INGOLD

Leading Process Analytics

Measurement of Oxygen Concentration

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in Blanketing and Inerting Operations

Gaseous oxygen measurement with amperometric

sensors is the most direct and easiest solution for
protection against oxidation and explosion.

Unwelcome oxygen
Tank blanketing is the process of filling the headspace in
storage vessels and reactors with an inert gas, usually to
protect its contents from exploding, degrading or polymer-
izing due to the presence of oxygen but also to protect equip-
ment from corrosion. A blanketing system is normally de-
signed such that it operates under higher than atmospheric
pressures, therefore preventing outside air from entering the
vessel. As the presence of oxygen and moisture in the air is
undesired in numerous processes and applications, blanket-
ing is performed in a wide range of industries, varying from
(petro)chemical to food and beverage, pharmaceutical to
pure water.

Inerting is done for similar reasons but is not limited to stor-

age tanks and reactors. Any confined space can be sparged
with an inert gas to create the desired atmosphere. This
ranges from packing food under protective atmosphere to
increase shelf life to lowering the oxygen concentration in
rooms where welding takes place to reduce risk of fire. Typical
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also is complete or partial inertization in process equipment and Slightly more sophisticated is pressure-based blanketing. In a
unit operations such as: traditional set-up, such a blanketing system consists of:
• Centrifuges; • A blanketing valve or regulator allowing the inert gas to enter
• Mills; the tank whenever required;
• Mixers; • A breather valve or vapor recovery valve to allow headspace
• Fluid bed dryers; gas to escape from the tank;
• Silos; • A safety pressure / vacuum relief valve to prevent tank over-
• Pneumatic transport; pressure or vacuum (the latter could lead to implosion of the
• Incinerator / flare feedstock supply. tank, a risk that grows with tank size)
• and of course piping and inert gas supply
For economic reasons and because of its availability the most
common type of inert gas used is nitrogen. In this operation the breathing valve opens when the headspace
volume decreases and lets headspace gases leave the tank. In case
The blanketing process the product is pumped out of the tank or when temperature de-
The simplest way to protect a vessel, for example a storage tank, creases, the blanketing regulator shall open and fill the tank
against either overpressure or negative pressure is to have an headspace with nitrogen, avoiding underpressure. Maintaining a
opening at the top of the tank. In that situation any excess air or constant gauge pressure makes sure that air, and thus oxygen,
gas can freely leave the tank when product is pumped into the does not enter the tank. Changes in temperature and weather
tank and, conversely, air can flow into the tank when product is conditions mean that the tank breathes continuously.
drained. Such a system also allows “breathing” of the tank due to
temperature fluctuations that normally can lead to significant Risks
volume changes. Wrongly engineered or poorly maintained blanketing systems
may lead to serious incidents. The statement that all blanketing
For a number of reasons this method is not suitable for all prod- systems leak one way or another is probably true. Their complex-
ucts. Air entering the tank might contaminate the product and, ity; valves with moving parts, packings and sealings, etc. are
especially when storing organic solvents and hydrocarbons, an prone to failure. A malfunctioning pressure transmitter may reg-
explosive gas/air mixture will form above the product. Also, un- ister the wrong headspace pressure causing too high a nitrogen
desired gases and vapors may be emitted into the atmosphere. As consumption. When a blanketing valve does not open far enough
these situations must be avoided, the tank needs to be sealed. The the inflow of nitrogen will be too low which may result in suffi-
tank does however need to be kept under constant pressure in ciently reduced headspace pressure as to cause the tank to im-
order to avoid overpressure when it is filled or when temperature plode or the leaking of air into the tank, which, as mentioned,
rises, and much more importantly, to avoid vacuum when product can have consequences with regard to product quality and, de-
is drained. Large storage tanks especially are not compatible with pending on the stored product, can seriously increase the risk of
low pressures. explosion.

