1-Air Liquide Gas Properties Safety HT VWT 2013

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
Laurent Coudurier Air Liquide
The world leader in industrial and medical gases
PHYSICAL, CHEMICAL
and SAFETY GAS PROPERTIES
Nitrogen
Hydrogen
Ammonia
GASES IN METAL HEAT TREATMENTS

N2, Ar : Neutral
Oxidizing
O2, H20, CO2
Me + 1/2 O2 MeO
Me + H2O MeO + H2
Me + CO2 MeO + CO
Reducing
H2, CO
MeO + H2 Me + H2O
MeO + CO Me + CO2
NH3 : Nitriding
Decarburizing
H20, CO2, O2
CO2 + C 2 CO
H2O + C CO + H2
O2 + C CO
Carburizing
CO, CxHy
H2 + CO C + H2O
GAS CLASSIFICATION
The five gas families
Oxidizing gas
Gas allowing and maintaining combustion

and who does not burn
Combustible gas
Gas who does burn only with an oxidizing gas

(air, oxygen, )
Neutral or inert gas
Does not maintain life

Does neither allow nor maintain combustion
Non flammable
Toxic gas
Poison of organism from certain concentration,

depending from exposure time
Corrosive gas
Chemical attack of a lot of products :

metals, clothes, skin,
NEUTRAL or INERT GAS
Identification
Gas who does not

maintain life
but is not toxic
Gas who neither

allow nor maintain
combustion
and who is
not flammable
Exemples
Nitrogen
Argon
Helium
Carbon dioxide
Rare gases :
Neon
Xenon
Krypton
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 (-196C) under its own vapor pressure.
D 1 liter LN2= 682 liters gas (15C / 1 atm)
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.
COMBUSTIBLE GAS
Identification
Combustion only possible :

- In the flammability range of combustible
- With energy input
Exemples
Acetylene
Hydrogen
Natural gas
Propane
Butane
Methane
Ethylene
Silane
10
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 (-253C) is limited to
high quantities consumers.
11
HYDROGEN: FLAMMABILITY
Flammability limits in air at 20 C, 1 atm

Dlower: 4% and upper: 74.5%
Minimum
The
auto-ignition temperature at 1 atm: 570 C
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)
12
FIRE TRIANGLE
13
EXPLOSIVITY DIAGRAM EXAMPLE
Non explosive mixture
Nitrogen
Oxygen
Explosive mixture
Hydrogen
14
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
Carbon monoxid
Ammonia
Chlorine
Corrosive
Ammonia
Chlorine
15
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 (15C / 1 atm.)
D1 kg liquid NH3 = 1370 liters of gas
16
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.
17
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
18
AMMONIA: MATERIAL COMPATIBILITY

Aluminium
Brass, Copper
Carbon & Stainless Steels
Polytetrafluoroethylene
Satisfactory
Non recommended
Satisfactory
(PTFE)
Polychlorotrifluoroethylene (PCTFE)
Polyamide (PA) (NYLON)
Polypropylene (PP)
Buthyl
Satisfactory
Satisfactory
Satisfactory
Satisfactory
(isobutene - isoprene) rubber (IIR) : Satisfactory
19
AMMONIA SPECIFICATIONS
NH3
quality for nitriding:
DN 40
assay: 99,99% weight
Dwith impurity H2O< 50 ppm weight

Dwith impurity Oil < 1 ppm weight
20
OXIDIZING GAS
Identification
Gas allowing and maintaining combustion

and who does not burn alone
Exemples
Air
Oxygen
Nitrous oxide
21
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
22
SAFETY
FOR
HEAT-TREATMENT
FURNACES
23
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
24

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

itself an explosive and flammable mixture
25

Safety - N2 purging
Purging without ignition of flammable atmospheres
DIf a flammable atmosphere gas is introduced into an
industrial furnace operating < 750C, 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.
26

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 furnaces volume, nitrogen flowrate
and purging time
DNumber of renewal is about 4 to 5 times the furnaces
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.
27
GASES:
SUPPLY, STORAGE, DISTRIBUTION
28
PRODUCTION MODES and DISTRIBUTION

