 99.5% minimum Water 25 F dew point or drier (130 ppm by weight)

Cylinder gas: welding grade

CO2 99.5% Water -40 F dew point (97 ppm by weight)

Bulk liquid: standard grade

CO2 99.98% minimum Water 60 F dew point or drier (34 ppm by volume) Oil 1 ppm by weight maximum Dry ice may have up to 25 white oil or propylene glycol

CO GRADE 4.5 RESEARCH

MAXIMUM IMPURITIES--PARTS PER MILLION BY VOLUME

Maximum % Purity Argon Carbon Monoxide Helium Hydrogen Krypton Neon Nitrogen Oxygen Nitrous Oxide THC Dew Point F Total hydrocarbons expressed as methane.

99.995 5 1 4 4 0 0 20 4 4 5 -86

CARBON DIOXIDE HAZARDS

Heavier than air-accumulates in low or confined areas Asphyxiant Even in normal concentrations of oxygen carbon dioxide can paralyze the respiratory system Concentrations of 10% CO2 or more can cause unconsciousness or death The seriousness of the symptoms of asphyxiation experienced depends on the concentration levels and length of exposure Carbon dioxide should only be used in areas with good ventilation

POTENTIAL HAZARDS
Safety relief valves Ball valves Lines anchored firmly Expansion & shrinkage of lines Unauthorized personnel Static electricity Flexible hoses Confined space Asphyxiation

SYMPTOMS OF ASPHYXIATION
Headaches Sweating Rapid breathing Increased heart beat Shortness of breath Dizziness Blurred vision Shaking Make it difficult to leave the area

FATALITIES DUE TO ASPHYXIATION

(not all due to nitrogen/argon)
Group Classification Number of Fatalities 82 67 24 173

Toxic Atmospheres in confined work spaces Asphyxiating atmospheres in confined work spaces Other hazards present in confined work spaces TOTAL FATALITIES

PREVENTATIVE MEASURES
Exercise caution when entering areas to ensure proper oxygen/ CO2 levels Monitor levels in all such areas An alarm should be sounded if either the oxygen level drops or CO2 levels rises During down time and maintenance use: Entry permits Lock out procedures Confined space entry standards

PREVENTATIVE MEASURES
All equipment using CO2 must be equipped with a properly designed exhaust system System design must ensure that CO2 concentrations in work areas never exceeds the allowable exposure limits Monitors may be set up to not only sound an alarm but turn on ventilation if needed (done by customer only).

EXPOSURE TO CARBON DIOXIDE

Response varies from person to person It is not constant with the same person at different times Since CO2 is the regulator for the bodys breathing, a change in levels will cause an immediate response Exertion will burn oxygen content within a person, thus increasing the bodys concentrations of CO2

EMPLOYEE EXPOSURE LIMITS FOR CO2

AGENCY MAXIMUM CONCENTRATION (IN AIR) EXPOSURE TIME LIMIT

Occupational Safety and Health Administration

1/2% or 5,000 parts per million (ppm)

Per 8 hour work shift/40 hour week

American Conference of Government Industrial Hygienists

3% or 30,000 parts per million (ppm) 5% or 50,000 parts per million (ppm)

15 minute period

immediately dangerous to life and health (IDLH)

HANDLING LEAKS & EMERGENCIES

Ventilate areas to prevent the formation of toxic concentrations of carbon dioxide. If carbon dioxide content exceeds 3% you must wear an SCBA to enter that area. Avoid contact of the skin or eyes with cold carbon dioxide. Evacuate the immediate area if the leak is large. If water spray is used to dissipate leak, a dense fog may form as well as carbonic acid. Leak will dissipate itself given time if the ambiant temperature is above freezing.

PREPARING FOR AN EMERGENCY

Pre-arranged emergency plan including: Transportation Medical attention First aid techniques for CO2 Evacuation plan Perimeter security Personnel should be trained to use approved skin and respiratory protection Persons required to shut off the CO2 source should be properly trained and adequately protected

COLD CONTACT
Solid (dry ice) and liquid CO2 are normally very cold. Contact with these may result in frostbite Contact could also result in lesions or more serious injury from deep freezing of the tissues Contact should also be avoided with gaseous CO2 coming out of a pressurized container since this gas can also be very cold

FIRST AID FOR COLD CONTACT

Frozen tissues are painless and appear waxy yellow Remove restrictive clothing and immerse affected part in warm water (approximately 105F) Do not rub frozen parts, tissue damage may result Never use dry heat

