CHAPTER 1

1.0 INTRODUCTION

For the last several decades, exploration and production industry has been trying
to develop efficient and cost effective methods to remove hydrocarbons from oil
water emulsion.

it has been found that one method alone is not sufficient to remove hydrocarbon
to the desired level(29ppm)

Typical hydrocarbons present in produced water include aliphatic, alicyclic and

aromatic compounds. that is why a combination of various techniques have to
be applied together to achieve the target level of hydrocarbon in produced
water, individually these techniques may perform differently but when applied
together, they act together towards better treatment of the produced water,
depending on the type of oil present in the produced water, these methods are
adsorption, filtration, absorption due to some gases present in the water,
extraction, precipitation and oxidation. Produced water primarily include crude
oil components and some residual hydrocarbons from drilling mud components.

Produced water is a major source of oil contaminated water, but it is possible to

turn this large volume of produced water into an economic asset, and therefore
the concept of using the treated water can be a great incentive. After proper
treatment, produced water could be used for a beneficial purpose. Therefore the
treatment process of produced water has the potential of converting a high cost
liability into an asset.

For the produced water to be used for beneficial purposes, it has to be free from
its salt and oil components. Adsorption is very efficient, cost effective and most
importantly has the capability of meeting the environmental compliance ass far
as the standard of the oil content of the produced is concerned. But combination
of adsorption and absorption as a method of produced water treatment can clean
produced water effectively by maintaining environmental compliance goal and
hopefully at a minimal cost.

1.1 STATEMENT OF THE PROBLEM

The liability of some commercially available adsorption and absorption

materials in the produced waste water treatment from industrial waste has
proved this research [into a more reasonable and reliable], adsorption material
such as such as activated carbon (charcoal) the forerunner of modern activated
carbon will be used, which has been recognized as the oldest absorbent in waste
water treatment.

1.2 OBJECTIVE OF THIS STUDY

To use adsorption and absorption in produced waste water treatment,

adsorption is commonly used in the treatment of industrial waste water
containing organic com pounds that is not easily biodegradable during
secondary treatment or toxic.

1.3 JUSTIFICATION OF THE STUDY

Adsorption and absorption combined together is the best way of treating

produced waste water to a standard that will give best economical uses.

Because adsorption separates the solid and oily waste component and some
organic compounds while absorption removes the unwanted gases that is in the
produced waste water.

1.4 SCOPE OF STUDY

This project work looks at the possible way of treating produced waste
water by combining the adsorption and absorption processes.

It further compares the different kind of adsorbents and finds the best for waste
water treatment, which is the activated carbon.
 CHAPTER 2

LITERATURE REVIEW

HYDROCARBON PRESENT IN WATER

The type of hydrocarbon s present in produced water include aliphatic, alicyclic

and aromatic compounds, that is why a combination of various techniques have
to be applied together to achieve the target level of hydrocarbon in produced
water (i.e. 29 ppm or less oil in water) individually these technique may perform
differently but when applied together, they act together, toward treatment of the
produced water. Depending on types of oil present in produced water, various
methods of removing oil, such as adsorption, filtration, extractive, precipitation,
absorption and oxidation, have been adopted to separate dissolved oil from oil
water emulsion.

Produced water primary consist of crude oil components and some drilling mud
components, but the major classification of oil and grease that contaminant
water and ground water are:

 Free oil and grease (FOG): these are oils that rise rapidly to the surface
under steady condition
 Mechanically emulsified oil: these are fine droplets of oil ranging in size
from micrometer to a few millimeter
 Chemical stabilized emulsion: these are active on the surface very stable
due to interaction at the oil-water interface. The droplet size for these
type is than 20um
 Chemically emulsified or dissolved oil : these are finely divided oil
droplet of 5um diameter or less or individual molecule
 Oil-wet solids: this type of oil, adhere to sediment or other particulate
materials of waste water.