Small quantities 1 to 50 Nm3/h
Industrial
Merchant
Large
Industries
Large quantities 1000 to 100 000 Nm3/h
29
NITROGEN SUPPLY SYSTEMS

Liquid supply
Cryogenic Process
N2 Purity
100%
Bulk Supply
APSA
APSA-L
APSA-LE
99.9%
Permeation
Process
SPI
AMSA
Small Membranes
Large Membranes
N2 Production (Nm3/h)
95%
10
100
1000
10000
30
NITROGEN: LIQUID DISTRIBUTION
Liquid nitrogen
storage
Liquid nitrogen
road tanker
for delivery
31
NITROGEN ON-SITE PRODUCTION

Cryogenic air separation with APSA
AMBIENT AIR
COMPRESSION
AIR PURIFICATION
HEAT
EXCHANGER
DISTILLATION
BACK UP
AIR
OFF
GAS
NITROGEN PRODUCT
COMPRESSED AIR
MONITORING
Analysis
NITROGEN GAN
NITROGEN LIN
32
NITROGEN ON-SITE PRODUCTION
33
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%
34
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 -253C
D 99,999%
35
HYDROGEN - ON SITE GENERATORS
H2 On site generators range
eH2
Methanol
HYOS-R
HYOS-E
10
Steam reforming
100
1000
Log (m3/h)
30-300m/h
36
HYDROGEN - LARGE PIPE LINES SUPPLY
37
AMMONIA STORAGES
Cylinders (44 kg)
Containers (250 or 500 kg)
Liquid supply
38
THANK YOU FOR ATTENTION !
ANY QUESTIONS ?.
39

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INDUSTRIAL CUSTOMERS

Laurent Coudurier Air Liquide Technology Center

CHEMICAL and SAFETY GAS PROPERTIES

D NITROGEN : Inert gas

FOR HEAT TREATMENT

SUPPLY, STORAGE, DISTRIBUTION

D NITROGEN: Liquid storage and on site production

The world leader in industrial and medical gases

Laurent Coudurier Air Liquide

The world leader in industrial and medical gases

GASES IN METAL HEAT TREATMENTS

The world leader in industrial and medical gases

Gas allowing and maintaining combustion

Gas who does burn only with an oxidizing gas

Neutral or inert gas

Does not maintain life

Poison of organism from certain concentration,

Chemical attack of a lot of products :

Laurent Coudurier Air Liquide

The world leader in industrial and medical gases

NEUTRAL or INERT GAS

Gas who does not

Gas who neither

Laurent Coudurier Air Liquide

The world leader in industrial and medical gases

NITROGEN: PHYSICAL PROPERTIES

is a gas in normal atmospheric conditions.

atmospheric pressure and temperatures below -196 C,

is supplied either as a pressurized gas in

Laurent Coudurier Air Liquide

The world leader in industrial and medical gases

is a physiologically inert and non toxic gas.

is incapable of maintaining respiration or

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

Laurent Coudurier Air Liquide

The world leader in industrial and medical gases

Combustion only possible :

Laurent Coudurier Air Liquide

The world leader in industrial and medical gases

HYDROGEN: PHYSICAL PROPERTIES

is colorless, odorless and tasteless.

is the smallest , fastest but less viscous molecule, so

is supplied most of the time as a pressurized

Laurent Coudurier Air Liquide

The world leader in industrial and medical gases

Flammability limits in air at 20 C, 1 atm

auto-ignition temperature at 1 atm: 570 C

minimum energy of combustion of hydrogen is very low:

Laurent Coudurier Air Liquide

The world leader in industrial and medical gases

Laurent Coudurier Air Liquide

The world leader in industrial and medical gases

EXPLOSIVITY DIAGRAM EXAMPLE

Non explosive mixture

The world leader in industrial and medical gases

TOXIC or CORROSIVE GAS

Toxic: Poison of organism from certain concentration,

AMMONIA: PHYSICAL PROPERTIES

is a gas in normal atmospheric conditions.

Laurent Coudurier Air Liquide

The world leader in industrial and medical gases

is capable of forming an explosive mixture with

limits in air at 20 C, 1 atm

Dlower: 15% and upper: 27%