Innovations in wastewater treatment
Industrial gases provide a wide range of options for treating wastewater from
petrochemical processes
Darren Gurney Linde Gases Division
T
he demand for efficient and cost-effective
wastewater treatment technology in the
refining and petrochemical sector is being
driven by not only ever-tightening environmen-
tal legislation, but also by the sector’s own desire
to follow a meaningful sustainability agenda and
to take its responsibilities around product stew-
ardship seriously. However, refining and
petrochemical companies are continually
confronted with the challenge of striking a
balance between making their activities profita-
ble while ensuring the industrial processes
involved in the production and application of a
chemical product, across its lifecycle, have mini-
mal impact on the environment.
Treatment of wastewater from petrochemical
plants can be a challenging and costly matter,
particularly when needing to comply with the
requirements of operational permits and national
environmental legislation governing the discharge
of treated wastewater into community treatment
plants or natural water bodies such as rivers,
lakes and oceans. The segregation, collection and
treatment of wastewater play a vital part in the
protection of public health, water resources and
wildlife. Refining and petrochemical facilities, as
part of their permit to operate, must demonstrate
that they are successfully able to treat all their
pollution streams to the appropriate regulatory
standards.
One of the most widely used strategies to meet
the ever-rising demand for water and increas-
ingly strict regulations governing water
protection is through improved water manage-
ment and strengthened investment in the
technologies that preserve and recycle process
wastewater.
The refining industry converts crude oil and
associated petroleum gas (APG) into hundreds
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of refined products, including petroleum, diesel
fuel, kerosene, aviation fuel, fuel oils, lubricat-
ing oils and primary feedstock for the
petrochemical industry, and in doing so it
employs a wide variety of physical and chemical
treatment processes in which large volumes of
water are utilised, especially for cooling systems,
distillation, filter backwashing and deionisation
techniques. Vessel cleaning, equipment flushing
and surface water run-off also generate addi-
tional volumes of wastewater that need to be
treated. In turn, the petrochemical industry
produces a multitude of essential products to
modern-day living including intermediates for
the pharmaceutical industry, aromatic organics,
solvents, alcohols, ketones, polymers and alde-
hydes, all of which are synthesised through
various process operations, which can produce
large quantities of wastewater that must be
treated.
Given the complex and diverse nature of refin-
ery wastewater pollutants, a combination of
physical, chemical and biological process trains
and treatment methods are usually required
before it is finally discharged into the aquatic
environment.
Wastewater treatment can be improved signifi-
cantly by harnessing industrial gases such as
pure oxygen, for example, to enhance the biolog-
ical assimilation and oxidation processes of
wastewater treatment plants or prevent unde-
sired odours in refinery mains or storage lagoons
and tanks. Carbon dioxide is a versatile and safe
substitute for corrosive mineral acids to effec-
tively neutralise alkali wastewater.
The technology used for refinery wastewater
systems is site specific and depends on the nature
of influent (incoming wastewater) conditions and
the level of treatment required by local regulatory
PTQ Q4 2012 1
 Oxygen tank
CO2 metering
Evaporator
Control
unit
Wastewater inlet
Figure 1 Solvocarb-R process
authorities. However, a typical refinery wastewa-
ter treatment plant usually consists of
physico-chemical pre- and primary treatment,
followed by secondary biological treatment and
tertiary treatment, if necessary.
In a refinery wastewater treatment system, two
steps of oil removal are typically required to
achieve the necessary removal of free oil from
the collected wastewater prior to feeding it to a
biological system. This oil removal is achieved by
using an American Petroleum Institute (API) or
equivalent oil water separator followed by a
dissolved air flotation (DAF) or induced air flota-
tion (IAF) unit.
The wastewater is then routed to the primary
treatment clarifier and to the aeration tank and
secondary clarifier, which constitutes the biologi-
cal system. The effluent from the clarifier is then
sent to tertiary treatment, if required, prior to
discharge. The activated sludge process is the
most widely used wastewater treatment technol-
ogy for the removal of soluble organic
contaminants in the oil refining and petrochemi-
cal industry. Often the pH of the raw wastewater
requires reducing before it can be accepted by
the bio-treatment stage, as the high pH could
potentially kill off the bacteria doing the
treatment.
2 PTQ Q4 2012
Solvocarb
reactor
Centrifugal
pump
pH
electrode
Discharge
Clear water
CO2: versatile acid alternative for pH control
In the UK, the industrial gases technology
company BOC Ltd, part of The Linde Group, has
seen wastewater treatment successfully imple-
mented at a major plant operated by one of the
world’s leading petrochemical manufacturers.
The 1700-acre site is highly integrated, exploit-
ing synergies between the petrochemicals plant
and adjacent refinery. The petrochemicals facil-
ity manufactures over 2 million tonnes of
chemicals products per annum and the refinery
has an annual capacity of 10 million tonnes.
