Chapter 2

Process selection
The petroleum wastewater treatments are classified into three types;
1. Primary Treatment
2. Secondary Treatment
3. Tertiary Treatment.
However, the treatment required a typical application of the integrated system due to the complexity
of characteristics of petroleum wastewater. Thus, the conventional treatment methods need
multistage process treatment. The first stage consisted of pre-treatment, which includes mechanical
and physicochemical treatments followed by the second stage which is the advanced treatment of
the pre-treated wastewater. Based on the literature review conducted, the techniques and methods
for petroleum wastewater treatment included physical, chemical, biological treatment processing.

Selection of wastewater treatment process

The selection of a wastewater treatment process or a combination of processes depends upon:
1. The characteristics of the wastewater. This should consider the form of a pollutants, i.e.,
suspended, colloidal, or dissolved, the biodegradability, and toxicity of the organic and
inorganic components.
2. The required effluent quality. Consideration should also be given to possible future restrictions
such as an effluent bioassay aquatic toxicity limitation.
3. The cost and availability of land for any given wastewater treatment problem.one or more
treatment combination can produce the desired effluent. Only one of these alternatives,
however, is the most cost effective. A detailed cost analysis should there for be made prior to
final process design selection.
EFFLUENT WATER FOR RESUE
Wastewater treatment technique
There are basically 3 major types of BTEX removal
BTEX (Benzene, Toluene, Ethyl benzene Xylene,)
 Primary treatment
 Secondary treatment
 Post treatment

PRIMARY TREATMENT
 Settling ponds are used as a first step in the treatment process. Here, a majority of suspended
solids are separated from the wastewater under the action of gravity and settle on the bottom.
 Oil and grease are floated on the surface and removed with the sludge. Heat is supplied to
accelerate the removal of insoluble heavy oily emulsions. After that, precipitation of different
chemicals is used for removing dissolved solids.
 Wastewater with high concentration of acids is treated by ammonia, lime, or sodium carbonate.
 Alkaline wastewater is treated with acids (usually sulfuric or hydrochloric), or carbon dioxide
gas.
 Sometimes additional treatment of suspended solids is needed. Precipitation of flocculation
agents (aluminium or iron salts) is used to agglomerate small particles and make them heavier
or lighter,
 depending on the treatment method
 sedimentation,
 filtration or air flotation.
 Soluble organic matters are removed with activated sludge digests.
It is possible to decompose sulphides and ammonia by vaporization. Soluble hydrocarbons and their
derivatives, especially phenols, are removed by solvents. To enhance the efficiency of this step, using
dissolved air flotation (DAF). Spraying air into water or bubbling air through the water removes
remaining traces of volatile chemicals such as petroleum hydrocarbons and ammonia. Significant removal
of total organic carbon (TOC), chemical oxygen demand (COD) and turbidity was achieved. Advantages
of this application are easy operation and low space requirement. In addition, electro coagulation–
flocculation has been combined with the traditional method for primary treatment. As a result of
ELECTROLYSIS, charged particles are neutralized in raw wastewater and subsequently form flocs. It is
possible to remove phenol, anions such as nitrate and nitrite, cations such as ammonia, and metals as well
as COD. This method is recommended as a high speed, non-expensive and environmentally friendly.

SECONDARY TREATMENT
Some reviews describe tertiary treatment methods. Traditional activated sludge system with aerobic and
anaerobic zones are usually enhanced by different applications. One common application is MBBR
(Moving Bed Biofilm Reactor). An aeration tank is filled with wastewater after pre-treatment and consists
of special plastic carriers with growing bacteria on their surface. The biodegradation process is resistant to
toxic and shock loads.

Drawbacks of this method are

 hard to operate a process
 high cost.
 high energy requirement
 production of polluted sludge may affect to the environment.
 However, this method shows high efficiency for removal COD,
POST TREATMENT
Additional treatment removes specific pollutants, including salinity, organic matters, BTEX and other
partially soluble hydrocarbons, such as PAH. Recently, sustainable schemes of wastewater treatment also
implement a post-treatment step, including membrane technologies, advanced oxidation processes.
Depending on pore size, different membrane technologies are
 Microfiltration (MF)
 ultrafiltration (UF)
 nanofiltration (NF)
 reverse osmosis (RO)
Different method for water quality and output water requirements. On the other hand, high amounts of
contaminants clog the membrane, which leads to high cleaning cost for constantly changing them. A
refinery could use this method if potential benefits from implementation are higher than expenditure.
Advanced oxidation processes (AOP) are suggested to solve the problem of removing hard-degradable
organic matters. Hydroxyl radical (•OH) is produced to provide a high oxidation potential, which destroys
organic molecules in wastewater. To initialize this reaction, ultrasound, ozonation, photocatalysis and
peroxide oxidation are used One of the most popular AOP methods is Fenton’s reaction, based on using
Fe2+ in an acidic aqueous environment to produce hydroxyl radical,
BLOCK DIAGRAM OF BTEX REMOVAL

THE SEVERAL NEW TECHNOLOGIES FOR REMOVING BTEX

Several technologies allow treatment of water to reduce the concentrations of BTEX and
other hydrocarbons. These technologies include
 UV/ozone oxidation,
 UV/peroxide oxidation
 high intensity UV destruction
 powdered activated carbon adsorption
 granular activated carbon adsorption
 air/gas stripping followed by carbon adsorption
 various membrane processes
 super critical water oxidation.
While all of these technologies work acceptably well, they all require a fairly large
physical plant to treat water produced on an industrial scale. For that reason, space-
critical producers, for example, offshore oil platforms and the like, require different
techniques to process the water they produce. A need exists for an effective water
remediation method easily usable in space-critical areas.

