INDUSTRIAL CUSTOMERS

INDUSTRIAL GASES
FOR HEAT TREATMENT
PROPERTIES, SAFETY and SUPPLY SYSTEMS

VWT - Brecht/Belgium - September,26th, 2013

Laurent Coudurier – Air Liquide Technology Center

 SUMMARY

„ PHYSICAL, CHEMICAL and SAFETY GAS PROPERTIES

D NITROGEN : Inert gas
D HYDROGEN : Properties and flammability
D AMMONIA : Specifications and safety

„ SAFETY FOR HEAT TREATMENT

D FURNACE ATMOSPHERE
D SAFETY PURGING

„ GAS: SUPPLY, STORAGE, DISTRIBUTION

D NITROGEN: Liquid storage and on site production
D HYDROGEN: Cylinders and Tubes trailers storages
D AMMONIA: Storages

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 PHYSICAL, CHEMICAL
and SAFETY GAS PROPERTIES
Nitrogen
Hydrogen
Ammonia

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 GASES IN METAL HEAT TREATMENTS

N2, Ar : Neutral NH3 : Nitriding

Oxidizing Decarburizing
O2, H20, CO2 H20, CO2, O2

Me + 1/2 O2 Æ MeO CO2 + C Æ 2 CO

Me + H2O Æ MeO + H2 H2O + C Æ CO + H2
Me + CO2 Æ MeO + CO ½ O2 + C Æ CO

Reducing Carburizing
H2, CO CO, CxHy
MeO + H2 Æ Me + H2O
H2 + CO Æ C + H2O
MeO + CO Æ Me + CO2

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 GAS CLASSIFICATION

The five gas families

Gas allowing and maintaining combustion
Oxidizing gas and who does not burn

Gas who does burn only with an oxidizing gas

Combustible gas (air, oxygen, …)

• Does not maintain life

Neutral or inert gas • Does neither allow nor maintain combustion
• Non flammable

Poison of organism from certain concentration,

Toxic gas depending from exposure time

Chemical attack of a lot of products :

Corrosive gas metals, clothes, skin, …

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 NEUTRAL or INERT GAS

‹ Identification

Gas who does not Gas who neither and who is

maintain life allow nor maintain not flammable
but is not toxic combustion

‹ Exemples
Nitrogen Rare gases :
Argon Neon
Helium Xenon
Carbon dioxide Krypton

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 NITROGEN: PHYSICAL PROPERTIES

„ Nitrogen is a gas in normal atmospheric conditions.

N2 is colorless, odorless, tasteless, density/ air= 0.97
N2 is the main ingredient of air with 78.08 % vol.

„ At atmospheric pressure and temperatures below -196 °C,

it is a colorless liquid, slightly lighter than water.

„ Nitrogen is supplied either as a pressurized gas in

cylinders (200 or 300 bars), or as a liquid at low
temperature (-196°C) under its own vapor pressure.
D 1 liter LN2= 682 liters gas (15°C / 1 atm)

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 NITROGEN: ANOXIA

„ Nitrogen is a physiologically inert and non toxic gas.

„ Nitrogen is incapable of maintaining respiration or

combustion. It is a non flammable gas.

„ By displacing the oxygen in the air (O2 content in air is

20.8 %), it may have harmful effects on the organism, by
reducing the partial pressure of oxygen and acting as an
asphyxiant.

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 COMBUSTIBLE GAS

‹ Identification

Combustion only possible :

- In the flammability range of combustible
- With energy input
‹ Exemples
Acetylene Propane Ethylene
Hydrogen Butane Silane
Natural gas Methane

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 HYDROGEN: PHYSICAL PROPERTIES
„ Formula : H2
„ Molecular weight : 2.0 g/mole
„ Density / air :0.07 kg/m3

„ H2 is colorless, odorless and tasteless.

„ H2 is the smallest , fastest but less viscous molecule, so

H2 generates easily leaks and accumulation in high spots

„ Hydrogen is supplied most of the time as a pressurized

gas in cylinders or tubes trailers (200 bars). Supply of
liquid hydrogen at low temperature (-253°C) is limited to
high quantities consumers.

