What makes speciality gases so special?

The complexities that go into the manufacture and handling of speciality

gases for the petrochemical sector, which differentiate them from other types
of industrial gases
Stephen Harrison and Steen Sorensen Linde Gases Division

dvanced industrial processes in the petrochemical sector continue to demand

speciality gases with ever higher levels of
purity and more precise accuracies. An increasing number of specifications for these gases now
go down to parts per billion (ppb) and sometimes even to parts per trillion (ppt). Gas supply
companies have to ensure that the speciality gas
supplied is the one that best corresponds to the
application it will be used for in this industry.
The characteristics of these exotic, non-standard speciality
gases, in comparison with
standard industrial and medical gases, divide the
gas supply market into specific segments. Within
the pure speciality grades, purity can reach up
to 99.99999% (7.0). Higher purity means fewer
and lower levels of the impurities that cause
problems with high-tech production processes or
instrumentation and analytical measurement.
This high level of purity, compared to the same
gas at an industrial or medical purity, is one of
the differentiators that make a speciality gas
special. Oxygen, for example, is a common
medical gas and its purity must be suitable for
people to breathe. Oxygen is also used in industrial applications, for instance, when it is mixed
with acetylene to create a flame to weld and cut
metal. In this application, the purity level of the
oxygen need only be sufficient to create a flame.
Oxygen is also used in speciality gas applications, such as laboratory instrumentation, but
the purity of oxygen required in this laboratory
gas application is much higher.
Another characteristic of speciality gases in
comparison to medical or industrial gases is the
complexity of the product. While a gas mixture
for a welding application could comprise a
mixture of argon and carbon dioxide to weld

www.digitalrefining.com/article/1000769

steel, and a gas mixture used in a medical application could harness a mixture of nitrous oxide
and oxygen for anaesthesia, speciality gas
mixtures are far more complex. Instead of two
or three different chemicals in the mix, there
could be a combination of 20 or 30 chemicals.
In addition, instead of blending these chemicals
to a tolerance of, say, plus or minus 5%, the end
user might require the component to be blended
at an accuracy of plus or minus 1%.
Refinery and petrochemical processing calibration mixtures can range from a simple 2.5%
methane/air mixture, to much more complex
mixtures of 20 or more hydrocarbon components. Most calibration mixtures are stored
outside the analyser stations - and with winter
temperatures often dropping to minus 15
degrees Celsius or more, gas mixtures must be
specially formulated to avoid the condensation
of
some
heavy
mixture
components.
Additionally, environmental mixtures need to
comply with requirements for Continuous
Emission Monitoring Systems (CEMS).
With any gas mixture used for calibration
purposes, the most important requirement is
that it must accurately and repeatedly report
values of the relevant instrument being calibrated. Calibration should be precise and must
be proved to be so. Many gas mixtures used to
conduct environmental monitoring are required
by national environmental authorities to be
accredited. Accreditation is therefore an important factor in the production of speciality gases,
proving to petrochemical plant operators that
the gas mixture has been prepared to the
required quality.
Speciality
gas plants and filling stations
should achieve certification as producers under

May 2013 1

ISO 9001, often with selected facilities independently accredited to programmes such as ISO
17025:2005 as testing and/or calibrating laboratories and ISO Guide 34 that provides the
highest level of quality assurance. Companies
such as Linde Gases can confidently state that
methods used to certify its accredited calibration
gas mixtures are accurate, consistent, documented and validated.
Scale of supply is another major differentiator
between speciality gases and industrial and
medical gases. The quantities in which speciality
gases are requested by end users are frequently
much smaller than the other gases. How much
of the gas will be used and how many customers
will want this particular product also influences
scale of supply.
Some of the most common industrial gases are
supplied to customers through pipelines in
quantities such as thousands of tons per day, or
in bulk format by 20-30 ton road tankers, where
the liquefied gas is supplied to customer facilities and vaporised on site to yield the gas
required. This is a cost effective way to buy high
quantities of standard industrial or medical
gases. In contrast, speciality gases are typically
supplied in cylinders containing about 10 cubic
metres of the gas or in small portable cylinders
that only contain one cubic metre of the
product.
There are often more than 1,000 gas cylinders
of different types on a large petrochemical site at
any given time, while an ASU (air separation
unit) supplies tonnage scale nitrogen or oxygen
requirements. Bulk storage tanks also contain
liquefied gases for intermediate volume supply
requirements.

Speciality gas production

In many cases speciality gases and mixtures are
unique one-off products developed for a
specific customer application and they require a
great deal more product engineering compared
to the standard industrial or medical gas products. For this reason, they are not always off the
shelf items and can even take several weeks to
produce in the most complex of cases.
Where a raw material of the required purity
cannot be sourced, the gas producer must buy
the highest purity available and introduce additional purification processes in-house to achieve
an end product of a sufficiently high purity.