At the petrochemicals plant, an environmen-
tally friendly CO2-based technology, Solvocarb, is
being used to control alkali aqueous wastewater
pH prior to discharge. The system uses gaseous
CO2 to neutralise alkaline waters through the
production of carbonic acid (see Figure 1).
The refinery, in compliance with legislation at
the time, had been discharging wastewater from
the plant into the local river estuary after
adjusting its pH using mineral acids, such as
sulphuric and hydrochloric. Variability in
discharge pH and the corrosive nature of strong
mineral acids led to concerns over potential
harm the discharge may cause to aquatic wild-
life resident in estuaries.
In addition to the plant needing to find a more
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environmentally friendly wastewater pH control
solution, it needed to find one that would give it
more robust control over the whole process. In
order to achieve the target pH range through the
use of mineral acids, the company observed peri-
ods of pH oscillation from too much acidity
dosing, requiring adjustment with additional alka-
linity. This inevitably leads to extra cost and
operating complexity arising from operating two
pH adjustment processes. The company ulti-
mately opted for a single process route involving
CO2, which preserves the natural alkalinity of the
wastewater and the process pH control is more
stable over the desired pH control range. BOC
was appointed to design the pH control system
for the newly designed wastewater treatment
plant.
Owing to strict environmental permits, waste-
water may only be discharged into the outlet
channels if it is within a narrow pH range —
usually between 9 and 6. The Solvocarb method
employs gaseous CO2 to neutralise alkaline
waters. When dissolved in water, CO2 forms
carbonic acid, which reacts with the alkalinity
to form a salt. The neutralisation reaction
controls the pH value to the appropriate
discharge level.
Awarded the contract to design two Solvocarb
systems to neutralise all plant wastewater,
anywhere between 10 000 and 20 000 cu m/d,
BOC engineers designed each system to simulta-
neously mix and dissolve CO2 into each 10 000
cu m tank, controlling the pH to the appropriate
set point. Consent permits dictated the site could
only discharge pH-corrected wastewater into the
estuary when the tide was in, allowing the
treated wastewater to dilute effectively into the
larger body of available water in the estuary.
However, this meant that the whole process had
to be completed within a restricted time period
of a six-hour window between the two tides.
It was critical for the wastewater to be neutral-
ised in the two tanks within the time available,
which called for challenging process hydrody-
namics. Large and variable volumes of
wastewater needed to be brought within the
correct pH range within a fixed timeframe — the
wrong pH value could result in the refinery being
unable to discharge the wastewater, causing
potential bottlenecks and resulting in backups
further up the process chain. A significant
amount of testing was conducted before the team
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was satisfied that the proposed system would
operate to the required parameters.
The new wastewater treatment plant was
commissioned in February 2000 and was
completed on time and on budget. BOC has
continued to supply the plant for nearly 12 years.
The continued successful operation of the plant
will help safeguard the environmental status of
aquatic areas in which the wastewater is
discharged.
Today, the main driver for treating effluent
high in alkalinity prior to discharging to the
outfall is the strict regulation to protect the
sensitive, biodiverse ecosystem within the estu-
ary. Using CO2 to neutralise an alkali effluent
avoids large swings in the discharge pH, a vital
component in creating a sustainable and suitable
environment for marine life.
Compared with mineral acids commonly used
in previous years, CO2 offers many advantages,
amounting to the best economical and ecological
alternative. CO2 is not categorised as a substance
that is harmful to water and does not lead to the
addition of unwanted anions in the water envi-
ronment, such as chlorides and sulphates. There
is also no over-acidification of the wastewater,
due to the self-buffering nature of CO2 in water,
which produces a flat neutralisation curve and no
corrosion of system and equipment components.
CO2 is also far safer than the acids previously
used. Simple to handle, it is delivered as a liquid
cryogen that is stored in tanks onsite and dosed
automatically into the process.
The fact that CO2 is sequestered and effectively
removed from the global carbon cycle means
that it is not available to take part in global
warming; therefore, less CO2 is being released
into the atmosphere. This gives the Solvocarb
process its green credentials.
Pure oxygen wastewater treatment
The application of pure oxygen has been success-
fully applied in the activated sludge process to
treat a variety of industrial and refining opera-
tions wastewaters for over 30 years. The
activated sludge process is the most widely used
form of biological treatment for organic contami-
nants in aqueous wastewater globally. There
have been numerous industrial wastewater
installations built around the world where pure
oxygen is routinely used. The application tech-
nology can be designed into the process during a
PTQ Q4 2012 3
 Oxygen tank
Evaporator Control
unit
Oxygen diffusion
Wastewater inlet
Sewage immersion pump
Venturi pipes
Figure 2 Solvox-V process
greenfield build or later as a retrofit application
to increase the capacity of an existing asset.
