Handling and knowledge about high purity gases and

Handling and knowledge about high purity gases and gas mixtures Melina van Meer, AGA Gas AB, Segment Specialty Gas 1

Agenda AGA Gas AB Laws, regulations and rules Gases Risks Handling Storage of gas cylinders Colour marking of gas cylinders Gas equipment Training Summary 2

AGA Gas AB

AGA Gas AB AB Gasackumulator was founded 1904 with 16 employees in Saltsjö-Järla 4

”Solve the problems of customers. Give them the opportunity to increase profitability, safety and quality in their operations. Help them to introduce new, better technology. ” GUSTAF DALÈN, President of AGA 1909 1937 5

AGA Gas AB – part of The Linde Group • 50. 000 employees in more than 100 countries • Turnover 2011 – 100 billion SEK AGA, Linde och BOC 6

The Linde Group Today Result of world´s biggest gas fusion Merging of Linde Gas, AGA and BOC with three principal operations: Industry Gases Engineering Healthcare 7 7 Page

Industry Gases are our main focus Air Gases • Nitrogen • Oxygen • Argon • Inert Gases (Kr, Ne, Xe) Other Gases • Acetylene • Carbon dioxide & monoxide • Helium • Hydrogen • Methane • Propane • Refigerants Specialty Gases • Hi. Q High Purity Gases • Hi. Q Specialty Mixtures Medical Gases • Medical Oxygen • Nitrous oxide • NO mixtures Working Areas • Temperatures: from 269 o. C up to +3. 500 o. C • Pressure: from 0 to 300 bar • Purity: up to 99, 99999% 8

Laws, regulations and rules

Swedish legislation Laws, Parliament EU directive Regulations, Government Rules, Authorities Standards, not law 10

Requirements of employer and users Lag om skydd mot olyckor – Law about protection against accidents Arbetsmiljölagen – Law about working environment Lag om brandfarliga och explosiva varor – Law about flammables and explosives Kemiska arbetsmiljörisker (AFS 2011: 19) – Risks in chemical work environment Gaser (AFS 1997: 7) – Gases Gasflaskor (AFS 2001: 4) – Gas cylinders Användning av tryckbärande anordningar (AFS 2002: 1) – Use of pressurised devices Brandfarlig gas i lös behållare (SÄIFS 1998: 7) – Flammable gas in a cylinder Arbete i explosionsfarlig miljö (AFS 2003: 3) – Working in explosive environment 11 Explosionsfarlig miljö vid hantering av brandfarliga gaser och vätskor

Regulations of Swedish Work Environment Authority AFS 1997: 7 1 § These regulations applies to all operations using gas. 3 § In all operations where gas is used a risk assessment needs to be done. Any change in process, equipment or operating conditions -> new risk assessment needs to be done. 4 § Working with gas can only be managed or performed by a person with enough knowledge about the gas, about the risks when using gases and how to avoid these risks. 12

Responsibilty of Gas Superintendent • Gas storage room locked and not accessible for unauthorized persons • Always a person attending at unloading/loading of gas deliveries • Safety signs according to legislations where gas cylinders are stored • Combustible gases (i e acetylen, LPG) should not be stored together with combustion supporting gases (i e oxygen, nitrous oxide), this also includes empty cylinder • Store cylinders vertically and securely to prevent them from toppling • Make sure that protection hood stays on cylinder • Inside and outside of gas storage room is clean • That staff are using safety shoes and clothes when working with gas • That handling of gases are according to regulations 13

Who appoints gas superintendent A person who is in charge of flammable products A signatory A suitable gas superintendent: ● Working in the daily operations ● Has knowledge and experience of working with gas 14

Risk Assessment Documented (Best before date 2004) Should be the basis of: • Actions • Program for continuos inspections • Register of gases and how dangerous they are • Information about possible risks • Competence of staff working with gases • Routines and instructions for working with gases • Design of working area • Storage/Handling • Warning signs • Documentation of explosive protection • Plan of emergency 15

Risk Assessment 16

Risk Assessment Matrix 1 2 3 4 5 >1 time per 5 1 month 1 time per 1 month-1 year High risk 1 time per 1 year-10 year 1 time per 10 year-100 year 4 Midddle risk 3 2 Low risk <1 time per 100 year Health Environment Property 1 Transient mild discomfort Single injured, lasting discomfort Single severe injured, severe discomfort Single death, several severe injured Several deaths , tens severe injured No actual damage. Small propagation. No cleanup. Transient, brief damage Small propagation. Simple cleanup. Prolonged damage. Small to big propagation. Simple cleanup. Permanent damage. Small propagation. Difficult cleanup. Permanent damage. Big propagation. Difficult cleanup. <0, 1 million SEK 0, 1 -1, 0 million SEK 1 -5 million SEK 5 -20 million SEK >20 million SEK 17

Consequenses When not following the legislation… Compensation from insurance company is based on legal requirements. 18

Risk- and safety services Give a status of your gas system Show the way to a safety gas system Safety Engineers at AGA Gas AB: Jan Fransson Magnus Olsson 19