The blanketing system is there to guarantee that the tank head- Nitrogen
space is kept both under inert atmosphere and at constant pres- Increased focus on both safety and quality has led to an uptake
sure. One way of achieving this is through continuous purging in the use of blanketing operations worldwide and consequently
with nitrogen, which is a relatively easy and safe alternative. in the use of nitrogen. For various reasons the demand for nitro-
Though this method requires low capital investment, it involves gen has increased globally to such an extent that nitrogen no
high operating costs as it consumes nitrogen continuously. longer has the status of being simply a by-product of oxygen
production but is now considered a main product in itself. The
growing demand has naturally had its impact on price but as

2 METTLER TOLEDO
energy costs make up half of the production costs of nitrogen, In more detail the process is as follows:
2008’s surge in energy prices only caused an average nitrogen The goal is to prevent the oxygen concentration from exceeding
price increase of over four percent. Obviously, transport costs play the so called Limiting Oxygen Concentration (LOC), which is
an important role here as well. The ways nitrogen arrives at end- specific for each product that is blanketed and also referred to as
user facilities can differ substantially. Smaller users get their MOC or Maximum Oxygen Concentration. These specific values
nitrogen supplied compressed in cylinders or in bulk tank trans- can be found in databases such as CHEMSAFE. For safety reasons,
port. Larger ones may have nitrogen delivered by pipeline but two threshold values are established; well below the LOC (the
such an infrastructure is limited to heavier industrialized areas. Lower Intervention Level) and the Upper Intervention Level.
Others choose to have a nitrogen generation plant on site. So the These two threshold values are the set-points that control the
average price increase does not paint the full picture. All in all, purging of nitrogen. The moment the oxygen concentration
smaller and mid-size users, especially in more remote locations, reaches the Lower Intervention Limit the nitrogen flow is inter-
reported price increases of 15 percent or more between the end of mitted. Purging of the vessel is resumed when the upper inter-
2008 and mid-2009. vention limit is exceeded. This means that the inerting system
keeps the consumption of nitrogen minimal while safe operation
Headspace gas analysis is ensured. Depending on individual process conditions and sol-
One way to increase safety and reduce the use of nitrogen simul- vents present, the oxygen level is usually maintained somewhere
taneously is to control inertization as a function of oxygen con- between 2 and 12 vol %. The system consists of an oxygen ana-
centration in the headspace. The idea behind this is the follow- lyzer system, a PLC, a blanketing regulator, a breathing valve, a
ing: Depending on the product and the reason for blanketing or safety relief valve, etc.
inerting, there are tolerances when it comes down to the maxi-
mum allowable oxygen concentration. Certain monomers require This method is suitable for most inerting operations and pro-
zero percent oxygen to prevent polymerization. Others require a cesses that require an exact oxygen level. For tank blanketing
small amount of oxygen for the same reason. In the case of explo- things are, however, slightly more complicated as the main objec-
sion protection, the oxygen concentration does not necessarily tive is still to allow breathing of the tank which, after all, depends
need to be zero. In fact, for all solvents a so-called limiting oxy- solely on headspace volume changes. It is obviously not possible
gen concentration exists. Below this concentration there is no risk to stop the nitrogen flow just because the oxygen level has reached
of explosion. It is obvious that controlling the nitrogen purge the set-point whilst product continues to be pumped from the
based on the oxygen concentration will seriously cut nitrogen tank. As discussed, the created vacuum could seriously damage
costs. Furthermore, the measurement of oxygen concentration in the tank. This problem can be overcome by replacing some of the
the tank headspace provides an important safety parameter. nitrogen by air. Once again, the aim is not zero oxygen. So in-

Fig. 1: Typical control of O2 in an

inertization process with oxygen
concentration based regulation.
12

Limiting oxygen concentration (LOC)