Linde’s Solvox wastewater applications are an
example of a pure oxygen wastewater technology
that can be employed in the original design of an
activated sludge plant or retrofitted as an
upgrading technology for existing wastewater
treatment plants (see Figure 2). The primary
application in most cases is to increase treatment
capacity in existing plants that are overloaded or
experience wide swings in dissolved oxygen
demand. The philosophy of Linde has been to
provide, where practical, performance improve-
ment in existing assets rather than building new
plant capacity to increase wastewater treatment
throughput. This approach allows the operator
to harness the benefits of pure oxygen within the
existing plant footprint and improve operational
performance; for example, lower surplus sludge
production, reduced volatile emissions, lower
operational power consumption, better settle-
ment of biomass and simple installation.
Efficient oxygen transfer and adequate process
mixing are essential components of all aerobic
wastewater treatment processes and these can be
readily achieved using air or pure oxygen
supplied equipment. However, traditional aera-
tion systems, designed as fixed mass transfer,
often cannot match the variability or increased
oxygen transfer intensity requirements of the
activated sludge process, especially when operat-
ing temperatures increase above aeration
performance design values, normally around
4 PTQ Q4 2012
Discharge
Aeration
Mixing pipes tank
20°C. Pure oxygen-based systems, on the other
hand, have the potential to significantly enhance
the aeration process by augmenting, or
completely replacing, portions of the installed
existing aeration systems, even at elevated
temperatures of >30°C.
Pure oxygen is able to maintain a higher aera-
tion intensity because air only contains one-fifth
oxygen by volume, and the limitation on oxygen
transfer is controlled by the partial pressure of
oxygen in air and the oxygen solubility at a given
water temperature. The activated sludge proc-
ess requires a positive dissolved oxygen level of
at least >2 mg/l to be effective. As the tempera-
ture increases and the background dissolved
oxygen remains constant, the driving force of air
effectively reduces. It is the driving force poten-
tial of pure oxygen, compared with air at the
same temperature, that proportionately
increases the rate of oxygen transfer into the
activated sludge treatment process. Combined
with effective mixing, a constant supply of
dissolved oxygen ensures that the micro-organ-
isms providing the biological wastewater
treatment perform to their maximum potential,
in an environment where oxygen transfer
matches their demand.
The Solvox concept is to introduce pure oxygen
into the wastewater treatment process via a
family of specially designed and developed pure
oxygen and air oxygen application equipment.
Equipment is configured to work alongside exist-
ing aeration equipment and meet the oxygen
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demand of the biomass generated during synthe-
sis and oxidation of biodegradable contaminants.
Within industrial wastewater treatment plants,
pure oxygen can be used in conjunction with air
to increase operational efficiency or overall treat-
ment capacity. Often the existing aeration
equipment has reached its maximum transfer
intensity due to limitations brought about by the
nature of the wastewater, plant operating
temperature or reduced efficiency due to equip-
ment wear and tear.
Solvox oxygen solutions can also be used to
prevent odour nuisance from wastewater that is
transferred in large pressurised pipelines and
mains, especially if the retention times are long.
The addition of oxygen prevents the naturally
occurring bacteria on the pipe walls from
consuming the chemically bonded oxygen and
producing highly odorous compounds such as
hydrogen sulphide and mercaptans. Such
compounds can quickly result in the corrosion of
pipework networks and ancillary equipment. The
addition of free oxygen creates ideal conditions
for successful preliminary treatment and aerobic
sealing of sludges in tanks and vessels.
Equipment and process knowledge can be
applied in a variety of ways to improve the oper-
ational performance efficiency of many industrial
wastewater treatment plants and processes.
Adding oxygen using Solvox equipment requires
an initial low capital investment and, once
installed, is designed to be operated flexibly so it
can be adjusted to seasonal needs or used to
Untreated Process
wasted water control
Bioreactor
Bio-treatment and oxygenation
Figure 3 Axenis wastewater treatment system
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track peak loading during ramp-ups in produc-
tion campaigns.
Water reuse and recycling
Recycled wastewater makes it possible for compa-
nies that use water in their processes to treat the
effluent on-site and reuse or recycle as much of it
as possible back into the industrial operation.
Many companies are turning to this alternative
against a background of increasing pressure in the
form of restrictions on allowable discharge
volumes, limitations on abstraction quotas and
mains supply, legislative pressure and the upward
spiralling increase in the “turnaround costs” of
water. The latter considers both incoming water
supply and trade effluent discharge costs. Linde’s
wastewater recycling technology, Axenis, employs
a high-rate membrane bioreactor treatment stage
and uses a combination of pure oxygen and air to
ensure optimal process performance (see Figure
3). The membrane replaces the secondary clarifier
used in conventional activated sludge plants.