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 HYDROGEN: FLAMMABILITY

„ Flammability limits in air at 20 °C, 1 atm

Dlower: 4% and upper: 74.5%

„ Minimum auto-ignition temperature at 1 atm: 570 °C

„ The minimum energy of combustion of hydrogen is very low:

Hydrogen= 0.02 mJ in air
Natural Gas= 0.28 mJ (x10)
Ammonia= 680 mJ (x10000)

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 FIRE TRIANGLE

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 EXPLOSIVITY DIAGRAM EXAMPLE

Non explosive mixture

Oxygen Nitrogen

Explosive mixture

Hydrogen
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 TOXIC or CORROSIVE GAS

‹ Identification
Toxic: Poison of organism from certain concentration,
depending from exposure time
Corrosive: Chemical attack of a lot of products : metals,
clothes, skin, …

‹ Exemples

Toxic Corrosive
Carbon monoxid Ammonia
Ammonia Chlorine
Chlorine
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 AMMONIA: PHYSICAL PROPERTIES

„ Formula: NH3
„ Molecular weight :17.03 g/mole
„ Gas density : 0.77 kg/m3
corrosive toxic flammable
„ Ammonia is a gas in normal atmospheric conditions.
„ It is a colorless, slightly flammable, toxic gas with a
suffocating odor.
„ Ammonia is stored in liquid form in metal recipients
without thermal isolation. In storage, liquid ammonia is in
equilibrium with its own vapor pressure: its pressure
varies with the temperature
D1 liter liquid NH3 = 947 liters of gas (15°C / 1 atm.)
D1 kg liquid NH3 = 1370 liters of gas

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 AMMONIA: FLAMMABILITY
„ Ammonia is capable of forming an explosive mixture with
air. However, its inflammation requires a high temperature
and a high energy ignition source.
Explosions can only occur in a closed area

„ Flammability limits in air at 20 °C, 1 atm

Dlower: 15% and upper: 27%

„ Minimum auto-ignition temperature at 1 atm: 690 °C

Note: the minimum energy of ignition of ammonia is very

high, 680 millijoules, which is 1000 to 10 000 times that of
hydrogen.

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 AMMONIA: BIOLOGICAL PROPERTIES

„ Main Hazards: Inhalation and skin contact

„ Health hazards: Toxic, irritant on the mucous membranes,

can cause serious damage to the eyes, severe skin burns

„ Recommended Threshold Limit Value (concentration in air to

which nearly all workers may be exposed during 8 hours/day
and 40hours/week without adverse effects)

DTLV (ACGIH) : 25 ppm exposure limit in air

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 AMMONIA: MATERIAL COMPATIBILITY

„ Aluminium Satisfactory
„ Brass, Copper Non recommended
„ Carbon & Stainless Steels Satisfactory

„ Polytetrafluoroethylene (PTFE) Satisfactory

„ Polychlorotrifluoroethylene (PCTFE) Satisfactory
„ Polyamide (PA) (NYLON™) Satisfactory
„ Polypropylene (PP) Satisfactory

„ Buthyl (isobutene - isoprene) rubber (IIR) : Satisfactory

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 AMMONIA SPECIFICATIONS

„ NH3 quality for nitriding:

DN 40 assay: 99,99% weight

Dwith impurity H2O< 50 ppm weight

Dwith impurity Oil < 1 ppm weight

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 OXIDIZING GAS

‹ Identification

Gas allowing and maintaining combustion

and who does not burn alone

‹ Exemples
Air
Oxygen
Nitrous oxide

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 DATA and NORMS ON GASES

„ Physical, chemical and safety data on all gases

Encyclopedia of Gas from Air Liquide edited by ELSEVIER

„ ISO/PDTR 15916: Basic considerations for the safety of

hydrogen systems.

„ EN 746-3 : Safety requirements for the generation and use

of atmosphere gases in furnaces

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 SAFETY
FOR
HEAT-TREATMENT
FURNACES

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FURNACE ATMOSPHERE - SAFETY
EUROPEAN SAFETY NORM EN 746-3 : Safety
requirements for the generation and use of atmosphere
gases in furnaces.