2 May 2013

Finally, the level of quality control associated

with speciality gas production is far higher than
with industrial and medical gases. Sophisticated
laboratory instrumentation is used to analyse
and verify the constitution of many products and
customers are then provided with a certificate
declaring the analytical results.
As many as 200 different multi-component
gas mixtures are often required at a large refinery complex. These are all made-to-order and
therefore require fairly lengthy production, certification and delivery lead times in comparison to
the standard off-the-shelf industrial gases
range. To facilitate timely repeat ordering of
these complex gas mixtures, plant instrument
tag numbers can be used to allow personnel to
reference exactly where the mixtures are
deployed in the different sections of the plant.
Packaging is an issue on its own. Since these
gases are generally required in small quantities,
they are typically supplied in cylinders and
extreme care must be taken when introducing
the speciality gas into the cylinder. The materials of construction for these cylinders are also
very important in maintaining the integrity of
product. While steel cylinders can be used for
most industrial and medical gases, and some
speciality gases, speciality gas products often
require aluminium alloy cylinders, which are
more compatible with the purities and chemicals
associated with speciality gases. The valves on
top of the cylinders must ensure that the
contents remain inside and contaminants from
the atmosphere remain outside. Specialist materials, such as stainless steel or a very high grade
brass, are therefore also needed for valve
construction.
Packaging of speciality gas mixtures is also a
challenging task because the tolerance, or accuracy, of the component percentages must be
maintained. Often these highly accurate mixtures
are needed to calibrate a measurement and gas
producers must utilise highly sophisticated filling equipment and processes to ensure the
products integrity. Speciality gas cylinders have
to be heated, evacuated and purged to expel any
traces of moisture or other impurities before the
product is introduced, creating yet another
production step that is not necessarily required
for the majority of industrial and medical gases.
Refinery process safety is supported by the
supply of calibration gas mixtures used to

www.digitalrefining.com/article/1000769

calibrate sensors that detect explosive environments. These sensors would detect the build-up
of an explosive gas, such as ethylene, and trigger
an alarm to implement corrective action if the
build-up reached a critical level. These sensors
require frequent calibration with highly accurate
calibration gas mixtures to ensure they function
correctly.

Maintenance and efficiency

The most practical way to reduce emissions from
a refinery is to ensure that the processes operate
optimally. This requires each unit to operate at
maximum productivity levels, so that less energy
is required and fewer waste gases are emitted.
To achieve this, plant personnel use process
control analysers, which also require frequent
calibration, to obtain accurate and reliable readings. These devices continuously consume high
purity gases in order to function and require
occasional calibration with high precision gas
mixtures.
Regular maintenance of refinery process
equipment is a vital intervention at longstanding
facilities. In addition to safety, maintenance is
targeted at maintaining optimal performance of
plant equipment and at minimising operating
costs, for example periodic de-scaling of heat
exchangers using large quantities of acidic gases
such as hydrogen chloride.
Additionally, the efficiency of a refinerys
refrigeration system relies to a large extent on
optimum heat exchange. The refrigeration plant
requires refrigerant gases and also oil to lubricate its moving parts and, over the course of this
operation, oil inevitably leaks into the refrigerant over time and this contamination of the
refrigerant gas compromises the plants efficient
function. Linde has installed patented technology in at least one of its primary refinery
customer sites a self contained, compact and
portable high-speed decontamination unit which
purifies the refrigerant, separates out the oil,
removes moisture, non-condensables and any
other potentially damaging particulates and then
returns the refrigerant gas to the system. All of
this is done during refrigerant plant operation,
to avoid the cost of process shut-down.

Speciality gas distribution equipment

Protecting the integrity of gas throughout the
supply chain, from manufacture to end user, is

www.digitalrefining.com/article/1000769

an ongoing challenge to gas suppliers, requiring

intense focus on the safety and integrity of gas
equipment. Many of the gases supplied are
corrosive, toxic, flammable or high purity, all of
which require a complex infrastructure of high
precision regulators, valves and piping to ensure
their safe supply. This equipment ages with use,
particularly the moving parts, and can deteriorate over time, owing to the harsh nature of the
gases passing through it, requiring regular
inspection and maintenance activities to prevent
incidents and accidents.
Complex petrochemical processing and instrumentation demand products of the highest
quality to maintain peak performance.
Distribution systems for speciality gases must
meet increasing demands for optimal standards
of performance, new analysing methods and
production refinements. Impurities occurring in
just a few ppm can have serious consequences to
end users in application. The demands made on
regulators and valves in these environments are
extremely high and components must be capable
of handling high and low pressures, large and
small flows and must also be suitable for
high-purity inert gases, as well as reactive, flammable, corrosive or toxic gases.
These often low concentration components in
speciality gases are easily compromised by a
reaction with contaminant gases in the atmosphere. In response Linde continues to develop
increasingly hi-tech containers, valves, regulators and supply systems, constructed from new
generation materials, to ensure that gas products
remain pure and uncontaminated throughout
their life cycle and mitigate risks to the environment or human health, protecting all parties
from the high cost of integrity failure. At critical
moments, quality of the gas is only as good as
the gas distribution system itself.
As dangerous substances can be constituents
in speciality gases mixtures, personal safety and
environmental protection are primary concerns.
Gas distribution systems must meet stringent
requirements to protect the health and safety of
the people who work with them.
Optimum gas handling equipment functionality is critical and must be equal to the
sophisticated gas being handled. This encompasses factors such as pressure reducing
regulators and purge functionalities. Materials
of construction are once again critical to the