DIFFERENT STEPS FOR THE REMOVAL

BTEX and other unwanted hydrocarbon components of diesel fuel and gasoline are
removed from oil field and refinery waste streams by countercurrent adsorption
techniques. The contaminated wastewater is contacted with adsorbent particles, selected to
adsorb BTEX and other hydrocarbons, that circulate counter current to the flow of the
wastewater stream.

A first method for removing BTEX from produced wastewater streams. The wastewater
stream containing BTEX is contacted with and flows through a moving bed of adsorbent
particles. The adsorbent particles form a bed moving counter current to the wastewater
flow and interact with BTEX to preferentially remove at least 75% of the total BTEX
from the wastewater stream.

A second method for removing a mixture of dissolved hydrocarbons that includes BTEX
from wastewater streams. The wastewater stream containing the mixture of hydrocarbons
contacts adsorbent particles that adsorb hydrocarbon compounds to remove at least 75%
of the total hydrocarbons from the wastewater stream.

Another aspect of the invention is a method of regenerating adsorbent particles used as

adsorbents in a system having a wastewater stream flowing with a plurality of particulate
adsorbent particles moving counter current to the flow of the wastewater. The particles
are selected to interact with BTEX to selectively remove them from the aqueous stream.
The particles move through a regeneration zone which contains a regenerant which
contacts the particles and flows over the particles contacting the particles counter current
to the direction of particle flow. The regenerant is selected from the group consisting of
organic solvents and steam.

LEVEL OF PPM OF BTEX IN OIL REFINERY

Hydrocarbon Level, ppm

Benzene 1,800
Toluene 470
Ethyl Benzene 150
Xylenes 150
TECHNIQUES CURRENTLY USED
Several techniques are available to control HAPs BTEX removal in wastewater
discharges. These are described and evaluated below.

Activated Carbon (liquid phase)

Percolating the wastewater through beds of activated carbon, which capture the BTEX,
reduces aromatics content to below acceptable limits. In addition, the carbon also
captures oil, grease and other organics. Working capacity of carbon in the liquid phase is
about 5% of carbon weight. The spent carbon is returned to the carbon factory for high
temperature kiln regeneration and reuse. Although effective, the operating costs are high.
One study found that to treat 500 gpm of wastewater entailed $400,000 capital cost and
annual operating costs exceeding $1,5 million (carbon removal, freight to/ from kiln, kiln
fuel, carbon make-up, etc.).

Steam Stripping
Bringing wastewater to the boil by live steam injection effectively strips volatiles such
that the discharge water contains less than 0.5 ppm aromatics. If overhead condensate
comprises equal amounts of aromatics and water, they will phase separate: with over 95%
of the hydrocarbons in upper phase which recycles to the refinery feedstock. Aqueous
phase, with solubility levels of organics, recycles to steam stripper for cleanup.
Steam stripping has several concerns:
– Fouling of equipment with oil/grease.
– Fouling of packing with salts (particularly those that precipitate at stripper operating
temperatures).
– Energy consumption (even with 75% heat recovery a 500 gpm unit requires 7,000
lbs/hr of steam).
– Capital cost is substantial since stripping column is of large diameter.

Gas Stripping
Stripping wastewater with gases, such as air, is very effective and readily reduces total
BTEX in the water to less than the required 0.5 ppm. Gas stripping is best at around
100oF. A lower temperature increases required packing height. At 60oF required packing
height doubles to attain same discharge. Typical stripping gas discharges contain 500 to
2,500 ppm aromatics and, environmental regulations require control of aromatic vapors
before gas is discharged.
When air is the stripping gas, the stripper and treatment unit operate in an open loop with
cleansed air discharging to atmosphere.
The BTEX rich gas is controlled either by oxidization (destruction to CO2 and water) or
adsorption onto vapor phase activated carbon.

Oxidation
Oxidation is an effective control method, however, requires heating BTEX rich air to over
1500oF which, even with 75% heat recovery, entails considerable fuel costs. And, with
today’s interest in “green”, it should be noted that the carbon footprint of oxidization is
many times that of in-situ regenerated vapor phase carbon adsorption.