FIRST AID FOR COLD CONTACT

If the exposure has been massive and general body temperature is depressed, immerse patient in a warm water bath Supportive treatment for shock should be provided Medical assistance should be obtained as soon as possible If the frozen part thaws before medical attention is obtained, cover with loose, dry, sterile dressing Alcoholic beverages or smoking are prohibited. Warm drinks and food may be administered

CARBON DIOXIDE SAFETY APPAREL

Wear clothing resistant to temperatures of -109 F Loose fitting gloves Steel toed shoes Hard hat Ear protection Eye protection Long sleeves (should not be rolled up while working )

CARBON DIOXIDE APPLICATIONS

Dry ice pellets Carbonation Refrigeration Crude Oil Recovery pH control Deflashing Industrial cleaning

CARBON DIOXIDE APPLICATIONS

Electronics Preserving Baked goods manufacturing Fumigation Inert blanketing and purging Shielding gas Solvent

CARBON DIOXIDE APPLICATIONS

Metallurgy (steel making) Textiles Pressurization Papermaking Plastics Agriculture Horticulture Chemical

LIQUID LEVEL GAUGES

Differential pressure Density NPSH Dead leg

CARBON DIOXIDE RECEIVER

CONFIGURATION VESSEL PRESSURE INSULATION HORIZONTAL/VERTICAL CARBON STEEL 350 PSIG (MAX) FOAM BLOCK SPRAY SCHEDULE 80 CARBON STEEL ELECTRIC AUXILIARY MECHANICAL

PIPING PRESSURE BUILDING VAPORIZER COOLING

SPECIFICATIONS ON TOMCO EQUIPMENT

Storage unit capacities: from one ton to 100 ton or greater. Pressure vessel: ASME coded for maximum working pressure of 350 psig, Code Specifications V1 1 1, Division 1. Piping: schedule 80 seamless pipe, 2,000 lb. forged steel fittings, ball type valves. Safeties: ASME approved direct spring loaded or pilot operated, sized for unconfined outdoors installations. Insulation: 4 polyurethane. Outer jacket: 063 aluminum.

TOMCO STORAGE VESSELS

Vaporizers (optional): Steam or electric capacities to 6,000 lb./hr and greater Liquid level gauges: Differential pressure indicators. Usually Barton gauges. Pressure gauges: 0-600 psig with 6 dial Style: Vertical or horizontal Minimum design temperature: -40 F Electrical: 208, 230/460 three-phase 60 cycles UL listed components

MAINTAINING PRESSURE IN LIQUID CO2 RECEIVERS - HORIZONTAL CONFIGURATION

CARBON DIOXIDE DELIVERY PIPING

PB SIDEARM VAPORIZER

STEAM VAPORIZER

DIRECT TO PROCESS VAPORIZER

FIGURE 2

GENERAL SITE REQUIREMENTS

Atmospheric conditions Clearance from exposures Underground interference Overhead interference Trailer access

UTILITIES
Electrical Phone Lighting

REGS GOVERNING INSTALLATIONS

Federal Laws State and Local Laws Boiler Pressure Vessel Laws Industry Guidelines Insurance Companies Other Experience

GUIDELINES & AGENCIES

BOCA: Building Officials Code Association CGA: Compressed Gas Association NFPA: National Fire Protection Association OSHA: Occupational Safety Health Administration UFC: Uniform Fire Code NEC: National Electric Code SFPC: Standard Fire Prevention Code

GUIDELINES & AGENCIES

SBCCI: Southern Building Code Congress International UBPVL:Uniform Boiler and Pressure Vessel Laws ASME: American Society of Mechanical Engineers ANSI: American National Standards Institute FDA: Food & Drug Administration BOC Gases Installation Standards BOC Gases National Training Center

CGA REGS FOR CO

CGA G-6 Carbon Dioxide CGA G-6.1 Standard for Low Pressure Carbon Dioxide Systems at Customer Sites CGA G-6.2 Commodity Specifications for Carbon Dioxide CGA G-6.3 Carbon Dioxide Cylinder Filling and Handling 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 Low Pressure Carbon Dioxide Systems

CGA REGS FOR CO

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)

EQUIPMENT AND COMPONENTS

Suitable for temperature Suitable for pressure Compression fittings Stainless steel Material construction Leak rate

