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 of refined products, including petroleum, diesel
wastewater treatment technology in the fuel, kerosene, aviation fuel, fuel oils, lubricat-
refining and petrochemical sector is being ing oils and primary feedstock for the
driven by not only ever-tightening environmen- petrochemical industry, and in doing so it
tal legislation, but also by the sector’s own desire employs a wide variety of physical and chemical
to follow a meaningful sustainability agenda and treatment processes in which large volumes of
to take its responsibilities around product stew- water are utilised, especially for cooling systems,
ardship seriously. However, refining and distillation, filter backwashing and deionisation
petrochemical companies are continually techniques. Vessel cleaning, equipment flushing
confronted with the challenge of striking a and surface water run-off also generate addi-
balance between making their activities profita- tional volumes of wastewater that need to be
ble while ensuring the industrial processes treated. In turn, the petrochemical industry
involved in the production and application of a produces a multitude of essential products to
chemical product, across its lifecycle, have mini- modern-day living including intermediates for
mal impact on the environment. the pharmaceutical industry, aromatic organics,
Treatment of wastewater from petrochemical solvents, alcohols, ketones, polymers and alde-
plants can be a challenging and costly matter, hydes, all of which are synthesised through
particularly when needing to comply with the various process operations, which can produce
requirements of operational permits and national large quantities of wastewater that must be
environmental legislation governing the discharge treated.
of treated wastewater into community treatment Given the complex and diverse nature of refin-
plants or natural water bodies such as rivers, ery wastewater pollutants, a combination of
lakes and oceans. The segregation, collection and physical, chemical and biological process trains
treatment of wastewater play a vital part in the and treatment methods are usually required
protection of public health, water resources and before it is finally discharged into the aquatic
wildlife. Refining and petrochemical facilities, as environment.
part of their permit to operate, must demonstrate Wastewater treatment can be improved signifi-
that they are successfully able to treat all their cantly by harnessing industrial gases such as
pollution streams to the appropriate regulatory pure oxygen, for example, to enhance the biolog-
standards. ical assimilation and oxidation processes of
One of the most widely used strategies to meet wastewater treatment plants or prevent unde-
the ever-rising demand for water and increas- sired odours in refinery mains or storage lagoons
ingly strict regulations governing water and tanks. Carbon dioxide is a versatile and safe
protection is through improved water manage- substitute for corrosive mineral acids to effec-
ment and strengthened investment in the tively neutralise alkali wastewater.
technologies that preserve and recycle process The technology used for refinery wastewater
wastewater. systems is site specific and depends on the nature
The refining industry converts crude oil and of influent (incoming wastewater) conditions and
associated petroleum gas (APG) into hundreds the level of treatment required by local regulatory

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 Oxygen tank

CO2 metering
Evaporator Solvocarb
reactor

Control
unit Centrifugal
pump

pH
electrode
Wastewater inlet Discharge

Clear water

Figure 1 Solvocarb-R process

authorities. However, a typical refinery wastewa- CO2: versatile acid alternative for pH control
ter treatment plant usually consists of In the UK, the industrial gases technology
physico-chemical pre- and primary treatment, company BOC Ltd, part of The Linde Group, has
followed by secondary biological treatment and seen wastewater treatment successfully imple-
tertiary treatment, if necessary. mented at a major plant operated by one of the
In a refinery wastewater treatment system, two world’s leading petrochemical manufacturers.
steps of oil removal are typically required to The 1700-acre site is highly integrated, exploit-
achieve the necessary removal of free oil from ing synergies between the petrochemicals plant
the collected wastewater prior to feeding it to a and adjacent refinery. The petrochemicals facil-
biological system. This oil removal is achieved by ity manufactures over 2 million tonnes of
using an American Petroleum Institute (API) or chemicals products per annum and the refinery
equivalent oil water separator followed by a has an annual capacity of 10 million tonnes.
dissolved air flotation (DAF) or induced air flota- At the petrochemicals plant, an environmen-
tion (IAF) unit. tally friendly CO2-based technology, Solvocarb, is
The wastewater is then routed to the primary being used to control alkali aqueous wastewater
treatment clarifier and to the aeration tank and pH prior to discharge. The system uses gaseous
secondary clarifier, which constitutes the biologi- CO2 to neutralise alkaline waters through the
cal system. The effluent from the clarifier is then production of carbonic acid (see Figure 1).
sent to tertiary treatment, if required, prior to The refinery, in compliance with legislation at
discharge. The activated sludge process is the the time, had been discharging wastewater from
most widely used wastewater treatment technol- the plant into the local river estuary after
ogy for the removal of soluble organic adjusting its pH using mineral acids, such as
contaminants in the oil refining and petrochemi- sulphuric and hydrochloric. Variability in
cal industry. Often the pH of the raw wastewater discharge pH and the corrosive nature of strong
requires reducing before it can be accepted by mineral acids led to concerns over potential
the bio-treatment stage, as the high pH could harm the discharge may cause to aquatic wild-
potentially kill off the bacteria doing the life resident in estuaries.
treatment. In addition to the plant needing to find a more

