MT CE Inerting in The Chemical Industry UK A5 RZ VIEW17 180614

Inerting in the chemical
industry.
02 Inerting in the chemical industry
Imprint.
Authors
Dr.-Ing. Hans-Jrgen Reinhardt
Dipl.-Ing. Hans-Rudolf Himmen
Dipl.-Ing. Johann Kaltenegger
Photography
Linde AG
Contact
Linde AG
Linde Gases Division,

Seitnerstrasse 70,
82049 Pullach, Germany
Phone +49.89.7446-0,
Fax +49.89.7446-1216,
www.linde-gas.com
Inerting in the chemical industry 03
Preface.
Industrial gases play an important role in the

chemical industry. Key applications include
reaction and maintenance processes, safety
measures and environmental protection.
Chemical process, plant and apparatus inerting

is often critical to personal, material and plant
safety. Hence inerting is extremely common in
both the chemical industry in particular and the
gases industry in general.
Many application engineers in the gases industry,

as well as technicians, engineers and chemists
working in the chemical industry, would welcome
a reference guide outlining various inerting
methods, their range of applications and the
associated hazards. The aim of this handbook is to
help meet the need for information in this area.
Contents.
Preface03
1. Introduction 06
2. Gases used for inerting 07
3. Overview of inert gas production

methods11
4. Applications of industrial
inerting gases 16
5. Inerting methods 17
6. Inerting equipment 23
6.1. Measurement and metering stations 24

6.2. Inert gas sluices 25
6.3. Nozzles for injecting liquid nitrogen
into a gas stream 27
6.4. Inert gas blanketing in tanks 28
7. Software for inerting 30
7.1. Linde Safety System 30

7.2. PAM Process Application
Management 31
8. Calculation equations
and examples 32
8.1. Dilution purging 32

8.2. Pressure swing purging 32
8.2.1. Vacuum purging 32
8.2.2. Overpressure purging 33
9. Safety through inerting 34
9.1. General 34
9.2. Explosion diagrams 34
9.3. Limiting oxygen concentrations 37
10. Hazards for personnel handling

nitrogen and carbon dioxide 40
11. Monitoring of inerting 41
12. Examples 42
12.1. Supplying nitrogen to a reactor

duringstartup and shutdown and
whencharging a solid 42
12.2. Industrial services 43
13. Treatment of exhaust gas 45
14. Services provided by

gases companies 48
15. List of abbreviations 49
16. References 50
Appendix 1: Explosive limits and ignition

temperatures for selected flammable gases
and vapours 51
Appendix 2: Glossary of terms 53
1. Introduction.
There are many chemical processes where it is Less frequently, carbon dioxide or other gases
necessary to: may also be used. The basic principle entails fully
or partially replacing air, which contains oxygen
prevent explosions and often moisture as well, or a flammable and/or
eliminate undesired reactions poisonous gas with an inert gas.
keep moisture away from products and
ensure safety during maintenance work. There are many situations in which inerting is the
only way to meet safety standards during industry
These goals cannot always be achieved through processes and maintenance. In other cases,
technology and equipment design alone and inerting is used to maintain and improve product
so engineers often also rely on inert gases and quality. Fields that make use of inerting include
special inerting equipment. Inerting is done to refining, basic chemistry, petrochemistry and the
minimise the level of oxygen in a given space and manufacture of speciality and fine chemicals.
prevent oxygen and/or moisture from coming
into contact with reactive or adsorptive products.
Nitrogen is the gas most commonly used for
inerting.
2. Gases used for inerting.
Nitrogen and carbon dioxide are the most widely By comparison, carbon dioxide reacts with a
used gases for inerting. Other gases such as longer list of substances, including strong bases,
argon and helium are applied in certain instances amines, anhydrous ammonia, lithium, potas-
and some industrial applications use steam and sium, sodium, magnesium, beryllium, aluminium,
exhaust gases. chromium, manganese, titanium, uranium and
acrolein. Since the decomposition temperature of
Criteria that influence the choice of inert gas carbon dioxide is 2000 C, this is rarely an issue.
include: Arise in pressure will, however, increase the solu-
bility of this gas.
Risk of fire and explosion and/or their impact
or behaviour Noble gases are usually too expensive to be used
Effects on product and exhaust gas for inerting and do not perform as effectively as
Cost nitrogen. They are, however, frequently used for
Availability inerting light metal dust. Argon, for example, is
Security of supply used to prevent aluminium dust explosions and
in the extinguishing systems for such explosions
Although nitrogen and carbon dioxide are not (VDI Reports No. 2024, 2008).
fully inert, they are the gases of choice. At room
temperature, nitrogen reacts with a very small If steam is used for inerting, the condensa-
number of substances, for example with lithium to tion that sometimes forms can compromise the
form lithium nitride. inertization.
6 Li + N2 2 Li3N In the shipping industry, readily available exhaust

gas is used in oil tanks, requiring careful control
At temperatures ranging between 400 C and of the fuel to air ratio.
1800 C, nitrogen can react with magnesium,
silicon, titanium and other metals to form nitrides: The specific heat of a given inert gas determines
its effectiveness. The higher the specific heat, the
2 Ti + N2 2 TiN better the inerting performance. Table 1 shows
the respective values [1].
Reactions with oxygen occur only at very high
temperatures.
Table 1: Specific heat of selected inerting agents according to [1] at 0 C and at constant pressure
Inerting agent Specific heat* (Btu/(lb mole/F)) Specific heat* (kJ/kmol/K)

Nitrogen 7.0 29.308
Carbon dioxide 8.8 36.844
Helium 5.0 20.934
Argon 5.0 20.934
Steam 17 71.176
* Values at constant pressure; steam at 27 C, other values at 0 C
The molecular structure of inert gases has a direct The reason for this is that dilution with an inert
impact on their effectiveness. Carbon dioxide gas that has a higher specific heat capacity
is a triatomic molecule, nitrogen is a diatomic reduces the area susceptible to flammability.
molecule and argon and helium are monatomic By this logic, carbon dioxide again would be
molecules. Polyatomic molecules can absorb more favoured over nitrogen, because a smaller volume
energy because they contain a larger number of of inert gas would be needed. In most cases,
free molecular degrees of oscillation [2]. however, nitrogen is favoured for the following
reasons [2]:
The inerting effect thus decreases in the
following order: Carbon dioxide is capable of reacting with a
much larger number of substances than the
CO2 N2 He, Ar other inerting gases.
Carbon dioxide is soluble in aqueous products.
Figure 1 shows the level of effectiveness of It is corrosive in the presence of moisture.
inerting agents, taking the flammability of If the pressure drops sharply, carbon dioxide
methane as an example. snow can form.
Environmental regulations may apply when
CO2 is emitted into the atmosphere.
Table 2: Density of selected gases [2] and their densities relative to air
Type of gas Density in kg/m at 1013 mbar and 0 C Density relative to air
Air 1.293 1.0
Nitrogen 1.2505 0.967
Hydrogen 0.0899 0.0695
Argon 1.7837 1.38
Oxygen 1.429 1.105
Carbon dioxide 1.9767 1.529
Density also plays a particularly important role. Figure 1: Influence of various inerting agents
If the density of the inert gas is greater than the on the flammability of methane [1]
density of the gas to be displaced, it is possible CO2 H 2O N2 He
that the headspace above the injection point of 16
the inert gas will not be inerted. This problem can
be solved either by thoroughly mixing the inert 14
gas inside the vessel or choosing an inert gas
with a different density. 12
Table 2 shows the density of selected gases and 10

Methane in vol.%
how they compare with the density of air.

