Feature

22
Feature
22 22
Cleaning wastewater:
Removing oil
from water with
organoclays
he negative impact of oil on our environment is all too familiar,
but seepage of oil in to watercourses or sewage can also have
far reaching detrimental effects. George Alther explains how
organoclays can assist with cleaning up the mess.
Oil is found in effluents from a variety of
sources. These include stormwater from parking
lots; landfill leachate; groundwater near storage
tanks, tank farms and wood treating sites;
boiler feed water, process water from factories,
vehicle wash water, tanker ballast water (bilge
water), oil field produced water and more.
The types of oil found in these waters ranges
from the insoluble hydraulic oils, crude oils
and bunker 3 oils to lubricant oils that contain
entire packages of additives, and others that
contain detergents and soaps. These oils can be
classified into different groups.
Free Oil (FOG: free oil and grease)
Oil that rises rapidly to the surface of the water
tank under calm conditions. The droplet size
is 150 micron+. This oil can be removed by an
overflow weir in the tank, a skimmer, and the
traces (100 ppm or less) can be removed by
running the water through a filter vessel filled
with organically modified clay (organoclay).
Mechanically emulsified oil
These oil droplets range in size from 20-
150 microns. Mechanically emulsified oil
is stabilised by electrical charges and other
forces. Such oils mix with water due to an
application of high shear which reduces
the size of the oil and water particles. This
is achieved by the use of pumps, mixers,
and other means of agitation. Over time,
these droplets rise to the surface on their
own due to the lower specific gravity of oil.
In groundwater, oil may be mechanically
emulsified due to confining pressure. If
time is of the essence, oil/water separators
and dissolved air flotation systems are used,
followed by polishing with organoclay and if
necessary, activated carbon. Surfacants are
only present in very small amounts, if at all.
Some of them may be of natural origin. Heat
from 150-220F may have to be applied to
cause splitting of an emulsion.
Chemically stabilised emulsions
Surface active agents (surfacants) provide
enhanced stability to the emulsion due to
interaction at the oil/water interface. The size of
the droplets is less than 20 microns. The color of
such contaminated water is usually white which
is an indication of what action if required to
split the oil from the water. Such oils contain
detergents, soaps, and other additives. The
source of oil is metal working fluids, coolants,
lubricants, motor oils, and others.
Dissolved Oil
These types include benzene, phenols, toluene,
and xylene. They can be removed by activated
carbon, distillation or membranes such as
reverse osmosis. The molecules are of less than
5 micron size.
Oil wet solids
This category includes oil that adheres to
sediments and other particulate matter which
is common in wastewater. Such oil is removed
with oil/water separators or filter presses,
followed by bag filters and absorbers filled with
organoclays. Sand filters are used at times,
but tend to get fueled (coated) with oil when
spikes occur. Polishing of the water is achieved
with organoclay and often the sand in the
sand filter is replaced with organoclay.
Techniques for splitting oily
emulsions
The design of oil/water separators is based on
Stokes law, the lighter oil droplets impact on
the slat ribs of the media, coagulate and rise
to the surface. Dissolved air flotation (DAF)
units use air bubbles for the oil to attach to and
coagulate. Chemically emulsified water requires
at least heat, which can become expensive
(150-220F), either by means of evaporators,
tanks with heating jackets, or heat exchangers.
More likely chemical treatment is required,
which is an art based on the technicians
experience, as much as science.
The first step is the addition of an inorganic salt
such as aluminum sulphate and/or of a cationic
polymer. The purpose is to neutralise the
electrical charges on the oil droplets and cause
coagulation. If this does not work, the pH is
adjusted downward, to as low as 3.5 in the case
of lubricants, with sulphuric or hydrochloric
acid. Then a cationic or anionic flocculant may
need to be added to cause flocculation of the
coagulated droplets, i.e. a rise to the surface of
the tank so they can be skimmed off.
This treatment requires a reaction tank prior
to the oil/water separator that allows for a
residence time of at least ten minutes. The
acids and polymers can be added to that tank
and mixed into the water with mechanical
mixtures, or injected in-line prior to the tank
and the pump, using the pump as a mixer.
Polishing of the water is finalized by filtration
through a bed of organoclay. The polishing step
is becoming more and more a necessity because
discharge limits in states such as Wyoming and
New Jersey are down to 10 ppm. The use of the
T
Feature
22
Filtration+Separation April 2008
fs4503_pg22_25.indd 22 17/03/2008 10:59:00
Feature
24
Filtration+Separation April 2008
Feature
24 24
Feature
24
organoclay serves as an insurance for the oil/
water separator (they reduce oil to 20-5 ppm),
and to allow recycling of the water.
Commercial laundries and truck washes easily
spend US$2,000 to US$5,000 per month
for water and sewer discharge permits. Steel
mills spend much more. Thus zero discharge
with the help of organoclays is an attractive
proposition for cutting operation costs.
Synthetic oils are more difficult to remove
than mineral oils. They require a higher
amount of chemicals to achieve clarity,
and below about 100 ppm are not visible to
the eye. Organoclays are also used as final
polishers, often followed by activated carbon if
recycling of the water is the goal.