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environmentally friendly wastewater pH control was satisfied that the proposed system would
solution, it needed to find one that would give it operate to the required parameters.
more robust control over the whole process. In The new wastewater treatment plant was
order to achieve the target pH range through the commissioned in February 2000 and was
use of mineral acids, the company observed peri- completed on time and on budget. BOC has
ods of pH oscillation from too much acidity continued to supply the plant for nearly 12 years.
dosing, requiring adjustment with additional alka- The continued successful operation of the plant
linity. This inevitably leads to extra cost and will help safeguard the environmental status of
operating complexity arising from operating two aquatic areas in which the wastewater is
pH adjustment processes. The company ulti- discharged.
mately opted for a single process route involving Today, the main driver for treating effluent
CO2, which preserves the natural alkalinity of the high in alkalinity prior to discharging to the
wastewater and the process pH control is more outfall is the strict regulation to protect the
stable over the desired pH control range. BOC sensitive, biodiverse ecosystem within the estu-
was appointed to design the pH control system ary. Using CO2 to neutralise an alkali effluent
for the newly designed wastewater treatment avoids large swings in the discharge pH, a vital
plant. component in creating a sustainable and suitable
Owing to strict environmental permits, waste- environment for marine life.
water may only be discharged into the outlet Compared with mineral acids commonly used
channels if it is within a narrow pH range — in previous years, CO2 offers many advantages,
usually between 9 and 6. The Solvocarb method amounting to the best economical and ecological
employs gaseous CO2 to neutralise alkaline alternative. CO2 is not categorised as a substance
waters. When dissolved in water, CO2 forms that is harmful to water and does not lead to the
carbonic acid, which reacts with the alkalinity addition of unwanted anions in the water envi-
to form a salt. The neutralisation reaction ronment, such as chlorides and sulphates. There
controls the pH value to the appropriate is also no over-acidification of the wastewater,
discharge level. due to the self-buffering nature of CO2 in water,
Awarded the contract to design two Solvocarb which produces a flat neutralisation curve and no
systems to neutralise all plant wastewater, corrosion of system and equipment components.
anywhere between 10 000 and 20 000 cu m/d, CO2 is also far safer than the acids previously
BOC engineers designed each system to simulta- used. Simple to handle, it is delivered as a liquid
neously mix and dissolve CO2 into each 10 000 cryogen that is stored in tanks onsite and dosed
cu m tank, controlling the pH to the appropriate automatically into the process.
set point. Consent permits dictated the site could The fact that CO2 is sequestered and effectively
only discharge pH-corrected wastewater into the removed from the global carbon cycle means
estuary when the tide was in, allowing the that it is not available to take part in global
treated wastewater to dilute effectively into the warming; therefore, less CO2 is being released
larger body of available water in the estuary. into the atmosphere. This gives the Solvocarb
However, this meant that the whole process had process its green credentials.
to be completed within a restricted time period
of a six-hour window between the two tides. Pure oxygen wastewater treatment
It was critical for the wastewater to be neutral- The application of pure oxygen has been success-
ised in the two tanks within the time available, fully applied in the activated sludge process to
which called for challenging process hydrody- treat a variety of industrial and refining opera-
namics. Large and variable volumes of tions wastewaters for over 30 years. The
wastewater needed to be brought within the activated sludge process is the most widely used
correct pH range within a fixed timeframe — the form of biological treatment for organic contami-
wrong pH value could result in the refinery being nants in aqueous wastewater globally. There
unable to discharge the wastewater, causing have been numerous industrial wastewater
potential bottlenecks and resulting in backups installations built around the world where pure
further up the process chain. A significant oxygen is routinely used. The application tech-
amount of testing was conducted before the team nology can be designed into the process during a