10
Oxygen concentration in Vol-%

Safety
margin
8
Upper intervention limit

Lower intervention limit

2

0
0 1 2 3 4 5
Time

METTLER TOLEDO 3
White Paper

stead of purging with pure nitrogen a mix of nitrogen and air can
be used. Technological developments in on-site nitrogen genera- Theory
tion make this even easier. With membrane filters or molecular Amperometric oxygen measurement is a well es-
sieve type technologies it is possible to produce any purity of ni- tablished method for both dissolved and gas
trogen up to 99.9 percent, on demand. The oxygen analyzer makes phase oxygen measurement. The basic principle
a reliable and cost efficient nitrogen supply and safe blanketing is the chemical reduction of an oxygen molecule
process possible. and the measurement of the resulting current be-
tween a cathode and an anode.
Oxygen analyzer solutions
Often, however, the use of oxygen analyzers encounters resistance; Cathode reaction
the reason typically being the high capital and operating costs of O2 + 2 H2O + 4 e– = 4 OH–
the oxygen analyzer system. A conventional system usually con-
sists of an extractive type oxygen analyzer, typically based on Anode reaction
paramagnetic or, less frequently, zirconium oxide technology. 4 Ag + 4 Cl– = 4 AgCl + 4 e–
Both types of analyzer require extensive sample conditioning, a
pump to drag the sample, tubing, valves, filters, coolers, heaters, Between the anode and the cathode a constant
dryers and so on. In short, it means a huge amount of mainte- voltage of around – 600mV is applied to induce
nance and potential for failure due to the complexity of the system the oxygen reduction. This reaction is linked to a
and the fragility of the analyzers. Apart from all the peripherals current flow which is proportional to the partial
that contribute substantially to the investment, the analyzer itself pressure of oxygen.
is very costly. The reluctance to install such a system to control a
blanketing operation is understandable. Different system options are available depending
on the process conditions and application re-
Advantages of direct in-line measurement quirements.
The solution can, however, be much simpler and definitely more
reliable. With amperometric oxygen measurement METTLER The advantages of amperometric measurement
TOLEDO offers a cost-effective and safe solution in a 12 mm probe are on the one hand in the robustness of the sen-
that totally eliminates the need for a sample conditioning system. sor that allows installation directly into the pro-
The amperometric or polarographic oxygen electrode can be cess without the need for complex and mainte-
mounted directly into the vessel or nitrogen discharge piping and nance intensive sample conditioning systems.
is not sensitive to dust, moisture or solvents. A retractable sensor The absence of such a sample handling installa-
mounting assembly allows retrieval of the sensor without inter- tion greatly reduces failure potential.
rupting the process, e.g. for ease of calibration. No special calibra-
tion gases are needed, as a one point calibration with air is all that On the other hand the simplicity of the analyzer
is required to maintain the probe’s accuracy. In very critical ap- also reduces the cost of ownership to a fraction
plications, the system can be equipped with redundant oxygen of that of extractive analyzer systems. Mainte-
probes for additional safety and self-check purposes. nance does not require specialist know-how and
can be carried out in just two minutes.
Compared to traditional extractive analyzer technology the
METTLER TOLEDO solution is available at only a fraction of the In summary, amperometric oxygen measure-
cost. Firstly, the analyzer itself is certainly lower priced, and sec- ment provides an attractive alternative to oxygen
ondly, the absence of the sampling and sample conditioning sys- analyzers based on extractive technology.
tem contributes to even lower costs. The most valued cost benefit
however is the enormous savings on maintenance. The only main-
tenance needed with a METTLER TOLEDO solution is the occa-
sional refilling of electrolyte, which is merely a two-minute
operation.

4 METTLER TOLEDO
Conclusion
Inertization and nitrogen blanketing of vessels and process Intelligent Sensor Management
equipment is gaining ground globally thanks to safety and prod- Though the principle of amperometric oxygen
uct quality awareness. Price increases on the world nitrogen mar- measurement is more than fifty years old, the
ket, however, are causing users to look for more economical technology has not ceased to develop. Significant
technologies with lower nitrogen consumption. One of the most improvements have been made to the cell itself
efficient ways of minimizing the use of nitrogen and increase and high performance membranes now allow for
safety at the same time is controlling the inerting or blanketing fast and accurate measurement in a wide range of
based on oxygen concentration. Drawbacks, however, are the applications. One of the most recent features is the
high maintenance demands and the high installation costs. Ad- integration of the Intelligent Sensor Management
vances in sensor technology and intelligent automation of the (ISM) platform. Using the power of intelligent sen-
measurement point enable reliable oxygen measurement in an sor technology greatly improves reliability and
extremely simplified way, eliminating the need for expensive reduces maintenance efforts at the same time.
sample conditioning. Nitrogen savings and the lowest possible Continuous self-diagnosis provides real-time sta-
maintenance needs allow for a fast pay-back of the oxygen ana- tus information and predicts maintenance require-
lyzer. ments in detail.

Comparison „Conventional vs. new Real In-Line Measurement Installation“

Simplified system setup with real in-line measurement
Off-Line N2 in

Valve Transmitter
ter

NEW! Real In-Line Measurement

Pump
„Bring the Sensor to the Sample“

Flow Meter
F

Filter

Washer

Cooler

Analyzer O2

Conventional Process Installation

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CH-8902 Urdorf
Switzerland