8
Table 3 presents some of the main properties
of nitrogen and carbon dioxide of relevance to 5
inerting.
4
The attached gas selector contains further infor-
mation on nitrogen, carbon dioxide and argon. 2
Since carbon dioxide has special properties,
attention should be paid to its phase diagram 0
(figure 2). 0 10 20 30 40 50
Injection of inert gas in vol.%

Table 3: Main properties of nitrogen and carbon dioxide [4]
Properties Nitrogen Carbon dioxide

Detectability by senses Colourless and odourless Colourless and odourless
Reactivity Inert because of NN Inert because of O=C=O
Flammability Non-combustible Non-combustible,
fire-extinguishing
Molar mass 28 g/mol 44 g/mol
Threshold limit value * 5000 ppm
Density at 1 bar, 0 C 1.250 kg/m 1.977 kg/m
Boiling point at 1 bar 195.8 C
Melting point at 1 bar 209.9 C 56.6 C (triple point)
Sublimation point at 1 bar Not applicable 78.5 C
Critical point 147.2 C (33.94 bar, 31.2 C (73.83 bar, 466 kg/m)
314 kg/m)
Solubility in liquids at 1 bar, 15 C Solubility in water: 20 mg/l Solubility in water: 2,000 mg/l
Health impact Cold gases/vapours are denser Harmful at higher concentrations,
than air, risk of suffocation lethal when > 8% by vol.
*max conc. value at workplace occupational exposure limit (OEL)
Figure 2: Phase diagram of carbon dioxide

10.000
Supercritical
1000
Solid CO2 Liquid CO2
(dry ice) (LIC)
100
Pressure (bar)
Critical
Triple point for point
10
carbon dioxide Operating param-
eters of LIC tanks Gaseous CO2
1
Sublimation point
for dry ice
0,1
-100 -80 -60 -40 -20 0 20 40
Temperature (C)
3. Overview of inert gas production methods.
Nitrogen and argon are obtained from air. Membrane and pressure swing adsorption plants
Figure 3 shows the gas composition of dry air. are suitable for small to mid-volume nitrogen
users where demand fluctuates widely. If high
purity nitrogen is required in large quantities,
Nitrogen the cryogenic rectification method is the only
valid option.
Air is separated using membrane technology,
pressure swing adsorption and cryogenic rectifi- The oxygen content in the air greatly influences
cation. These methods differ not only in terms of the energy input needed to separate the nitrogen
the underlying separation technology, but also in in the membrane separation and pressure
terms of target applications and costs. For details, swing adsorption techniques. Figures 4, 5 and
see table 4. 6 show typical plants for cryogenic air separa-
tion, pressure swing adsorption and membrane
separation.
Figure 3: Composition of dry air [5]

Oxygen O
20.95 vol% Argon Ar
0.93 vol%
CO ~400 ppm
Neon 18 ppm
Helium 5.2 ppm
Krypton 1.138 vol%
Xenon 0.086 vol%
Nitrogen N
78.08 vol%
Figure 4: Cryogenic air separation plant Figure 5: Adsorption plant
Table 4: Overview of technologies used to generate nitrogen [5]
Capacity in Nm/h Purity Separation technology Operating range

11000 < 99.5% Membrane 30100%
55000 < 99.99% Pressure swing 30100%
adsorption
200 to 400,000 Down to ppb purity Cryogenic rectification 60100%
levels
Figure 6: Small membrane separation plant
Noble gases The hydrogen reacts with the oxygen in the

presence of the noble metal catalysts to form
Helium, neon, argon, krypton, xenon, radioactive water. In a further column, the argon, which has
radon and synthetic ununoctium all belong to the become concentrated at the bottom of the column,
group of noble gases. These are monatomic gases is separated from the remaining nitrogen so that
with low reactivity and are found in air. Helium the resulting gas has a purity of 99.9999%[5].
is also sourced from natural gas in significant
volumes. Argon can also be captured during ammonia
and synthesis gas production processes, for
Since argon is the most widely used noble gas for example during methanol production. In these
inerting, more attention will be given to its pro- processes, which rely on air as the feedstock,
duction process. Pure argon is sourced exclusively argon and other noble gases are enriched and can
from air. Argon gas is not separated from the main be isolated from the gas mixture. Here too, the
constituents of air in the main air separation frac- various gases are separated by adsorption or rec-
tioning column, but in a separate argon column. tification, leaving pure argon.
Here, a rectification process initially produces
crude argon, which still contains around 35%
oxygen and 1% nitrogen. The crude argon is then
purified in a number of stages. The gas mixture
is first warmed to room temperature and com-
pressed to a pressure of 46 bar. Hydrogen is then
injected to remove the residual oxygen.
Carbon dioxide 1. Water-irrigated scrubbing to remove dust and

sulphur dioxide
Carbon dioxide is obtained from natural sources 2. Dissolution of carbon dioxide in a solvent, such
and purified, or procured by gas companies from as methanol
the chemical industry. Carbon dioxide is usually 3. A heating step to release the carbon dioxide
separated from combustion gases. Generator gas, from the loaded solvent
for instance, contains 1618% carbon dioxide. 4. Compression step to liquefy the released
Processing of this crude gas can be done in the carbon dioxide for transport in railcars or
following stages: tankers.
Figure 7: Gas cylinders

Supply modes The following parameters are possible:
Nitrogen is supplied in several different modes: Pressures up to 700 bar

Volume flow rates up to 25,000 Nm/h
Nitrogen in cylinders/cylinder bundles (10 l, Temperatures up to 400 C
200 bar; 50 l 300 bar) (figure 7), purity grades:
4.6, 5.0, 5.3, 5.6, 6.0 and 7.0 Figure 8 shows a mobile tank system.
Liquid nitrogen (LIN) in tank systems, typical
purity: 99.999% by vol., nitrogen capacity: Carbon dioxide is also supplied in pressurised gas
3,000 to 80,000 l cylinders or tankers. The pressure in the cylinder
Gaseous nitrogen (GAN) via pipelines or is temperature-dependent. The value is 52 bar at
on-site plants a temperature of 15 C. The gas is transported in
Nitrogen mixed with other gases, for example tankers at a temperature between 20 and 30C.
synthetic air (20% O2 and 80% N2) The pressure would then be in the range from 20
to 14 bar.
For larger inerting one-off jobs that require large
amounts of nitrogen, e.g. during revamps, high- Given the wide range of production and supply
capacity mobile systems can deliver a stable options available, an optimum solution can be
supply of this gas. found for each customers individual needs.
Figure 8: Mobile high duty vaporiser

4. Applications of industrial inerting gases.
The chemical industry uses a wide range of sub- A distinction is also made between continuous
stances, technologies and apparatus. Conse- and intermittent applications:
quently, the spectrum of inerting applications
using nitrogen, carbon dioxide and argon is Continuous applications:
equally broad. Inerting is used in particular for:
Blanketing of production processes to
Reactors, stirring tanks preventfire and explosion and avoid oxida-
Centrifuges and vacuum filters tion(to safeguard quality)
Grinding and mixing plants Inerting of solvent containers and transport
Tank farms, vessels equipment to prevent fire and explosion
Dryers, silos
Filling facilities Intermittent applications:
Oil and fuel pipelines
Industrial services Purging of pipelines
Purging of tanks
The main aims of these inerting activities are to: Inerting of filtering installations
Inerting of silo installations
1. Prevent explosive atmospheres from forming Inerting of grinding plants
in apparatus such as reactors Extinguishing of smouldering fires in silos
2. Ensure safe startup and shutdown of plants
and apparatus Inerting can also be carried out on a partial or
3. Avoid explosion risks during storage and trans- complete basis. With partial inerting, the oxygen
port of combustible substances concentration is reduced to such a low level that
4. Protect products against atmospheric oxygen the mixture ceases to be explosive. Complete
when oxidation reactions would impair quality inerting involves increasing the ratio of the
5. Protect against atmospheric moisture, either inerting gas to the combustible material to such a
to maintain product quality or to ensure level that even adding any amount of air cannot
optimal downstream processing, for example lead to an explosive mixture [6].
in grinding
6. Prevent health and safety hazards during
maintenance of plants, apparatus and
pipelines
5. Inerting methods.
Different inerting techniques are available for Sparging

different application challenges. With partial
inerting (see Chapter 4), the objective is to reduce Sparging involves passing finely dispersed gas
the concentration of oxygen in the mixture to bubbles through a liquid. This helps to improve
such a level that it ceases to be explosive. The mixing and increase the surface area for gas-
main methods employed are: liquid mass transfer. The technique is used in
chemical and biological reactions, but also in
stripping. Nitrogen is used for example to strip
Purging oxygen from oil, wastewater and other products.
In this process, an inerting gas is introduced to

an apparatus or pipeline in order to displace a
process gas from it.
Blanketing
Blanketing helps to ensure that constant, inert

conditions are maintained for a product, for
example in a vessel. The objective is to prevent
explosions, discolouration, polymerisation and
other undesirable changes in quality. The opera-
tion is monitored through the flow rate and
pressure of the inert gas stream and/or the
oxygen level in the exhaust gas.
There are several different purging methods: Figure 9 shows how nitrogen is used for displace-
ment purging of a vessel. The gas is supplied in
Displacement purging a tanker. The liquid nitrogen (LIN) is vaporised in
In displacement purging, inert gas is injected into an evaporator, and the gaseous nitrogen (GAN)
an open apparatus to displace a dangerous or is then injected into the vessel. The nitrogen
harmful gas. A slow flow rate will be maintained, squeezes the atmosphere out of the vessel via
e.g. < 10 m/s. This method is used primarily the exhaust gas valve. The quantity of nitrogen
when the H/D ratio* is high. The inert gas should required is relatively small, typically 1.2 times the
ideally have a higher density than the gas to be capacity of the vessel.
displaced.
* H/D = Height/Diameter
Displacement purging (plug effect)
Exhaust gas
LIN
GAN
Figure 9: Displacement purging configuration