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 Oxygen tank

Evaporator Control
unit

Oxygen diffusion

Wastewater inlet Discharge

Sewage immersion pump

Aeration
Venturi pipes Mixing pipes tank

Figure 2 Solvox-V process

greenfield build or later as a retrofit application 20°C. Pure oxygen-based systems, on the other
to increase the capacity of an existing asset. hand, have the potential to significantly enhance
Linde’s Solvox wastewater applications are an the aeration process by augmenting, or
example of a pure oxygen wastewater technology completely replacing, portions of the installed
that can be employed in the original design of an existing aeration systems, even at elevated
activated sludge plant or retrofitted as an temperatures of >30°C.
upgrading technology for existing wastewater Pure oxygen is able to maintain a higher aera-
treatment plants (see Figure 2). The primary tion intensity because air only contains one-fifth
application in most cases is to increase treatment oxygen by volume, and the limitation on oxygen
capacity in existing plants that are overloaded or transfer is controlled by the partial pressure of
experience wide swings in dissolved oxygen oxygen in air and the oxygen solubility at a given
demand. The philosophy of Linde has been to water temperature. The activated sludge proc-
provide, where practical, performance improve- ess requires a positive dissolved oxygen level of
ment in existing assets rather than building new at least >2 mg/l to be effective. As the tempera-
plant capacity to increase wastewater treatment ture increases and the background dissolved
throughput. This approach allows the operator oxygen remains constant, the driving force of air
to harness the benefits of pure oxygen within the effectively reduces. It is the driving force poten-
existing plant footprint and improve operational tial of pure oxygen, compared with air at the
performance; for example, lower surplus sludge same temperature, that proportionately
production, reduced volatile emissions, lower increases the rate of oxygen transfer into the
operational power consumption, better settle- activated sludge treatment process. Combined
ment of biomass and simple installation. with effective mixing, a constant supply of
Efficient oxygen transfer and adequate process dissolved oxygen ensures that the micro-organ-
mixing are essential components of all aerobic isms providing the biological wastewater
wastewater treatment processes and these can be treatment perform to their maximum potential,
readily achieved using air or pure oxygen in an environment where oxygen transfer
supplied equipment. However, traditional aera- matches their demand.
tion systems, designed as fixed mass transfer, The Solvox concept is to introduce pure oxygen
often cannot match the variability or increased into the wastewater treatment process via a
oxygen transfer intensity requirements of the family of specially designed and developed pure
activated sludge process, especially when operat- oxygen and air oxygen application equipment.
ing temperatures increase above aeration Equipment is configured to work alongside exist-
performance design values, normally around ing aeration equipment and meet the oxygen

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demand of the biomass generated during synthe- track peak loading during ramp-ups in produc-
sis and oxidation of biodegradable contaminants. tion campaigns.
Within industrial wastewater treatment plants,
pure oxygen can be used in conjunction with air Water reuse and recycling
to increase operational efficiency or overall treat- Recycled wastewater makes it possible for compa-
ment capacity. Often the existing aeration nies that use water in their processes to treat the
equipment has reached its maximum transfer effluent on-site and reuse or recycle as much of it
intensity due to limitations brought about by the as possible back into the industrial operation.
nature of the wastewater, plant operating Many companies are turning to this alternative
temperature or reduced efficiency due to equip- against a background of increasing pressure in the
ment wear and tear. form of restrictions on allowable discharge
Solvox oxygen solutions can also be used to volumes, limitations on abstraction quotas and
prevent odour nuisance from wastewater that is mains supply, legislative pressure and the upward
transferred in large pressurised pipelines and spiralling increase in the “turnaround costs” of
mains, especially if the retention times are long. water. The latter considers both incoming water
The addition of oxygen prevents the naturally supply and trade effluent discharge costs. Linde’s
occurring bacteria on the pipe walls from wastewater recycling technology, Axenis, employs
consuming the chemically bonded oxygen and a high-rate membrane bioreactor treatment stage
producing highly odorous compounds such as and uses a combination of pure oxygen and air to
hydrogen sulphide and mercaptans. Such ensure optimal process performance (see Figure
compounds can quickly result in the corrosion of 3). The membrane replaces the secondary clarifier
pipework networks and ancillary equipment. The used in conventional activated sludge plants.
addition of free oxygen creates ideal conditions Against a conventional wastewater treatment
for successful preliminary treatment and aerobic solution, the innovative, patented process offers
sealing of sludges in tanks and vessels. very substantial cost savings across the industrial
Equipment and process knowledge can be water lifecycle. This includes much reduced capi-
applied in a variety of ways to improve the oper- tal investment, lower energy costs and superb
ational performance efficiency of many industrial final effluent quality. When combined with
wastewater treatment plants and processes. reverse osmosis as a tertiary treatment step to
Adding oxygen using Solvox equipment requires provide high-quality softened water, Axenis
an initial low capital investment and, once makes wastewater reuse a possibility for a large
installed, is designed to be operated flexibly so it number of organisations. By unlocking the
can be adjusted to seasonal needs or used to resource they already have available, operators