May 2013 3

integrity of the distribution system, particularly

where speciality gases contain corrosive components. Joints, seals, moving parts and fittings in
regulators and valves must be absolutely tight
and impermeable much more so than for the
equipment used to supply industrial and medical
gases.
In these applications, the term helium leak
tightness is often used to determine leak potential, referring to how much helium will leak out
within one second under certain circumstances
from the inside of the system to the outside.
Typically, with industrial and medical equipment, one cubic centimetre of helium could leak
within an hour from a component. On the other
end of the scale, speciality gas distribution
systems might display far lower leak rates, capable of maintaining their integrity up to and even
far beyond 30 years for the loss of one cubic
centimetre of helium.
To avoid any reaction between the speciality
gas product and the material of construction of
the distribution system, sophisticated materials
such as stainless steel or Hastelloy can be
utilised to construct the system components,
owing to their excellent anti-corrosive characteristics and their first-rate sealing qualities once
welded. These components must also be impermeable, both in terms of gas leaking out of the
system and atmospheric gases infiltrating into
the system. The sum of the leaks is critical and
all connections, components, piping and tubing
must be as tight as possible. Bar stock and
forged components are favoured for speciality
gas applications, rather than the cast componentry suitable for industrial and medical gas
distribution systems, which does not provide
sufficiently tight housings required for speciality
gases.
In these speciality gases distribution systems,
connections between the gas cylinder, the gas
distribution system and the application are
generally comprised of polytetrafluoroethylene
(PTFE) hoses or thin walled, flexible stainless
steel hoses, because rubber hosing, which is
often used for industrial gases, is slightly porous.
In addition, compression fittings and orbital
welds are used to ensure uncontaminated and
unyielding joins. Where very low ppm or
particularly corrosive mixtures are being
supplied, metal gaskets are also favoured above
rubber or plastic alternatives.

4 May 2013

Another factor is the internal roughness of the

distribution system and this must be very
smooth to ensure contaminants such as oxygen
and water cannot attach to the rough surface
during the purging process. Stainless steel
tubing is less rough internally and is therefore
preferred over copper. It is imperative that no
impurities remain in the system when a new
installation is commissioned or when a cylinder
is changed out. For this reason, extreme care
must be taken when making or breaking a
connection in an existing speciality gas pipeline
to conduct maintenance or change out a cylinder
connected to the gas distribution system. In
these instances, technicians are effectively opening up a closed system to the atmosphere.
When this kind of activity is associated with an
industrial gas distribution system, new tubing
can simply be soldered or welded in. Pressure
testing can then be undertaken using water or
compressed air. Medical gas distribution systems
are more complicated and require particular care
to ensure the correct gas has been returned to
the system.
But before speciality gas distribution systems
can be brought back on stream, several precautionary processes are necessary. These systems
should not remain open more than necessary
and, during maintenance or building operations,
all open ends must be properly sealed to ensure
that no contaminants enter the system from the
atmosphere.
High purity argon is generally used as a shielding gas during welding of stainless steel
pipework for speciality gases applications to
ensure that the joints are smooth and non-porous. Furthermore, the gas used to pressure test
the system after any welding activity must be of
a similar quality to the product the system is
being used for. Purging with a lower quality gas
could introduce moisture and other impurities
into the system that can be difficult or impossible to remove afterwards. Other tests prior to
bringing a speciality gases piping installation
online might include vacuum testing and helium
leak testing, depending on the sophistication of
the system and the customers requirements for
the process gas.
Once maintenance activities have been
completed, gas pipes and process units are
generally flushed through with nitrogen to purge
them of any atmospheric air and moisture,

www.digitalrefining.com/article/1000769

which could pose a safety risk related to an

explosive chemical reaction when a flammable
gas, such as ethylene, re-enters the process.

LINKS
More articles from: Linde HiQ
More articles from the following categories:
Automation & Process Control Emissions Control
Laboratory/ R&D/Quality Control
Mechanical Engineering
Storage & Handling

www.digitalrefining.com/article/1000769

May 2013 5