Dilution purging Dilution purging should not be used if there is

Dilution purging involves injecting an inert gas to dead space in the vessel, because this cannot
lower the concentration of a harmful or danger- normally be reached by the inert gas. The con-
ous gas. This method is used when the apparatus figuration in figure 10 shows how gaseous
has a lower H/D ratio. The amount of nitrogen nitrogen is vaporised and injected into an appa-
required will be around 3.5 times the capacity of ratus with an open discharge valve. The diluted
the vessel. The best way to achieve a good degree gas, composed of the harmful gas and nitrogen,
of mixing is to have wide spacing between the is then discharged into the atmosphere or further
inlet and outlet ports and to choose an inert gas processed.
with a similar density to the harmful gas.
Dilution purging
Exhaust gas
LIN
GAN
Figure 10: Dilution purging configuration

Pressure swing purging Vacuum purging is particularly well suited for

In pressure swing purging, a closed apparatus is apparatus with several areas of dead space.
pressurised with an inert gas. When the gas is
vented, the dangerous or harmful gas escapes. Inerting of pipelines
The process (closing injection opening The following methods are used to expel process
release) is continued until the desired concen- gases or liquids from a pipeline and to inert the
tration of the harmful gas in the apparatus is system:
achieved. Pressure swing purging is used for
example when the inlet and outlet ports are 1. The process gas is forced from the pipeline by
located close together. In addition, the apparatus a plug of inert gas.
must be a pressure vessel. 2. A pig driven by nitrogen pressure displaces
the process gas. The pig can be made of solid
Vacuum purging material or foam.
Vacuum purging involves extracting the harmful
gas with a vacuum pump and then introducing an Figure 11 shows a schematic view of both
inert gas to the evacuated apparatus. This process versions.
is repeated until the desired concentration of
harmful gas is reached.
Inerting of pipelines
Filling with inert gas
Inert gas plug
Use of a pig (e.g. solid or foam pig)
Figure 11: Methods for inerting of pipelines

The inerting time and the amount of inert gas As the H/D ratio increases, the flow approaches
required depend not only on the inerting method plug flow and fewer vessel volume changes are
used, but also on the degree of mixing (e.g. plug needed. This also means that nitrogen consump-
flow, ideal mixing or bypass). Factors that influ- tion and inerting time decrease when the vessel
ence the flow include the properties of the gas, volume is the same. Figure 12 shows the rela-
the geometry of the space being inerted, the inlet tionship between the exit concentration and the
and outlet port configuration and last, but not number of vessel volume changes with the inert
least, the flow velocity. gas at different H/D ratios.
An example is the H/D ratio of the vessel. If the aim of inerting is to achieve a very low con-
The following rule of thumb generally applies: centration of the harmful gas, e.g. oxygen, high-
purity nitrogen must be used. Figure 13 shows
H/D < 1: that if the maximum permissible oxygen concen-
No plug flow Dilution purging tration is very low (< 1%), the nitrogen purity
H/D > 10: must be higher than 99%. Using a higher purity
Predominantly plug flow Displacement purging makes it possible to reduce the number of vessel
volume changes.
Exit concentration of gas to be displaced

H/D = 3 H/D = 1 H/D = 1/3
100
90
80
Exit concentration in vol.%
70
60
50
40
30
20
10
0
0 0.5 1 1.5 2 2.5 3 3.5
Number of vessel volume changes (purge gas)
Figure 12: Exit concentration of gas to be displaced as a function of vessel volume changes at different H/D ratios
Max. permissible oxygen concentration
Nitrogen concentration in purge gas [vol.%]

Max. permissible O2 concentration [vol.%]
2
99.995
4 99.9
99.09
98.5
6
98.0
10
1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6
Number of vessel volume changes (purge gas)
Figure 13: Maximum permissible oxygen concentration as a function of the number of vessel volume changes at different
nitrogen purities [4]
The properties of carbon dioxide permit its use Constant purging with an inert gas or
not only for inerting, but also for extinguish- Introducing and maintaining slight inert gas
ing smouldering fires in waste bunkers and silos overpressure
containing organic material. A special nozzle
(figure14) has been developed for this purpose. The second option should be chosen if feasible,
because it requires less inert gas, which in turn
The nozzle ensures that the carbon dioxide is means lower emissions.
completely vaporised while remaining as cold as
possible. In particular, this prevents the formation
of CO2 snow. The gas is blasted from the nozzle
at a low velocity so that a stable layer can form
above the bulk material.
In certain cases, as in the production of food sup-

plements, argon is used instead of nitrogen as the
inerting agent. The principal reason is that argon,
being heavier than air, remains in the vessel
when it is opened. Argon is therefore more effec-
tive at preventing contact between oxygen and
the product. If an inert atmosphere needs to be
maintained in a vessel in continuous operation,
one of two options can be chosen:
Figure 14: Special nozzle for vaporising carbon dioxide [4]

6. Inerting equipment.
All inerting equipment and supporting installa- Whereby:

tions must meet the strictest leak-proof stand- L = Leak rate in kg/h
ards. Equipment must be designed to prevent air p = Measured pressure increase in mbar
from entering the system and explosive gases and t = Measuring time in min
vapours from exiting the system. Appropriate leak VB = Vessel volume in m
tests should therefore be carried out. The tests
are often performed at a pressure of < 0.5 bar To meet the needs of the chemical industry,
(abs.), i.e. following evacuation. Table 5 contains special equipment has been developed, built and
empirical values in relation to pressure. successfully deployed for inerting. This equipment
will be described in the following sections.
The leak rate can be calculated using the follow-
ing equation [7]:
p
L = 0,0072 VB
t
Table 5: Reference values for pressure

increases per minute following evacuation
to 0.5 bar (abs.)
p/t in mbar/min Application

> 0.2 Installation works under
atmospheric pressure,
e.g. driers
~0.51.0 Stirring tanks or similar
closed systems
< 0.2 Tightly closed systems,
e.g. vacuum distillation
equipment at 110 bar
(abs.)
0.00020.2 Installations for highly
toxic substances
Figure 15: Simple measuring and metering station for the Figure 16: Complex measuring and metering station for
inerting of silos nitrogen intended for the inerting of vessels, mixers and
reactors [4]
6.1 Measurement and metering stations Figure 16 shows a complex measuring and
metering station for nitrogen intended for the
Figure 15 shows a simple measuring and metering inerting of vessels, mixers and reactors. The
station for nitrogen intended for the inerting of key features of this station are its flow and
silos. pressure regulators and the corresponding indi-
cator displays. For safety and portability reasons,
the individual components are arranged in an
enclosed and suitably ventilated cabinet.
6.2 Inert gas sluices The main advantages of inert gas sluices are:
In fine and speciality chemicals manufacturing, Admission of very little oxygen when the
some process stages such as reactions in stirring vessel is opened and charged
tanks involve not only liquids and gases but also Low inert gas consumption
solids. Certain situations can require the manual Easy to retrofit on the charging port of existing
charging of solids. This means that air/oxygen vessels
will enter the vessel along with the bulk material. Simplicity of routine operation
Inert gas sluices have been developed to reduce Low investment and operating costs
this admission of oxygen to a minimum. This helps Design versatility allowing adaptation to
to ensure safe handling during manual charging specific applications
and prevent any secondary reactions such as
oxidation. As a rule, nitrogen is used as the inert gas.
The gas can be supplied from the plants own
The concept ensures that very little (atmos- network, from cylinder bundles or in liquid form,
pheric) oxygen is admitted when opening and i.e. from a vacuum-insulated tank combined with
manually charging vessels. For this, the charging an evaporator.
port is purged with inert gas via inert gas sluices.
The inert gas sluices can be permanent instal- Figure 17 shows an inert gas sluice integrated into
lations or positioned on the charging port as the charging port of a mixer. To adjust the height,
and when required for filling. A variety of differ- the (threaded) bolts of the cover hinge merely
ent sluices are available and they can be easily need to be extended.
adapted to any given usage scenario. A specially
adapted inert gas regulator and supply system A schematic view of an inert gas sluice is shown
and, optionally, an oxygen analysis system ensure in figure 19. The inert gas is injected at the top
safe operation. Inert gas sluices can be deployed and flows inside the hollow body of the lock in
wherever manual charging of reactors or mixers a downwards direction. It emerges in the main
is required and an inert atmosphere needs to be body of the interior in the direction of the sluices
maintained, whether for safety and/or quality central axis.
reasons.
Figure 17: Inert gas sluice (shown here: N2LOCK Figure 18: Nozzles for injecting liquid nitrogen into a gas
from Linde) stream [4]
Preventing the admission of (atmospheric)

oxygen when opening a vessel
N2
Figure 19: Design and function of an inert gas sluice N2