Against a conventional wastewater treatment
solution, the innovative, patented process offers
very substantial cost savings across the industrial
water lifecycle. This includes much reduced capi-
tal investment, lower energy costs and superb
final effluent quality. When combined with
reverse osmosis as a tertiary treatment step to
provide high-quality softened water, Axenis
makes wastewater reuse a possibility for a large
number of organisations. By unlocking the
resource they already have available, operators
Oxygen and air injection
controlled by DO and pH
feedback loops Oxygen
Air
Membrane
modules
Separation of biomass
/ treated water
Treated
water
RO process and Water re-use /
water re-use final disposal
PTQ Q4 2012 5
 have the potential to increase production capac-
ity in a more sustainable manner without further
depleting a finite natural resource. All this can
often be achieved at much lower cost than paying
for the supply and disposal of process water.
Advanced oxidation, ozone solutions
Oxygen can also be applied in other wastewater
treatment applications such as ozone water treat-
ment, where in combination with either hydrogen
peroxide (H2O2) or ultraviolet radiation (UV) it
is effective in partial or total oxidation of many
non-biologically treatable wastewater
compounds, colour removal and as a chlorine
replacement for primary disinfectant. Ozone (O3)
is a molecule consisting of three oxygen atoms
and is created by passing oxygen through ultra-
violet light or a “cold” electrical discharge. Under
ambient conditions, ozone is very unstable, read-
ily giving up one atom of oxygen within its short
lifespan of usually less than 10 minutes.
However, this process results in a powerful
oxidising agent called a free radical, which is
toxic to most waterborne organisms. This prop-
erty makes ozone a very strong, broad spectrum
disinfectant and biocide that will oxidise many
organic and inorganic substances. For this
reason, it is used widely throughout the world.
Its strong oxidising properties make ozone an
effective chemical for water treatment, but to use
ozone it must be created on-site and added to
the water by bubble contact. A major advantage
of ozone includes the production of fewer
dangerous by-products in comparison to chlorin-
ation, for example.
Due to the growing concerns over chlorinated
by-product formation, the use of ozone in water-
based evaporative cooling towers is becoming an
increasingly attractive option, particularly within
process industries. It can also provide wider
environmental benefits in comparison to the
more traditional chemical treatment
programmes.
Typically, chemicals such as chlorine and
chelating agents are added to cooling tower
water to control microbiological growth and
inhibit mineral build-up. However, as the volume
of water in a cooling tower is reduced through
evaporation, the concentration of water treat-
ment chemicals and their by-products contained
within the tower increases. To maintain chemical
and contaminant concentrations at prescribed
6 PTQ Q4 2012
levels, water is periodically removed from the
system through a process called blowdown. The
blowdown wastewater needs to be subsequently
discharged to a local wastewater treatment facil-
ity or treated on-site to permit conditions before
it can be discharged. A key benefit of ozone is
that it dissipates quickly and reduces the overall
chemical load found in the discharged water,
making it easier to comply with regulations.
A further wastewater treatment process is
supercritical water oxidation (SCWO). This proc-
ess takes advantage of the unique temperature
and pressure properties displayed by water when
it is used above its thermodynamic critical point;
that is, 374°C (705°F) and 220 bar (3210 psi).
Under these conditions, water develops unique
properties that can be applied to completely
oxidise a multitude of complex biologically inert
organic compounds, inorganic complexes and
organic sludges.
Virtually all the organic content of the waste-
water is effectively converted to CO2, water and
salts with almost no production of carbon
monoxide, NOx or SOx and has significant envi-
ronmental compliance credentials.
SCWO is often categorised as “green chemis-
try” or as a clean technology, and the elevated
pressures and temperatures required for SCWO
are routinely and conveniently produced in
industrial applications, including petroleum
refining and process industries. It is also possible
to incorporate the excess energy into power
generation schemes providing a source of waste
to green energy on-site.
At the other end of the scale, low-pressure
oxidation (LoProx) is a wet air oxidation applica-
tion historically used to pretreat recalcitrant
high-strength industrial wastewater prior to
conventional aerobic bio-treatment. The treated
wastewater is then blended with biodegradable
wastewater and treated through an industrial
wastewater treatment plant.
Conclusion
There are a myriad approaches to dealing with
industrial wastewaters that have their own place
on the water technology map and there is no
single solution that fits all. The desired level of
treatment required, available budget and nature
of the wastewater water, among other factors,
determine the elements that make up the final
wastewater treatment process train.
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Darren Gurney is a Senior Process Engineer with Linde Gases
Division’s global aquaculture and water treatment business
Links
based in Munich, Germany, and the UK. He holds a master’s in
More articles from: Linde Engineering
chemical engineering from the University of Manchester, UK,
and is a member of the British Chartered Institute of Water and More articles from the following categories:
Environmental Engineers. Petrochemicals Process Chemicals
Water/Wastewater Management

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