Adsorption
Advantages of adsorption were low cost, simplicity, and adaptability. Organophilic clays
were effective as adsorbents for the removal of organic substances with high toxicity,
such as phenols and BTEX compounds.
Adsorption technology mainly refers to activated carbon adsorption. It is commonly
utilized for organic compounds, ammonium and toxicity characteristics in treatment of
petroleum wastewater. An addition of sorbent and coupling the activated sludge to form a
biologically activated carbon system improve the treatment through adsorption.
An activated carbon adsorption is effective in removing organic compounds residual after
biological treatment. In addition, low molecular weight pollutants are specially adsorbed.
This method is limited by high consumption of activated carbon or the requirement for
frequent regeneration of columns.
Oxidation
Many volatiles will be chemically oxidized using conventional or advanced chemical
oxidants.
Membrane
Membranes could be generally classified into biological membranes and synthetic
membranes. Membrane technologies such as electrodialysis and ultra-filtration are being
applied increasingly. Membrane separation was found useful in treating organic matter
and more acceptable and economic than other physical treatment techniques.
Membrane technologies, particularly reverse osmosis (RO), are relatively new processes
that seem to be a more effective alternative than conventional methods for petroleum
wastewater treatment. The process involves separating two solutions at different
concentrations by a semipermeable membrane. Naturally, water would flow from the less
concentrated solution to the more concentrated solution. However, the membrane
processes have some major disadvantages such as; the generation of a great amount of
residual concentrate and membrane fouling. Membrane fouling needs chemical cleaning
of membranes or wide pre-treatment and leads to a little lifetime of the membranes and
decreases efficiency of the
Removal of BTEX Contaminants with O3 Processes
Ozone is a very powerful oxidizing agent (E° = 2.07 V). Ozone may react with organic
compounds in two ways: by direct reaction as molecular ozone or by indirect reaction
through formation of secondary oxidants like free radical species. Both mechanisms may
occur depending on the type of chemical wastewater pollution at low Ph predominant
reaction mechanisms are the direct electrophilic attack by molecular ozone i.e.,
ozonolysis. Under such conditions, ozone is a selective oxidant and reacts with multiple
bonds (C=C, C=N, N=N, etc.), but only at low rates with single bonds (C-C, C-O, O-H).
At high pH, indirect reaction occurs, i.e., organics are degraded by secondary
oxidants/chain reaction involving powerful radicals including OH, which are produced by
ozone decomposition. These radicals are very strong and nonselective oxidants. Hydroxyl
radicals can be formatted by increasing pH or by decomposition of O3 with homogeneous
and heterogeneous catalysts.
The main goal of our research was to study the feasibility of ozone and combination of
O3 processes for removal of selected benzene, toluene, and xylenes (BTEX) from
Wastewater.
Experimental methods
Experimental equipment
Ozonation trials were performed in a laboratory ozonation jet loop reactor was operated
in batch mode with regard to wastewater and in continuous mode with regard to gas.
Active volume of the reactor was 3.5 L. The treated wastewater was transferred into
ozonation reactor before starting operation of the actor. A membrane pump was used to
maintain external circulation of liquid reaction mixture. Pulsation of recirculated external
flow was minimized with diaphragm pulsation damper. Ozone was generated sing a
Lifetech generator with maximum production of 5 g h-1. Ozone was generated at 50% of
the maximum ozone generator's power and maintaining continuous oxygen flow of 60 L
h-1. A mixture of O3 and O2 was injected into a wastewater sample through a
Venturi ejector. At the same time, the ejector sucked the mixture of O3 and O2 from the
reactor headspace This together with external circulation, should improve the efficiency
of ozone utilization in the ozonation reactor. Pen‐Ray UV lamp with wavelength 254 nm
was used to generate hydroxyl radicals in the reactor. The outfall of reaction‐gas mixture
was transported into a destruction glass column by a fine‐bubble porous distributive
device. The destructive reactive column contained a potassium iodide solution. The active
volume of the destructive reactor column was 1.0dm3. A n excessive O3 was destructed
in this device

Analytical methods
For determination BTEX compounds in model wastewater, gas chromatography was used
with MS detector in connection with headspace autosampler.
Gas chromatographic method after static headspace extraction was used for quantification
of the BTX in water. Headspace part was analyzed by gas chromatography with MS
detector (Agilent Technologies 7890A GC Systems).
3. Results of the work
The removals of studied compounds with the ozonation time are presented in . The
initial concentrations of benzene, toluene, o‐xylene, and p‐xylene were 800, 1600, 800,
and 600 μg l-1, respectively. It is obvious that for all studied pollutants measured, the
highest removal rates were observed within the first 5 min of the process. The highest
affinity of ozone was measured toward p‐xylene (59.6% removal efficiency). On the
other hand, the lowest treatment efficiency was measured for benzene (20%) within the
same ozonation time
The treatment efficiencies of BTEX components increased with the increase of ozonation time .
The highest treatment efficiency was observed for p‐xylene (81.3% during the first 20 min of
ozonation). The second highest treatment efficiency (72.2%) was measured for o ‐xylene. Final
removal efficiencies of BTEX constituents were observed in the range from 86.4 to 90%. The
values of removal efficiency during O3 process are summarized
Benzene [%] Toluene [%] p‐Xylene [%] o‐Xylene [%]
t [min]
5 20.1 26.4 59.6 44.4
20 53.9 68.3 85.7 86.4
60 84.6 89.6 90.0 89.9

The best fit of experimental degradation data of all studied pollutants was obtained by the first‐
order kinetic model.