Change in O2 concentration in vessel

sluice inactive sluice active
6
Increase in oxygen concentration [vol.%]
0
70 80 90 100 120 130 140 150
Bulk charge volume (l)
Figure 20: Change in oxygen concentration in vessel as a function of bulk charge volume when sluice is active and
inactive
Using an inert gas sluice when manually charging 6.3. Nozzles for injecting liquid nitrogen
a vessel makes it possible to keep the oxygen into a gas stream
concentration in the vessel at the desired low
value. Using special nozzles, liquid nitrogen can be dis-
tributed in piping over a wide range of flow
Figure 20 compares two charging operations with rates in such a way that the mixing zone is short
the same vessel (volume approx. 2.3 m; charging and virtually no liquid nitrogen reaches the pipe
port approx. 500 mm; O2 concentration prior to wall or downstream apparatus. The danger of
charging approx. 2% by vol.). There is a linear embrittling the material of the pipeline or appara-
dependency between the increase in O2 concen- tus is greatly reduced as a consequence. Figure 18
tration and the bulk charge volume. By activat- shows nozzles used for injecting liquid nitrogen
ing the inert gas sluice pressurised with nitrogen into a stream of gas flowing in a pipe to a reactor
(consumption approx. 5 to 20 Nm/h depending or another apparatus.
on type), the oxygen concentration level can
be significantly reduced, i.e. the inert gas sluice
effectively reduces the admission of air/oxygen
when the material is being charged.
6.4 Inert gas blanketing in tanks being used. Figure 21 shows a schematic view
of an inert gas blanketing system that automati-
Inert gas blanketing is used for oxygen-sensitive cally ensures that the headspace above the liquid
liquids in tanks to protect product quality or for is continuously filled with inert gas, regardless of
safety reasons. The process involves blanket- whether the tank is being filled or emptied.
ing the headspace above the liquid level in
the tank with an inert gas atmosphere, which Such inert gas blanketing systems often work
is maintained even during filling and emptying on a purely mechanical basis and usually do not
operations with a specially designed system require any auxiliary electrical or pneumatic
incorporating valves. power. They can easily be installed as a complete
package, tailored for the tanks specific require-
A constant overpressure of a few millibars is auto- ments (see figure 22).
matically maintained inside the tank while it is
Figure 21: Automatic system for inert gas blanketing in tanks
PISA 102
PIC 101 PIC 103
max.
100mbar
AB 103 AB 104
Figure 22: Inert gas blanketing system with pressure reducing valve, back pressure regulator and safety valve
(shown here: GAXINERTER from Linde)
7. Software for inerting.
Inerting is one of the most common processes With the Linde Safety System application, engi-
used in the chemical industry. An estimated neers can create a flammability diagram (safety
6070% of the nitrogen consumed in the chemical triangle) for the substance or mixture found at the
industry is used for this purpose. To provide customers site (provided the data on the pure
additional support for the application engi- substances is contained in the DIPPR database).
neers who advise customers on-site, software The key features of the programme are as follows:
was developed in the 1980s to create ignition
range diagrams for flammable gas mixtures. This Flammability diagrams can be calculated for
software has undergone continuous develop- substance mixtures containing up to 99 (flam-
ment over the years, with several modules added. mable) components
Lindes application engineers can now build on a Freely selectable temperature range
package of supporting programmes to help their (dependent on substance properties of the
customers calculate safety thresholds, the amount components)
of nitrogen required, or the purging time. These Choice of inert gas (N2, CO2, Ar, He or H2O)
support tools have proven their worth time and Variable oxygen concentration (1 to 100 vol.%)
again in the chemical industry. The following On-screen preview and print-out possible
sections will provide brief descriptions of the two Cannot be used for dust
main programmes, the Linde Safety System and Values are always calculated for pressure of
PAM Process Application Management. 1bar(a)
Temperatures higher than the auto-ignition
temperature of individual components cannot
7.1. Linde Safety System be calculated
The Linde Safety System is a programme to Figure 23 shows a flammability diagram calcu-
compute flammability diagrams. The data is lated with the Linde Safety System.
drawn from the Design Institute for Physical Prop-
erties (DIPPR) database. The DIPPR is a techni-
cal society of the American Institute of Chemical 7.2. PAM Process Application
Engineers AIChE. DIPPR is one of the worlds best Management
and most well-known sources for critically evalu-
ated thermodynamic property data. The database With the current programme module, calculations
contains thermodynamic constants and tem- can be made for inerting processes like dilution
perature-dependent properties (in the form of purging and pressure swing purging. For optimum
equation parameters) for approx. 2,000 industri- support of each application, the user can select
ally relevant substances. different geometrical parameters for the vessel
or tank. Other parameters include pressure limits,
the available inert gas volume flow rate and local The PAM module is linked with the SST (Linde
and process-related conditions. Safety System) module. During data entry, the
flammability diagram (based on the DIPPR pure
If the user enters data that is not consistent or substance data) is calculated in the SST module
plausible in view of previous entries, warnings and the results are fed to the PAM module.
are displayed, or else the user cannot continue
until the value entered has been changed. This The output which the application engineer
prevents scenarios whereby, for example, exces- receives contains data on, for instance, the
sively high pressure builds up because the inert inert gas requirement, the purging time, and
gas volume flow rate in the vessel is too high and the number and ultimate pressure of inert gas
the outlet cross-section of the ventilation opening purge cycles (for pressure swing purging). This
or pipe is too small. data will be used to prepare for and carry out
the inerting operation. Figure 24 shows a sample
datacalculation.
Safety system flammability triangle
At 25 C and 1 bar (a) for mixture (fuel)

[L] Lower flammability limit (3.3 vol.% fuel), [U] Upper
flammability limit (14.8 vol.% fuel), [S] Min. 02 for
flammability (9.2 vol.% oxygen, 3.7 vol.% fuel), [C] Start
up (max. 9.5 vol.% oxygen), [B] Shut down (max. 6.5vol.%
oxygen)
Inert gas: Nitrogen. Fuel mixture [vol.%]: methane [75],
propane [15], isobutane [10]
Oxygen concentration [vol.%]
L
20
U
15
Figure 24: Sample data calculation with PAM
10
C S
5
B
0
0 2 4 6 8 10 12 14 16 18 20
Fuel concentration [vol.%]. No safety factor included
Figure 23: Safety triangle calculated using the Linde

Safety System
8. Calculation equations and examples.
Chapter 5 described the various inerting tech- i = ln (1004) = ln 25 = 3.22

niques in detail. This chapter will compile the cal- VN = 3.22 2,000 = 6,440 m
culation equations for each method and provide
examples to describe their use. To achieve the final concentration of 4 vol.%, 3.22
volume changes are needed. The nitrogen volume
required is 6,440 m minimum.
8.1 Dilution purging
According to the reference source [7], the 8.2 Pressure swing purging
following calculation equations can be used for
this method: In pressure swing purging, a distinction is made
Number of volume changes: between vacuum purging and overpressure
i = ln (ca ce) (EQ1) purging. One of the main objectives of pressure
swing purging is to arrive at a certain concentra-
Volume of inert gas required: tion of a dangerous or harmful substance, e.g.
VN = i VB (EQ2) oxygen. The residual concentration of the harmful
substance can be calculated using the following
Whereby: equation [8]:
i = Volume change
( )
n
p1
Ca = Initial concentration C SR=
p2 (C SG C SI) + C SI (EQ3)
Ce = Final concentration
VN = Volume of inert gas Whereby:
VB = Volume of vessel CSR = Residual concentration of harmful substance
CSG = Concentration of harmful substance in mixture
Sample calculation: CSI = Concentration of harmful substance in inert
A vessel is filled with methane. Its volume is gas
2,000 m. The initial concentration is 100 vol.%. n = Number of pressure swings
After inerting, the final concentration should be p1 = Pressure 1 (prior to inerting)
4vol.%. The dilution purging method is to be p2 = Pressure 2 (following inerting)
used. How many volume changes are needed?
How much nitrogen will be needed?
8.2.1 Vacuum purging
Calculation:
Vessel volume: 2,000 m The effective inert gas requirement [7,8] is calcu-
Initial concentration: 100 vol.% lated as follows:
Target final concentration: 4 vol.%
VN = VB f n (EQ4)
Whereby: Number of volume changes:

VN = Inert gas requirement in m i = (lnca lnce) (lnp2 lnp1) (EQ6)
VB = Vessel volume in m
f = Pressure change ratio Volume of nitrogen:
n = Number of pressure swings VN = VB i (p2 p1)/p0
The pressure change ratio equation is as follows: Whereby:

Ca = Initial concentration
p1 p1
f = 1 , < 1 (EQ5) Ce = Final concentration
p2 p2
p1 = Pressure after pressure increase
f = Pressure change ratio p2 = Pressure after pressure release
p1 = Pressure prior to inerting p0 = Pressure prior to pressurisation
p2 = Pressure following inerting VB = Volume of vessel
i = Volume change
Sample calculation:
Calculation of residual concentration [7,8] Sample calculation:
A vessel is filled with methane. Its volume is
The pressure is reduced from atmospheric 2,000 m. The initial concentration is 100 vol.%.
pressure to 0.5 bar. The oxygen concentration After inerting, the final concentration should be
in the mixture is 21 vol.% and 0.5 vol.% in the 4% by volume. The overpressure purging method
inert gas. Two pressure swings are carried out. is to be used. The pressure following the pressure
From this, the following residual concentration increase is 2 bar; following the pressure release it
of oxygen can be calculated according to the is 1 bar; and prior to pressurisation it is 1 bar. How
equation (EQ3) above: many volume changes are needed? How much
inert gas will be needed?
2
cOR = (0.5/1.0) (210.5) + 0.5 = 5.62 vol.%
Calculation:
Calculation of inert gas requirement [7] Vessel volume: 2,000 m
How much inert gas is needed to reach a final Initial concentration: 100 vol.%
concentration of 5.62 vol.% if the vessel has a Desired final concentration: 4 vol.%
volume of 10 m?
Number of pressure swings:
The equations (EQ4) and (EQ5) show that: i = (ln100ln4) (ln2ln1) = 4.6
[ 0.5
]
VN = 10 1 2 = 10 m
1.0
3
Volume of inert gas required:
VN = 2,000 4.6 (21) 1 = 9,200 m
In this case, 10 m of nitrogen is required.
With pressure swing purging, 4.6 pressure swings
and 9,200 m of inert gas are needed.
8.2.2 Overpressure purging
The following equations are used for overpressure

purging:
9. Safety through inerting.
9.1 General 9.2 Explosion diagrams
One of the main reasons for inerting is to prevent Determining the approach to take and conditions
explosions. The following factors are needed for to apply when inerting requires familiarity with
an explosion to occur: a flammable substance, the explosive range. This can be gained by exam-
oxygen and a source of ignition. The risk of explo- ining explosion diagrams. Triangular diagrams
sion can be averted by avoiding the formation are the most commonly used format. The advan-
of an explosive atmosphere, reducing oxygen tage of this type of diagram is that the substance
concentration through the use of inert gas and quantities of the individual components are
excluding ignition sources. shown. Figure 25 shows a sample diagram.
The following sections will describe how the for- To aid understanding, the diagram will be
mation of an explosive mixture can be avoided explained in detail based on the description in [9]:
through the use of inert gas. The main terms
used in connection with explosion protection are A is a substance mixture comprised of 65 mol%
explained in Appendix 2. flammable gas, 17.5 mol% oxidising agent
(also known as the oxidiser) and 17.5 mol%
Sample triangular diagram inert gas. The values are identified by translat-
ing the coordinate lines to point A and reading
100 0
the values on the corresponding coordinates
90 10
of the triangle. Since substance mixture A lies
B
l%
80 20
outside of the explosive range, there is no risk
mo
+Br
Ine
70 30
of explosion.
s in
A
rt g
60 +Ox 40
ga
+In The explosive range is arrived at by entering

as
le
50
in
50
ab
the experimental values obtained and through

mo
mm
40 60 graphical or mathematical interpolation. If

l%
Fla
UEL 30 70 the composition of the gas mixture lies in

LEL 20 Explosive range 80 the explosive range, then it is explosive. This
10 90 means that the presence of an ignition source
0 100 will cause dangerous reactions. But what
100 90 80 70 60 50 40 30 20 10 0
about mixtures with a composition that puts
Oxidiser in mol%
them on the borderline? According to German
and EU regulations, these compositions do not
Figure 25: Triangular diagram showing explosive range of
a flammable gas [9]. LEL is the lower explosive limit and cause dangerous reactions.
UEL the upper explosive limit.
Another way to present the explosive range of a Explosive range of a flammable gas
flammable gas in graphic form is to use cartesian
coordinates. Figure 26 provides an example. 100
90
Flammable gas in mol%

80
The disadvantage of this type of diagram is that +Br B
70
A +In
it does not show the third component. This can, 60
+Ox
however, be calculated as follows: 50
40
30
XOxidiser = (100 XFlammable gas XInert gas) 20
Explosive range
10
The advantage here is that a spreadsheet pro- 0
0 10 20 30 40 50 60 70 80 90 100
gramme can be used. There are no mixtures in the
shaded area because the sum of the individual Inert gas in mol%
components would produce mixtures exceeding
100 mol%. Figure 26: Explosive range of a flammable gas in the
cartesian coordinates system [9]
For A and the explosive range, see the expla-

nations for the triangular diagram. A number of
different methods can be used to determine the
explosive limits [9]:
Method according to DIN 51649-1/DIN EN 1839

Method according to ASTM E 681-04
Method according to prEN 1839 (tube and
bomb methods)
These methods are carried out at atmospheric

pressure and a maximum temperature of 200 C.
In all methods, defined gas mixtures are produced
and subjected to ignition attempts. The differ-
ences between the measuring methods lie in the
ignition vessels, the ignition sources, the criteria
for ignition, the incrementation applied and
the number of check tests. As a result, different
explosive limits will be found depending on the
method used. More information can be found in
the reference sources, such as [9].
The explosive limits are pressure- and tempera- The ignition power also influences explosive
ture-dependent. The higher the temperature, the limits, as table 8 demonstrates. In the tables, LEL
wider the explosive range. Table 6 shows some stands for lower and UEL upper explosive limit.
examples of this. When the initial pressure rises,
the explosive range likewise expands. This leads Additional explosive limits and ignition tempera-
to only a slight change in the lower explosive tures are indicated in Appendix 1.
limit, but the upper explosive limit increases by a
significant factor, as seen in table 7.
Table 6: Influence of temperature on the lower and upper explosive limits in air at 1 bar
Gas 20 C 400 C
LEL in vol.% UEL in vol.% LEL in vol.% UEL in vol.%
Hydrogen 4.0 75.6 1.3 85.4
Carbon monoxide 12.5 74.0 8.0 84.7
Methane 4.4 17.8 2.8 34.4
Table 7: Influence of pressure on the lower and upper explosive limits in air at 20 C
Gas 1 bar 100 bar

Methane 4.4 17.8 4.3 46.6
Table 8: Influence of ignition power on the lower and upper explosive limits in air at
20 C and 1 bar
Gas 1 Joule 10,000 Joules

Hydrogen 4.9 13.8 3.6 17.5
9.3. Limiting oxygen concentrations about determining the safe concentration margin:
The safety margin between the experimentally
From a safety standpoint, the limiting oxygen determined limiting oxygen concentration and
concentration (LOC) is a key criterion for inerting. the maximum permissible oxygen concentra-
For a specific fuel/air/inert gas mixture, this tion must be specified taking account of spatial
parameter is the highest concentration of oxygen and temporal variations resulting from opera-
at which no explosion takes place by itself. The tional factors and malfunctions and of the delay
LOC is a specific value which must be determined between triggering of protective measures and
by experiment. their becoming effective. Table 9 shows selected
examples of flammable gases and vapours with
Mathematical correlations for this do not exist. nitrogen and carbon dioxide as inerting agents.
The values for simple substance mixtures have The LOC values for carbon dioxide are significantly
been compiled in tables. higher in some cases. The values also depend
on the temperature. For flammable gases and
The maximum permissible oxygen concentra- vapours, the rule of thumb is that the limiting
tion is obtained by deducting a safe concentra- oxygen concentration falls by 0.5 to 1.0 vol.%
tion margin from the experimentally determined when the temperature rises by 100 C.
limiting oxygen concentration. The explosion
protection rules BGR 104 [6] state the following
Table 9: Selected LOC values of flammable gases and vapours with nitrogen and carbon dioxide as
inerting agents [10]
Fuel LOC in vol.% LOC in vol.%