Bringing the COD/BOD into compliance
with discharge regulations is often achieved
by removing the oil with organoclay, even
though the oil may be in compliance with the
permit. COD determines the amount of organic
compounds present that can be oxidised, which
includes oil and grease. Thus, if an operator has a
permit for COD of 50 ppm, his COD is 60 ppm
and the oil content is 20 ppm with a limit of 30
ppm, he may not realize that removing the oil
with organoclay will bring him into compliance,
even though oil by itself is not a problem.
The wastewater engineer should be aware of
different methods of splitting oil emulsions,
and work with the vendor of the separation
equipment and the chemical suppliers to achieve
the best results. The unknown in this equation
to achieve recyclable water, in spite of the
presence of oil, has hitherto been the organoclay.
Description of organoclays
Organoclays are manufactured by modifying
bentonite with quaternary amines. The
nitrogen end of the quaternary amine is ion
exchanged onto the clay platelet for sodium or
calcium, the most common cations that balance
the charges of a montmorillonite clay platelet.
Montmorillonite constitutes 90% of the
composition of an industrial grade bentonite.
The bentonite has a charge of 70-90 meq/
gram, of which the quaternary amines use
30-40 meq/gram. The quaternary amines
are surfactants which have a water loving
(hydrophilic) and an oil loving (lipophilic)
end. The lipophilic end partitions into
oil droplets and other sparingly soluble
chlorinated hydrocarbons.
In this fashion, organoclays can remove 50%
or more of their dry weight in oil, diesel
fuel, PNAHs, PCBs, and other chlorinated
hydrocarbons. The main function of
organoclays has been the prevention of fouling
of activated carbon, ion exchange resins and
membranes. Organoclays are blended with
anthracite to prevent early blinding and add
BTU value when the media is exhausted with
oil. In spite of this blending, the organoclay
removes seven times the amount of oils as does
activated carbon, saving the operator 50% or
more of the filtration costs. A combination of
organoclay/activated carbon can easily achieve
non-detectable levels of most organics. Such a
combination is often used to remove such PNA
compounds as anthrazene, flourene, pyrene
and others, while the carbon then removes the
BTEXs. Antifreeze and aquieous cleaners are
filtered through organoclay beds to remove oils
and allow for reuse. The absorbers are the same
ones as those used for activated carbon, except
that they use an air pressure relief valve on top
due to its higher bulk density (56 l/ft3).
Industrial applications for organoclay use
include air compressors, cooling water,
deburring and metal plating process water,
boiler blowdown, boiler feed water and various
types of wastewater.
Examples in practical use
Wastewater collection
A manufacturer had 3% oil in its wastewater
collection system. The wastewater was treated
with conventional coalescing equipment,
followed by a bag filter for dirt removal,
followed by organoclay and activated carbon
as a final polish. Now, the company reuses the
water hauled to a landfill. The system paid for
itself in less than two years.
Cleaning groundwater
In a groundwater cleanup project at an air
force base, the oily water contains about 1,000
ppm oil when it enters the settling tank. After
letting it settle for several hours, 200 ppm
still remain in the water, the remainder that
rose to the surface is skimmed off. One pass
through a drum with 250 lbs of organoclay
lowers it to 5 ppm of oil or less, acceptable for
discharge. The organoclay was changed out
after it removed more than 100 lbs of oil.
Sewage
Three fabricators located in Kentucky that
are not connected to sewer lines have to meet
discharge limits for oil and grease of 5 ppm
before discharge to surface water. The source of
this oil is washwater from the manufacturing of
tubing and cabinets. The water passed through
a 10 micron filter bag, followed by one drum
of organoclay, at one quarter gpm. The inflow
contains 30-50 ppm of oil and grease, the
outflow contains less than 5 pp, meeting all
requirements. The clay is changed twice a year,
operating costs are less than $5,000 per year.
Compressed air
Air compressor condensate containing
automatic transmission fluid (ATF) oil (3%)
resisted all emulsion breaking techniques
including heating, acidification and polymers.
It had a milky white appearance (chemically
emulsified, less than 20 ppm). After settling for
72 hours, a faint brown ring of free oil appeared
on top of the tank. After passing through the
oil/water separator, the oil content was 3,300
mg/l. After the first organoclay/anthracite
vessel, it retained 200 mg/l. After the second
vessel, it retained less than 5 mg/l.
Discharge from metals
A metal plater in California has to meet
discharge limits for zinc of less than 1 ppm.
This is achieved by using a vessel filled with
natural zeolite (clinoptilolite). To prevent
fouling of the zeolite by oil, an oil/water
separator was installed, followed by a vessel
with organoclay preceding the zeolite. The
operator has had no permit violations since
the installation of this system three years ago.
Conclusion
The owner of a facility needs to evaluate the
entire wastewater treatment system, including
meeting discharge permits, possible recycling
of the water, and the benefits of an oil/water
separator/organoclay/activated carbon treatment
system, versus having the water hauled away
with all its potential liability and costs.

Contact:
George Alther
Email: biomin@aol.com
Oil is removed with oil/water separators, followed by bag filters and absorbers filled with organoclays.
fs4503_pg22_25.indd 24 17/03/2008 10:59:17