Oxygen and air injection

Untreated Process controlled by DO and pH
wasted water control feedback loops Oxygen

Bioreactor

Air

Membrane
modules
Separation of biomass
/ treated water
Treated
water
RO process and Water re-use /
Bio-treatment and oxygenation water re-use final disposal

Figure 3 Axenis wastewater treatment system

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 have the potential to increase production capac- levels, water is periodically removed from the
ity in a more sustainable manner without further system through a process called blowdown. The
depleting a finite natural resource. All this can blowdown wastewater needs to be subsequently
often be achieved at much lower cost than paying discharged to a local wastewater treatment facil-
for the supply and disposal of process water. ity or treated on-site to permit conditions before
it can be discharged. A key benefit of ozone is
Advanced oxidation, ozone solutions that it dissipates quickly and reduces the overall
Oxygen can also be applied in other wastewater chemical load found in the discharged water,
treatment applications such as ozone water treat- making it easier to comply with regulations.
ment, where in combination with either hydrogen A further wastewater treatment process is
peroxide (H2O2) or ultraviolet radiation (UV) it supercritical water oxidation (SCWO). This proc-
is effective in partial or total oxidation of many ess takes advantage of the unique temperature
non-biologically treatable wastewater and pressure properties displayed by water when
compounds, colour removal and as a chlorine it is used above its thermodynamic critical point;
replacement for primary disinfectant. Ozone (O3) that is, 374°C (705°F) and 220 bar (3210 psi).
is a molecule consisting of three oxygen atoms Under these conditions, water develops unique
and is created by passing oxygen through ultra- properties that can be applied to completely
violet light or a “cold” electrical discharge. Under oxidise a multitude of complex biologically inert
ambient conditions, ozone is very unstable, read- organic compounds, inorganic complexes and
ily giving up one atom of oxygen within its short organic sludges.
lifespan of usually less than 10 minutes. Virtually all the organic content of the waste-
However, this process results in a powerful water is effectively converted to CO2, water and
oxidising agent called a free radical, which is salts with almost no production of carbon
toxic to most waterborne organisms. This prop- monoxide, NOx or SOx and has significant envi-
erty makes ozone a very strong, broad spectrum ronmental compliance credentials.
disinfectant and biocide that will oxidise many SCWO is often categorised as “green chemis-
organic and inorganic substances. For this try” or as a clean technology, and the elevated
reason, it is used widely throughout the world. pressures and temperatures required for SCWO
Its strong oxidising properties make ozone an are routinely and conveniently produced in
effective chemical for water treatment, but to use industrial applications, including petroleum
ozone it must be created on-site and added to refining and process industries. It is also possible
the water by bubble contact. A major advantage to incorporate the excess energy into power
of ozone includes the production of fewer generation schemes providing a source of waste
dangerous by-products in comparison to chlorin- to green energy on-site.
ation, for example. At the other end of the scale, low-pressure
Due to the growing concerns over chlorinated oxidation (LoProx) is a wet air oxidation applica-
by-product formation, the use of ozone in water- tion historically used to pretreat recalcitrant
based evaporative cooling towers is becoming an high-strength industrial wastewater prior to
increasingly attractive option, particularly within conventional aerobic bio-treatment. The treated
process industries. It can also provide wider wastewater is then blended with biodegradable
environmental benefits in comparison to the wastewater and treated through an industrial
more traditional chemical treatment wastewater treatment plant.
programmes.
Typically, chemicals such as chlorine and Conclusion
chelating agents are added to cooling tower There are a myriad approaches to dealing with
water to control microbiological growth and industrial wastewaters that have their own place
inhibit mineral build-up. However, as the volume on the water technology map and there is no
of water in a cooling tower is reduced through single solution that fits all. The desired level of
evaporation, the concentration of water treat- treatment required, available budget and nature
ment chemicals and their by-products contained of the wastewater water, among other factors,
within the tower increases. To maintain chemical determine the elements that make up the final
and contaminant concentrations at prescribed 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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