Nitrogen/air Carbon dioxide/air
Benzene 11.2 13.9
Butadiene 10.4 13.0
Cyclopropane 11.7 13.9
Ethylene 10.0 11.7
Hexane 12.1 14.5
Methane 12.0 14.5
Propane 11.5 14.5
Hydrogen 5.0 5.2
Methanol 10.0 12.0
Limiting oxygen concentrations for various types With light alloy dusts, noble gases are often used
of dust have also been determined for inerting for inerting because there is a risk of reaction
dust/air mixtures. The fineness of the dust was a with carbon dioxide or nitrogen. Combustible dust
factor taken into consideration. Table 10 contains deposits can give rise to glowing and smoulder-
some examples for inerting with nitrogen. ing fires.
The values are higher here, too, when carbon To prevent dust explosions in such situations, the
dioxide is used as inerting agent instead of oxygen concentrations chosen must be signifi-
nitrogen. The limiting oxygen concentration cantly lower than the LOC values. These must be
does not just depend on the inerting gas, but determined separately [6].
also on the pressure and temperature. The LOC
values decrease as the temperature and pressure With mixtures of gaseous and dusty mixtures, the
increase. As a general rule for combustible maximum permissible oxygen concentration must
types of dust, when the temperature increases be determined using the component with the
by 100C, the LOC value decreases by approx. lowest limiting oxygen concentration.
1.6vol.% [1].
Table 10: LOC values of selected dust types when inerting dust/air mixtures at 20 C and 1 bar [11]
Type of dust Fineness (median) in m Limiting oxygen concentration in

vol.% in gaseous phase
Aluminium 22 5
Lignite 63 12
Cellulose 25 15
Urea <10 10
Wood 27 10
Hops 500 17
Rubber 95 11
Methyl cellulose 70 10
Wheat flour 60 11
The LOC cannot itself be used for process control Table 10 also indicates that working with many
because of uncertain variables like: hydrocarbons is often safe when the oxygen con-
centration is lower than 10% and a safety margin
Accuracy of the LOC values of e.g. 2 vol.% is assumed. However, this is only
Fluctuations in pressure and temperature the case at atmospheric pressure and ambient
during the process temperature.
Stability of the process
Speed control system reacts to process As a general rule, when the temperature
changes increases by 100 C, the LOC decreases by
Accuracy of the oxygen measurement 0.51.0vol.%.
Various levels are therefore determined for In apparatus in which the oxygen concentration is
process control. Cunliff [12] has proposed four continuously measured, a safety margin of 2vol.%
levels, for instance: is often applied. If the concentration is not con-
tinuously measured, the permissible oxygen con-
LOC centration should be 60% of the LOC or lower.
Maximum permissible oxygen concentration This precaution should provide a sufficient safety
First alarm level margin on the one hand while also preventing
Normal operating conditions false alarms, which could for example result in
shutdown of the plant.
10. Hazards for personnel handling nitrogen

and carbon dioxide.
Guaranteeing safety is paramount when inerting. toughness of some materials, such as carbon
The following hazards in particular must therefore steel, so that they become embrittled and may
be addressed when using inert gases: fracture. LIN should not therefore be used for
such materials. Suitable materials include stain-
Asphyxiation less steel, copper and aluminium. Carbon dioxide
When it is necessary for personnel to work in a has certain characteristics that differentiate it
partly inerted environment, for example during from nitrogen and argon. The CO2 concentration in
cleaning, the oxygen level must be kept at a air is around 0.03 vol.%. At higher concentrations,
minimum of 15 vol.%. Table 11 provides further the human body cannot differentiate between
information. metabolically produced CO2 and the CO2 present in
the atmosphere. The initial effect is faster breath-
Contact with cryogenic liquid nitrogen leads to ing. The effects felt at higher concentrations are
cold burns and frostbite. Protective clothing, par- detailed in table 12. Inert gases must therefore be
ticularly safety gloves and safety glasses, must handled with extreme care, especially as they are
therefore be worn when handling liquid nitrogen. for the most part colourless and odourless.
In light of the low temperatures involved, liquid

nitrogen (LIN) can diminish the ductility and
Table 11: Effects of atmospheric oxygen concentration on humans and the flammability of
materials, see also [1]
Oxygen level in Effects on human body Effects on flammability of materials

apparatus (vol.%)
46 Coma in 40 s, convulsions, death Non-flammable
68 Death after 8 min at the latest Non-flammable
810 Danger of death, unconsciousness, Non-flammable
nausea, inability to move
1012 Poor judgement and pain perception, Non-flammable
blue lips
1214 Fatigue, increased respiration and Low flammability
pulse rate, impaired judgement
1519 First signs of oxygen deficiency, Low flammability
decreased ability to work
21 None None
11. Monitoring of inerting.
Regardless of the method used for inerting, moni- Such conditions/factors might include:
toring by taking careful measurements is essen- Do flow and pressure fluctuations occur?
tial. Variables that should be measured and moni- How fast should the reaction times be?
tored include oxygen concentration, inert gas The sensor must work reliably and be easy to
concentration, and mass flows of inert gas and calibrate. The time delay must not be longer
flammable materials/oxygen. The use of moni- than60s [12].
toring equipment, such as oxygen analysers, can
help to improve safety, optimise inert gas con- Measuring accuracy of 1 vol.% [13] is sufficient.
sumption and reduce emissions to a minimum.
Systems to measure oxygen concentration must Typical varieties of oxygen analysers are:
fulfil the following important criteria: Electrochemical cell
Paramagnetic sensor
The sensor must be adapted to the particular con- Zirconium oxide sensor
ditions/risk factors of the measuring point.
Table 12: Effects of carbon dioxide inhalation [1]
Carbon dioxide in vol.% Effects of CO2 inhalation

1 Breathing rate increases slightly.
2 Breathing rate increases by up to 50% of normal level. Prolonged inhala-
tion leads to headache and fatigue.
3 Breathing increases to twice the normal rate and becomes laboured. Slight
narcotic effect. Impaired hearing, headache, increased blood pressure and
pulse rate.
45 Breathing increases to approx. four times the normal rate. Symptoms of
intoxication become evident and slight choking may be felt.
510 Characteristic pungent odour is noticeable. Very laboured breathing,
headache, visual impairment and ringing in the ears. Judgement may be
impaired, followed within minutes by loss of consciousness.
50100 A concentration in excess of 10% rapidly leads to fainting. Prolonged
exposure to high concentrations may eventually result in death from
asphyxiation.
12. Examples.
12.1. Supplying nitrogen to a reactor monitoring the oxygen level in the headspace of
during startup and shutdown and when the apparatus, and an inert gas lock for charging.
charging a solid In an example drawn from synthetic fibre manu-
facturing, molten polyamide is produced using
Figure 27 illustrates how nitrogen can be supplied nitrogen as inert gas. The reason is that molten
to a reactor or mixer. There are three options for polymer suffers from marked oxidation by oxygen.
nitrogen delivery. The system includes a meas-
urement and control unit, an oxygen analyser for
Figure 27: Supply of nitrogen to a reactor

Liquid nitrogen (LIN)
Plant process
control system
Evaporator
Measuring & O2-plant

control unit
Tank
Lock
On-site plant
Central supply pipeline

12.2. Industrial services Figure 28 shows an inerting and cool down opera-
tion at a reactor. Inerting and accelerated cool-
The chemical industry often requires large down of a fixed bed reactor with liquid nitrogen
volumes of nitrogen for tasks associated with leads to:
preparing for and executing repeat shutdowns.
Nitrogen is used to inert the system during Accelerated inerting of the catalyst
shutdown and cooling, in pressure testing, in Shorter cool-down time
drying (of catalysts in particular) and in pre- Saving in cost because piping does not have to
heating under inert conditions preparatory be reconfigured
to startup. An example is the shutdown of an
ethylene cracker, where the following conditions Figure 29 shows the technical configuration for a
were needed: reactor cool-down through the controlled injec-
tion of liquid nitrogen in the recycling gas flow of
Nitrogen consumption: 1,0006,000 Nm/h the reactor.
Pressure: 940 bar
Temperature: ambient to +200 C
Exhaust Reactors
gas
Compressor CATCOOL
Recycle flow
LIN pump
LIN
Figure 28: Use of liquid nitrogen to cool down a reactor Figure 29: Technical configuration for accelerated
cool-down of three reactors
Pigging and other pipeline maintenance opera-

tions are also often carried out under nitrogen
inerting.
Nitrogen pushes a pig through a pipeline or piping

system (figure 30). The advantages of using
nitrogen to move the pig include:
Inerting
Anti-corrosion action of dry gas
Wide range of volume flow rates, pressures
and temperatures
Figure 30: Pipeline pigging using nitrogen
Refinery
LIN
Tank farm
GAN
Pig
Pig pipeline
13. Treatment of exhaust gas.
Exhaust gases from inerting and cleaning opera- Flexible solvent loading
tions are often contaminated with hydrocarbons. Fast startup and shutdown of plant
These must be removed before the gas is vented Simple and fully automatic operation
into the atmosphere. This can be done by means
of cryocondensation, an adsorber or a combus- The temperature required to undercut the dew
tion plant. point or comply with the statutory exhaust
emission standards can easily be set and con-
Cryocondensation [14] can be especially advan- trolled using liquid nitrogen (196 C at 1 bar) as
tageous because the cryogenic effects of the the cooling agent. Cryocondensation thus enables
nitrogen used for inerting is utilised. Other temperatures of 150 C and lower, which will be
advantages include: required in some cases. Figure 31 shows how cry-
ocondensation can be integrated into the process
No auxiliary materials, as is the case in adsorp- for cleaning an exhaust gas flow.
tion for example
Low investment costs
Small number of moving parts
Figure 31: Cryocondensation block diagram [15]
Liquid
nitrogen
LIN
Source of emissions Crude gas Clean gas Atmosphere