SUITABLE MATERIALS FOR CO

Schedule 80 threaded steel pipe Forged steel fittings rated at 3000 psf Seamless schedule 40 steel pipe, welded joints Stainless steel Copper Brass

LABELING AND MARKINGS

The Corporate Identification Logo Product Identification CAS Number UNC Number Safety Venting Decals Product Hazard Warning

LABELING AND MARKINGS

Pipeline Labeling Authorized Personnel Pressure Vessel Identification Corporate Identification Number Emergency Information Valve and Component Identification Annual Safety Inspection

SIGN INFORMATION
Carbon dioxide Causes severe burns Liberates a gas which may cause suffocation Avoid contact with skin and eyes-- do not taste Do not put in stopped or closed containers Use and store only in well ventilated areas Liquid under pressure Emergency phone numbers

EQUIPMENT INSPECTION POLICY

Equipment must be inspected yearly Safeties must be changed out and re-tested every five years

CUSTOMER TRAINING
MSDS (Material Safety Data Sheet) General site review Emergency contact information

REFRIGERATION LAWS

RECOVER
To remove refrigerant in any condition from a system and store it in an external container without necessarily testing or processing it in any way.

RECYCLE
To reduce contaminants in used refrigerant by oil separation, non-condensable removal and single or multiple passes through devices which reduce moisture, acidity and particulate matter, such as replaceable core filter-dryers. This term usually applies to procedures implemented at the field job site or in a local service shop.

RECLAIM
To reprocess refrigerant to new product specifications by means which may include distillation. Chemical analysis of the refrigerant is required to determine that appropriate product specifications are met. This term usually implies the use of processor or procedures available only at a reprocessing or manufacturing facility.

FACTORS-RECOVERED REFRIGERANT
Reason system is being serviced Condition of refrigerant and system Equipment manufactures' policies Refrigerant cleaning capability of recycling equipment Feasibility and owner's preference

RECOVERED REFRIGERANT OPTIONS

Option 1: Put refrigerant back into the system without recycling it. Option 2: Recycle refrigerant and put it back into the system from which it was removed or back into a system with the same owner. Option 3: Recycle the refrigerant, test to verify conformance to ARI Standard 700 prior to reuse in a different owner's equipment provided that the refrigerant remains in the contractor's custody and control at all times from recovery through recycling to reuse. Option 4: Send refrigerant to a certified reclaimer

CONTAMINANT LEVELS
Because there are no means at this time to determine all contaminant levels (other than by laboratory testing), assurance that these contaminant levels are not exceeded can be accomplished by: The proper use and maintenance of refrigerant recovery/recycling equipment that is capable of recycling refrigerants to or below the levels in the table or Laboratory analysis (the appendix to ARI Standard 700 describes laboratory analysis procedures).

MAXIMUM CONTAMINANT LEVELS-RECYCLED REFRIGERANT / SAME OWNERS EQUIPMENT

CONTAMINANTS LOW PRESSURE SYSTEMS 1.0 ppm 20 ppm R-12 SYSTEMS ALL OTHER SYSTEMS 1.0 ppm 20 ppm 2.0 percent .02 percent Visually clean Visually clean 2.0 percent

Acid Content by Weight Moisture by Weight

1.0 ppm 10 ppm 2.0 percent .02 percent Visually clean Visually clean 2.0 percent

Non Condensable Gas N/A (By Volume) High Boiling Residues 1.0 percent (vol.) Chlorides by Silver Nitrate test Particulate Other Refrigerants No turbidity Visually clean 2.0 percent

SALE OF REFRIGERANTS
Used refrigerants shall not be sold, or used in a different owner's equipment, unless the refrigerant has been analyzed and found to meet requirements of ARI Standard 700 (latest edition), Specifications for Fluorocarbon and Other Refrigerants".

NITROGEN vs CARBON DIOXIDE

Both asphyxiants, but CO2 is considered toxic Liquid CO2 is not subject to the same level of refrigerant losses associated with LN2 Vacuum insulated pipe is sometimes considered necessary for longer LN2 lines (usually at twice the piping cost) Phase separators sometimes necessary for LN2 lines & for CO2 lines in chilling applications LN2 has a greater temperature difference available (-320 F for LN2 vs -109 F LN2 contains about 12% greater refrigeration capacity per unit weight than CO2 For bulk tank installations, LN2 usually requires less capital