Services Legal Requirements Voluntarily Risk assessment Safety Review Counseling Flow chart List of components Documentation of explosion protection Documentation Plan of classification C 1, C 2 20

Gases

Content of the air that we breathe % ppb ppt Nitrogen 78, 09 Hydrogen 500 R 12 ca 200 Oxygen 20, 95 Nitrous gas 280 R 11 ca 200 70 Argon 0, 93 Carbon monoxide 60 -240 R 22 Sum about 100 Xenon Iodine Ozon ppm Carbon dioxide Neon Helium 340 15 5 Krypton 1, 1 Methane 1 -2 90 25 -45 Acetylene 10 Formaldehyde 10 Ammonia 4 -40 2 -20 Hydrogen sulfide 2 -20 Sulfur dioxide 0 -20 Hydrogen fluoride 1 -18 Ethylene Nitrogen oxide Chlorine 3 1 -4 ca 1 22

Air separation unit – Oxygen • Nitrogen • Argon 7 1 3 4 1. Filter 2 2. Compressor 3. Cleaning/purification 5 4. Cooling 5. Expansion 6. Separation 7. Argon 8. Nitrogen 9. Oxygen 10. Pump 11. Evaporator 8 8 9 7 6 10 11 23

Permanent gases Oxygen Argon Nitrogen Hydrogen °C Helium O 2 Ar N 2 -183 °C -186 °C -196 °C H 2 He -253 -269 °C 24

How much gas in a cylinder? 200 bar 50 litres Atmospheric pressure 10 000 litres = 10 m 3 200 x 50 = 10 000 litres = 10 m 3 25

Condensed gases is liquid in the cylinder LPG 95% Propane C 3 H 8 - 42 °C 5% Butane C 4 H 10 ± 0 °C Carbon dioxide CO 2 - 78 °C Nitrous oxide N 2 O - 88 °C 26

Liquid gases = Cryogenic gases Kryos is from greek language, meaning very cold 27

Liquid gas 1 litre of liquid gas -> 500 -800 litres of gas in gas phase 28

Absorbed gas Acetylene is a special case Acetylene C 2 H 2 - 84 °C Can not be stored in high pressure due to risk of spontaneously decay: • Porous mass • Acetone • Acetylene solved (absorbed) in acetone 29

Light and heavy gases Hydrogen 0, 07 Helium 0, 14 Acetylene 0, 91 Nitrogen 0, 97 Air 1, 0 Oxygen 1, 11 Argon 1, 38 Carbon dioxide 1, 53 LPG (propane) 1, 56 30

Gas cylinders Gas Phase of the gas Acetylene Oxygen + Carbon dioxide LPG other air gases Dissolved in acetone in a porous mass Gas Liquid Pressure of gas (bar) 17 200 50 7 Temp risk for bursting 100 °C valve 350 °C 100 °C No Bursting disc Safety valve Somewhat heavier Heavier Excess pressure protection No Somewhat lighter Weight gas compare to air Heavier 31

Risks with gases

Risks with gases Combustible Combustion supporting gas Inert/asphyxiating Oxygen O 2 Permanent Nitrogen N 2 Argon Ar Helium He Hydrogen H 2 Carbon dioxide Condensed CO 2 Nitrous gas N 2 O Absorbed LPG C 3 H 8 Acetylene C 2 H 2 33

Risks with gases • High pressure • Inert/asphyxiating gas • Fire and explosion • Poisonous gas • Low temperature 34

Asphyxiating – Invisible danger Most accidents with asphyxia happends because rules have not been followed. Typical causes could be: ● Deviated from current working environment rules. ● Training and control of work not sufficient. ● Defiencies in supervision team. AFS 1997: 7 6 § In working area the ventilation should be good enough that oxygen content normally is not less than 20%. When oxygen content in a working area is below 18% breathing apparatus should be used. KVÄVNINGSRISK 35

Risks when oxygen content decreases 21 % 15 % 13 % 10 % 36

Poisonous gases LD 50 0, 5 2 mg gas / litre air Ammonia Arsenic pentafluoride Bromine chloride Dicyan Dichlorinesilane 1, 1 Dichlorine difluoroethylene Disilane Ethylene oxide Formaldehyde Phosphor penta Germanium tetrahydride Carbonylsulfide fluoride Silicon tetra fluoride Chlorine trifluoride Carbon monoxide Methylbromide Methylchlorinesilan Nitrosyl chloride Perchlorylfluoride Selenium hexa Selenium hydrogen Sulfuryldifluorid Sulfur dioxide Sulphur tetra fluoride Sulfur trioxide Tellurhexafluoride Trifluoracetylklorid Hydrogen chloride fluoride 37

Very poisonous gases LD 50 < 0, 5 mg gas / litre air Arsenic hydrogen Boron trifluoride Bor tri chloride Cyanogenchloride Diborane Fluorine Fluorväte Phosphine Karbonylfluorid Carbonylchloride Chlorine dioxide Chlorinepentafluoride Nitrogen dioxide monoxide Nitrogen Ozone Hydrogen sulphide Syredifluorid Vinyl fluoride Volframhexafluorid Hydrogen cyanide 38