Cryocondensation
plant
Re-use Condensate GAN Inerting

Cryocondensation can be used to clean exhaust

gas flow rates of up to 1,000 Nm/h and different
contaminant loads, e.g. solvents.
Both standard units (figure 32) and customised

solutions are available. These units can also be
implemented as mobile systems.
CIRRUS M50 CIRRUS M150 CIRRUS M500
Figure 32: Standard cryocondensation units for exhaust gas flow rates of 50, 150 and 500 Nm/h [15]
Customised cryocondensation units are available

for higher throughputs and more complex sepa-
ration tasks (figure 33). Figure 34 shows a dia-
grammatic view of a customised cryocondensa-
tion unit. It consists of three heat exchangers and
enables effective recovery of resources.
A sample application is described below:

After an air separation unit was purged with
perchloroethylene, the atmosphere within the
unit was saturated with gaseous perchloroeth-
ylene. The perchloroethylene atmosphere was
to be eliminated by purging with nitrogen. The
nitrogen flow then contained perchloroethylene,
which was removed through cryocondensation.
ACIRRUS M50 unit, shown in figure 32, was used
for this purpose. The residual load of the nitrogen Figure 33: CIRRUS CD, cryocondensation unit
flow was 10 ppm, which corresponded to a load
of 80 mg/m [15].
Figure 34: Flow diagram for three-stage cryocondensation [15]
LIN
Source of emissions Crude gas
HE 1 HE 2 HE 3
TIC
Re-use
Condensate
GAN Inerting
Clean gas Atmosphere

14. Services provided by gases companies.
When it comes to inerting, chemical companies Performance of safety and cost-efficiency

can often benefit from partnering with a gases analyses
supplier, which will invariably have a wealth of Tests at customers site or pilot plant to check
experience in different inerting processes and effectiveness of inert gas sluices, for instance
methods. Gas suppliers can offer the following Leasing or fabrication and delivery of inerting
services: hardware
Supply of required quantities of inert gas
Application-specific advice on the optimal
supply mode, safety and hardware
specifications
15. Abbreviations.
Abbreviation Measurement Unit

c a Initial concentration Vol.%, g/m
ce Final concentration Vol.%, g/m
cOR Residual concentration of oxygen Vol.%, g/m
cSG Concentration of harmful substance in mixture Vol.%, g/m
cSI Concentration of harmful substance in inert gas Vol.%, g/m
cSR Residual concentration of harmful substance Vol.%, g/m
D Diameter m
p Pressure change bar
f Pressure change ratio
H Height m
i Number of volume changes
L Leak rate m
LIN Liquid nitrogen
LOC Limiting oxygen concentration Vol.%, g/m
n Number of pressure swings
UEL Upper explosive limit Vol.%, g/m
p0 Pressure prior to pressurisation bar
p1 Pressure at state 1 bar
p2 Pressure at state 2 bar
t Time s, min, h
LEL Lower explosive limit Vol.%, g/m
V B Vessel volume m
V N Inert gas volume m
x Molar fraction Mol.%
16. References.
[1] AICHE, 38th Annual Loss Prevention Sympo- [9] M. Molnarne, T. Schendler and V. Schrder:
sium, April 2529, 2004, New Orleans, Louisiana. Sicherheitstechnische Kennzahlen, Vol. 2,
Explosionsbereiche von Gasgemischen, 2003,
[2] M. Nitzsche, Bevors knallt, Chemie Technik Wirtschaftsverlag NW, Verlag fr neue Wissen-
No. 6, 2003 (Vol. 32). schaft GmbH, Bremerhaven.
[3] GESTIS substance database, Institut fr [10] Inertisierungsanlagen, Sichere Chemie

Arbeitsschutz der Deutschen Gesetzlichen arbeit, January 1998, p. 9.
Unfallversicherung.
[11] GESTIS-STAUB-EX, combustion and explosion
[4] H.-J. Reinhardt and H.-R. Himmen, Improve characteristics of dusts database (H. Beck, et al.,
inerting practices at your facility, Hydrocarbon Brenn- und Explosionskenngren von Stuben,
Processing April 2010, p. 51. BIA-Report, 12/97 BIA, Sankt Augustin).
[5] Industrial Gas Processing, 2007, Wiley-VCH [12] B. J. Cunliff, Avoiding Explosions by Means
Verlag GmbH & Co. KGaA, Weinheim. of Inerting Systems, IChemE Symposium Series
No. 148.
[6] BGR 104, explosion protection rules,
Regeln fr das Vermeiden der Gefahren durch [13] T. Hoppe and N. Jaeger, Practical Designs
explosionsfhige Atmosphre mit Beispiel- for Inerting in Production Plants, Process Safety
sammlung, December 2002, SMBG, Sddeutsche Progress, Vol. 25, No. 4.
Metall-Berufsgenossenschaft.
[14] H.-R. Himmen and H.-J. Reinhardt, Industrial
[7] T. Hoppe and N. Jaeger, Inerting, A Reliable Gas Applications, Chemical Engineering, March
and Effective Preventive Measure Against Explo- 2009.
sions, 39th Annual Loss Prevention Symposium,
April 1113, 2005, Atlanta, Georgia. [15] H.-D. Obermeyer, Umweltschutz mit
technischen Gasen, presentation, Linde Gas,
[8] T. Hoppe and N. Jaeger, Reliable and Effective Munich, 2003.
Inerting Methods to Prevent Explosions, Process
Safety Progress, Vol. 24, No. 4.
Appendix 1: Explosive limits and ignition

temperatures for selected flammable gases
and vapours.
Explosive substance Explosive limits in air Ignition temperature

in vol.% in g/m3 in C
Acetaldehyde 4.057.0 731040 140
Acetone 2.513.0 60130 540
Acetylene 2.483 1530.2 305
Ammonia 15.030.2 105215 630
Aniline 1.211.0 48425 425
Benzaldehyde 1.4 60 190
Benzene 1.28.0 39270 555
Prussic acid 5.446.6 60520 535
(hydrogen cyanide)
Butadiene 1.416.3 31365 415
n-butane 1.58.5 37210 365
tert-Butanol 1.410.0 43310 340
Chlorobenzene 1.37.0 60330 (590)
Diethyl ether 1.736 501100 180
Dioxane 1.922.5 70820 375
Acetic acid 4.017.0 100340 485
Acetic anhydride 2.010.2 85430 330
Ethane 3.012.5 37155 515
Ethanol 3.515.0 67290 425
Ethyl acetate 2.111.5 75420 460
Ethyl bromide 6.711.3 300510 510
Ethyl chloride 3.614.8 95400 510
Ethylene 2.728.5 31330 425
Ethylene glycol 3.253.0 801320 410
Ethylene oxide 2.6100 471820 440
Carbon dioxide 12.574.0 145870 605
Explosive substance Explosive limits in air Ignition temperature

in vol.% in g/m3 in C
o-Cresol 1.3 58 555
Methane 5.015.0 33100 (650)
Methanol 5.531.0 73410 455
Methyl acetate 3.116.0 95500 475
Methyl bromide 8.620.0 335790 535
Methyl chloride 7.619.0 160410 625
Methylene chloride 13.022.0 450780 605
Nitrobenzene 1.8 90 480
Phthalic anhydride 1.710.5 100650 580
Propane 2.19.5 39180 470
Isopropyl alcohol 2.012.0 50300 425
Carbon disulphide 1.060.0 301900 95
Toluene 1.27.0 46270 535
Vinyl chloride 3.831.0 95805 415
Hydrogen 4.075.6 364 560
o-Xylene 1.06.0 44270 465
Explosive limits and ignition temperatures of