„ Flammable atmosphere gas

DAny gas mixture that is capable of forming flammable
mixtures with air or oxygen under the conditions of
temperature and pressure used in the process

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FURNACE ATMOSPHERE - SAFETY
EUROPEAN SAFETY NORM EN 746-3 : Safety
requirements for the generation and use of atmosphere
gases in furnaces.

„ Atmospheres (H2+CO+CH4)<= 5% v/v with CH4 < 1% v/v

are non flammable.

„ Atmospheres with more than 1% v/v CnHm are flammable

„ Atmospheres with more than 2.5 % v/v NH3 are flammable

„A flammable gas with less than 1% v/v O2 can not form

itself an explosive and flammable mixture

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FURNACE ATMOSPHERE - SAFETY
Safety - N2 purging
„ Purging without ignition of flammable atmospheres

DIf a flammable atmosphere gas is introduced into an

industrial furnace operating < 750°C, then its introduction
shall be preceded by an inert gas purge to remove air until
the oxygen content is 1%(v/v) or less.

DWhen the furnace atmosphere is flammable, nitrogen

purging is also mandatory at the end of any treatment's
cycle to avoid creation of a flammable mixture while opening
the furnace.

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FURNACE ATMOSPHERE - SAFETY
Safety - N2 purging
„ How to purge ?
DOxygen concentration before purging is 20.8% (air)
DOxygen concentration after purging must be under 1% v/v
DPurge is function of the furnace´s volume, nitrogen flowrate
and purging time
DNumber of renewal is about 4 to 5 times the furnace´s
volume per hour.
DAt the end, another purge is performed during cooling phase
to decrease the (H2+CO) concentration < 5% (v/v) and
CnHm concentration < 1%(v/v) to be safe before opening
the furnace.

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 GASES:
SUPPLY, STORAGE, DISTRIBUTION

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PRODUCTION MODES and DISTRIBUTION
Small quantities 1 to 50 Nm3/h
Industrial
Merchant

Large
Industries
Large quantities 1000 to 100 000 Nm3/h
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 NITROGEN SUPPLY SYSTEMS

Liquid supply
Cryogenic Process
N2 Purity

100%

APSA-L
Bulk Supply
APSA
APSA-LE
99.9%

Permeation
Process

SPI AMSA
Small Membranes Large Membranes

N2 Production (Nm3/h)
95%
10 100 1000 10000

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 NITROGEN: LIQUID DISTRIBUTION

Liquid nitrogen
storage

Liquid nitrogen
road tanker
for delivery

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 NITROGEN ON-SITE PRODUCTION
Cryogenic air separation with APSA

AMBIENT AIR AIR PURIFICATION HEAT DISTILLATION

COMPRESSION EXCHANGER
BACK UP

AIR

OFF
NITROGEN PRODUCT
GAS

COMPRESSED AIR

NITROGEN GAN
MONITORING Analysis
NITROGEN LIN

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 NITROGEN ON-SITE PRODUCTION

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HYDROGEN - PACKAGED SUPPLY

„ Cylinders
D 0,7 - 2 - 6 -10 m3
D 200 bars
D 99,9% - 99,995% - 99,999%

„ Bundles
D 120 m3 (12 cylinders)
D 9kg
D 200 bars
D 99,9% - 99,99% - 99,995% - 99,999%

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HYDROGEN - BULK SUPPLY
„ Tube trailers
D 2000 - 5600 m3 GH2
D 150 - 420 kg
D 200 bars
D 99,99%

„ Liquid trailers & tanks

D 45000 l LH2
D 3200 kg
D -253°C
D 99,999%
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HYDROGEN - ON SITE GENERATORS

„ H2 On site generators range

eH2 Methanol Steam reforming

HYOS-E HYOS-R

1 10 100 1000
Log (m3/h)
30-300m/h

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HYDROGEN - LARGE PIPE LINES SUPPLY

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AMMONIA STORAGES

„ Cylinders (44 kg)

„ Containers (250 or 500 kg) „ Liquid supply

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 THANK YOU FOR ATTENTION !

ANY QUESTIONS ?.

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