Handling

Handling of gas cylinders • Wear personal protective equipment (PPE) i. e. safety shoes and gloves, gas detector • Read safety data sheet • Handle cylinders gently • Protect cylinder from high temperature and mechanical impact • Store cylinders vertically and securely to prevent them from toppling • When transporting gas cylinder use a cart • Open valve carefully • Make sure that oxygen is not in contact with grease • Liquid gases always a risk of frost bite if contact with skin – wear correct PPE 40

Carbon dioxide – Handling dry ice • Handle and store in well ventilated spaces • Not stored in sealed container • Use personal protective equipment • In contact with skin –> frost bite 41

LPG Pressure and liquid volume at different temperature for a filled LPG cylinder 15 °C 7 bar 50 °C 18 bar 65 °C 24 bar 42

LPG-bottle should always be standing Safety valve Outlet Gas Liquid 1 kg leaking LPG in liquid phase > 525 litre gas 43

Personal safety – liquid gases • Safety googles/Visor What is suitable working clothes? • Gloves • Boots • Covered working clothes 44

How to treat frost-bite? 1. Frost-bites are treated as burns - Water! - Do not put any bandage or similar on the wound! Can cause more damage. 2. If necessary go to hospital 45

Handling of cryogenic gases Always pant legs outside boot shafts! 46

Handling liquid gases What is missing? 1. Safety googles / visor 2. Gloves 3. Protect environment to damages 4. Personal gas detector What else to remember? Always pant legs outside boot shafts! 47

Equipment • Use proper and approved equipment designed for cryogenic gases 48

Combustion gas – what does the law says? § Handling and storage should be with precaution to avoid risk for fire. § Storage room performed in a safety way, preventing fire to occur. § Equipment installed carefully and with competence. 49

Actions when fire Warn staff and evacuate the area Call 112 If possible with safety respect Shut off gas cylinders, take away cylinders Cool cylinders with water from a safe space Mark gas cylinders that has been in a fire, contact AGA 50

Actions when gas leaking out of cylinder Close the valve of gas cylinder Ventilate the area Evacuate If a bigger gas leakage – rope off the area Alarm rescue department if a big gas leakage Identify what was causing the gas leakage – change broken part If gas is liquid or cold – measure gas content in lower areas 51

Storage of gas cylinders

Storage of gas cylinders • Separate combustible gases from others gases • Well closed cylinders Gas storage • Protect against abnormal heating • Well ventilated area • Store cylinders inaccessible for unauthorized people Acetylene Oxygen • Warning signs 53

Colour marking of gas cylinders

Colour marking – safety • Colour marking according to european standard – EN 1089 3 • The colour of the cylinder breast informs about the property of the gas in the cylinder • Identification of gas property from a long distance • Important for emergency personnel 55

Cylinder colours Colour of cylinder not regulated by standard. AGA has choosed following colours: Industrial gases Acetylene Food gases Specialty gases Medical gases Black Maroon Green Silver grey White 56

Specialty gases – Pure gases 57

Gas mixtures 58

What information on cylinder label? 1. Product name 2. Product information 1 3. Warning symbol(s) 2 3 4 4. Material number 5. Transport information 6. Safety information 5 6 59

Gas equipment

Gas equipment • Gas panels • Point of use • Cylinder regulators • Flame barrier C 2 H 2 • Setback protection C 2 H 2 • Central gas supply system 61

Continous supervision AFS 2002: 1 Use of pressurised devices, central gas supply system • Control • That controls and ev inspections are performed • Function control • Gas panels, point of uses, setback protection (C 2 H 2) etc • Leak detection and ocular inspection of pipe system • Recommendation 2 times/year when combustible gases • Known defiencies corrected • Control of risk assessment, safety inspections, reports of incident • Marking, visible • Media, flow direction, safety sign • Instructions for operation • Flowchart, updated 62

Continous supervision, continued • Ocular control/change of hose (both high and low pressure hose) • Control of gas system according to supplier both daily and yearly inspections • Control that gas cylinders are chained • Controll of setback protection (C 2 H 2) every 24 st month Part or all of supervision of gas system can be done by another company but it is the responsibility of the owner of the gas system that the supervision is done. 63

Use of gas detectors Stationary CO 2 alarm Portabel gas detector 64

Training

Training AGA Gas AB offers following trainings: 1) Open courses at AGA Gas AB: ● Safety handling of gas ● Gas safety according to laws, regulations and rules ● Superintendent training for a bigger gas system 2) Courses at customer site More information at: www. aga. se or from your local sales representative 66

Summary • Gas superintendent • Competent staff • Risk assessment • Be aware of risks with gases: high pressure, asphyxiating, poisonous, combustible, coldness • Correct handling and storage of gas cylinders: chained, separate combustible gases from other gases, well ventilated working areas, personal protective equipment, gas detector • Colour marking of gas cylinders, especielly yellow and red colours • Continous supervision / yearly maintenance of gas equioment • Continous training 67