selected flammable gases and vapours according
to the Nabert-Schn/Rmpp Chemie Lexikon,
published by Jrgen Falbe, Manfred Reglitz,
Georg Thieme Verlag Stuttgart, New York 1995.
Appendix 2: Glossary of terms.
Some of the main terms used in connection with explosion protection have been compiled and defined in
the following table. The definitions were largely based on the ATEX equipment directive 94/9/EC.
Auto-ignition temperature Auto-ignition is a process whereby a substance ignites in the

presence of air without an external source of ignition. The
process is based on an exothermic oxidation reaction which
mainly occurs in solids with a large surface area (e.g. dust), but
also in low-volatility organic liquids when distributed on base
materials with a large surface area. The auto-ignition tempera-
ture is then defined as the temperature at which the rate of heat
production exceeds the heat dissipated. The data that has been
published can only be used as reference values, however, the
temperatures can depend a great deal on other variables (e.g.
shape and size of the material or sample and the test method
used). The auto-ignition temperature is often referred to as the
ignition temperature.
Density ratio The ratio of a gas or vapour to the density of air.
Evaporation number Time a liquid takes to evaporate relative to the evaporation time
of diethyl ether.
Explosion An explosion is an exothermic chemical reaction of a flammable
substance in gaseous or dispersed solid form with another sub-
stance, such as atmospheric oxygen. The explosive velocity will
range between 11000 m/s and the pressure increase will be in
the order of 310 bar.
Explosive atmosphere An explosive atmosphere contains explosive mixtures of gases,
vapours, mists or dusts with air, including usual admixtures
(e.g.humidity), under atmospheric conditions.
Explosive mixture An explosive mixture is a mixture of gases or vapours, which may
also include mists or dusts, in which a reaction propagates by
itself after ignition has occurred.
Explosive limit, lower (LEL) in vol.% The lower limit of the concentration of a flammable substance in
a mixture with air within which a flame that is independent of
the ignition source is no longer able to propagate by itself after
EN 1839 ignition.
Explosive limit, upper (UEL) in vol.% The upper limit of the concentration of a flammable substance
in a mixture with air within which a flame that is independent
of the ignition source is no longer able to propagate by itself
EN 1839 after ignition. The upper explosive limit is considerably higher
in mixtures containing oxygen than in those containing air. Both
explosive limits are temperature- and pressure-dependent.
Flammable liquids Flammable liquids are substances that have a flash point; at
35C they are neither solid nor unctuous and at 50 C they have
a vapour pressure of 3 bar or lower. They are grouped into a
number of hazard classes.
Flammable gases Flammable gases are gases that have an explosive range on
contact with air at normal pressure.
Flash point (TFl) The flash point of a flammable liquid is the lowest tempera-
ture at an air pressure of 760 torr (1013 mbar) at which vapours
emerge from the liquid contained in an open or closed cup in
such a quantity that a flammable vapour/air mixture forms on
application of an external source of ignition.
Hazard classes The German Regulation on Flammable Liquids (VbF) groups flam-
mable liquids into the following hazard classes:
A: Water-insoluble liquids with a flash point under 100 C
AI: The flash point lies under 21 C.
AII: The flash point lies between 21 C and 55 C.
AIII: The flash point lies between 55 C and 100 C.
B: Liquids with a flash point lower than 21 C which are soluble
in water at 15 C in any proportion.
Hazardous explosive atmosphere An explosive atmosphere present in hazardous quantities. An
atmosphere is considered hazardous when, if ignited, personal
injury can be caused as a direct or indirect result of an explosion.
Ignition temperature (T) The ignition temperature is the lowest temperature of a hot
surface determined in a specified experiment set-up at which
EN 14522 the most ignitable flammable gas/air mixture can be caused to
combust with a flame at a total pressure of 1.013 bar.
Limiting oxygen concentration (LOC) This is the maximum concentration of oxygen in an air/inert
gas/gas mixture at which no explosion can occur.
Minimum ignition energy (Emin) The minimum ignition energy of a gas/vapour and air mixture
is the smallest amount of electrical energy occurring upon dis-
charge of a capacitor which sufficiently ignites the most ignit-
able mixture of a gas or vapour with air at atmospheric pressure
and a temperature of 20 C.
Maximum experimental safe gap A standard method is used to determine the maximum experi-
(MESG) mental safe gap for each gas mixture. The level of ignitability is
determined by the gas mixture that emerges from a gap. Gases
IEC 60079-1 and vapours are classified into the following explosion groups on
the basis of their maximum experimental safe gap:
MESG Explosion group

> 0.9 mm II A
0.5 mm 0.8 mm II B
< 0.5 mm II C
Minimum ignition energy (Emin) The minimum ignition energy of a gas/vapour and air mixture
is the smallest amount of electrical energy occurring upon dis-
charge of a capacitor which sufficiently ignites the most ignit-
able mixture of a gas or vapour with air at atmospheric pressure
and a temperature of 20 C.
Temperature class (T1 bis T6) The temperature classes define ignition ranges into which flam-
mable gases and liquids are classified according to their specific
IEC 60079-4 ignition temperature.
Temperature class Ignition range Max. surface temp.

in C in C
T1 > 450 450
T2 > 300 450 300
T3 > 200 300 200
T4 > 135 200 135
T5 > 100 135 100
T6 > 85 100 85
13152_0615_LCS
Linde AG
Linde Gases Division, Seitnerstrasse 70, 82049 Pullach, Germany
Phone +49.89.7446-0, Fax +49.89.7446-1216, www.linde-gas.de
Linde Safety System, CATCOOL, GAXINERTER, NLOCK and CIRRUS are trademarks of The Linde Group.

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Inerting in the chemical

Linde Gases Division,

Industrial gases play an important role in the

Chemical process, plant and apparatus inerting

Many application engineers in the gases industry,

2. Gases used for inerting  07

3. Overview of inert gas production

6.1. Measurement and metering stations  24

7. Software for inerting  30

7.1. Linde Safety System 30

8.1. Dilution purging 32

9. Safety through inerting  34

10. Hazards for personnel handling

11. Monitoring of inerting  41

12.1. Supplying nitrogen to a reactor

13. Treatment of exhaust gas 45

14. Services provided by

15. List of abbreviations  49

Appendix 1: Explosive limits and ignition

2. Gases used for inerting.

6 Li + N2 2 Li3N In the shipping industry, readily available exhaust

Inerting agent Specific heat* (Btu/(lb mole/F)) Specific heat* (kJ/kmol/K)

Table 2 shows the density of selected gases and 10

how they compare with the density of air.

Injection of inert gas in vol.%

Table 3: Main properties of nitrogen and carbon dioxide [4]

Properties Nitrogen Carbon dioxide

Figure 2: Phase diagram of carbon dioxide

3. Overview of inert gas production methods.

Figure 3: Composition of dry air [5]

Figure 4: Cryogenic air separation plant Figure 5: Adsorption plant

Table 4: Overview of technologies used to generate nitrogen [5]

Capacity in Nm/h Purity Separation technology Operating range

Figure 6: Small membrane separation plant

Noble gases The hydrogen reacts with the oxygen in the

Carbon dioxide 1. Water-irrigated scrubbing to remove dust and

Figure 7: Gas cylinders

Supply modes The following parameters are possible:

Nitrogen is supplied in several different modes: Pressures up to 700 bar

Figure 8: Mobile high duty vaporiser

4. Applications of industrial inerting gases.

Different inerting techniques are available for Sparging

In this process, an inerting gas is introduced to

Blanketing helps to ensure that constant, inert

Displacement purging (plug effect)

Figure 9: Displacement purging configuration

Dilution purging Dilution purging should not be used if there is

Figure 10: Dilution purging configuration

Pressure swing purging Vacuum purging is particularly well suited for

Filling with inert gas

Inert gas plug

Use of a pig (e.g. solid or foam pig)

Figure 11: Methods for inerting of pipelines

Exit concentration of gas to be displaced

Max. permissible oxygen concentration

Nitrogen concentration in purge gas [vol.%]

In certain cases, as in the production of food sup-

Figure 14: Special nozzle for vaporising carbon dioxide [4]

All inerting equipment and supporting installa- Whereby:

2. Gases used for inerting 07

6.1. Measurement and metering stations 24

7. Software for inerting 30

7.1. Linde Safety System 30

8.1. Dilution purging 32

9. Safety through inerting 34

11. Monitoring of inerting 41

13. Treatment of exhaust gas 45

15. List of abbreviations 49