Emulsion were thoroughly discussed by George, et al. these are defined as

heterogeneous system unit is made up of at least one immiscible liquid
thoroughly dispersed droplet form, whose average diameter size is more than
0.1um. As soon as the droplets come close to each other, they have a tendency
to coalesce and rise to the surface. Droplet size is one of the factors that
determine the stability of the emulsion. George, et al. mentioned that the smaller
droplet size increases the stability of the emulsion. When the oil-water mixture
is not emulsified, the oil floats on the top of the water as a slick or sheen.
Emulsification can e achieved mechanically or chemically. A surfactant, which
has a hydrophobic-oliophobic end and a hydrophilic end, has to be added for
chemical emulsification. Both end act as a coupling agent between oil-water
phases. Emulsifiers having a polar end (i.e. it has a charge) and a non-polar end,
prevent the oil droplets from coming close to each other and coalescing.
Surfactant boasts the stability of the emulsion because they pass on a like charge
on the oil droplets, causing them to keep away from each other and scatter.
Mechanical emulsions can be made by stirring the oil-water mixture at a high
speed. In the mechanical emulsion process, higher concentrated emulsions need
higher rpm and time to emulsion stable.

AN OVERVIEW OF WATER AND WASTEWATER TREATMENT

NPDW Regulations for Organic Chemicals

Organic Mclg1 MCL Or Potential Source Of
Chemicals (Mg/L) Tt1 Health Contaminant In
2 2
(Mg/L) Effected Water
From
Ingestion Of
Water
Acrylamide Zero TT Nervous Added to water
system or during
blood sewage/wastewate
problems; r treatment
increased risk
of cancer
Alachlor Zero 0.002 Eye, liver, Runoff from
kidney or herbicide used on
spleen row crops
problems;
anaemia;
increased risk
of cancer
Atrazine 0.003 0.003 Cardiovascula Runoff from
r system hercide used on
problems; row crops
reproductive
difficulties
Benzene Zero 0.005 Anemia; Discharge from
 decrease in factories; leaching
blood from gas storage
platelets; tanks and landfills
increased risk
of cancer
Benzo (a) pyrene Zero 0.0002 Reproductive Leaching from
(PAHs) difficulties; linings of water
increased risk storage tanks and
of cancer distribution lines
Carbonfuran 0.04 0.04 Problems with Leaching of soil
blood or fumigant used on
nervous rice and alfalfa
system;
reproductive
difficulties
Carbon Zero 0.005 Liver Discharge from
tetrachloride problems; chemical plants
increased risk and other
of cancer industrial
activities
Chlordane Zero 0.002 Liver or Residue of banned
nervous termiticide
system
problems;
increased risk
of cancer
Chlorobenzene 0.1 0.1 Liver or Discharge from
kidney chemical
problems agricultural
chemical factories
2,4-D 0.07 0.07 Kidney, liver, Runoff
or adrenal fromherbicide
gland used on row crops
problems
Dalapon 0.2 0.2 Minor kidney Runoff from
changes herbicide used on
rights of way
1,2-Dibromo-3- Zero 0.0002 Reproductive Runoff/leaching
chloropropane difficulties; from soil
(DBCP) increased risk fumigant used on
of cancer soybeans, cotton,
pineapples, and
orchards
o- Dichlorobenzene 0.6 0.6 Liver, kidney, Discharge form
or circulatory industrial
system chemical factories
problems
p- Dichloroethane 0.075 0.075 Anemia; liver, Discharge from
kidney or industrial
spleen chemical factories
damage;
changes in
blood
1,2-Dichloroethane Zero 0.005 Increased risk Discharge from
of cancer industrial
chemical factories
1,1- 0.007 0.007 Liver Discharge from
Dichloroethylene problems induatrial
chemical factories
Cis-1,2- 0.07 0.07 Liver Discharge from
Dichloroethylene problems industrial
chemical factories
Trans-1, 2- 0.1 0.1 Liver Discharge from
Dichloroethylene problems induatrial
chemical factories
Dichloromethane Zero 0.005 Liver Discharge from
problems; pharmaceutical
increased risk and chemical
of cancer factories
1, 2- Zero 0.005 Increased risk Discharge from
Dichloropropane of cancer industrial
chemical factories
Di(2-ethylhexyl) 0.4 0.4 General toxic Leaching from
adipate effects or PVC plumbing
reproductive systems;
difficulties discharge from
chemical factories
Di(2-ethylhexyl) Zero 0.006 Liver Discharge from
phthalate problems; rubber and
increased risk chemical factories
of cancer
Dinoseb 0.007 0.007 Reproductive Runoff from
difficulties herbicide used on
soybeans and
vegetables
Dixocin (2,3,7,8- Zero 0.0000000 Reproductive Emissions from
TCDD) 3 difficulties; waste
increased risk incinerationand
of cancer other combustion;
discharge from
chemical factories
Diquat 0.02 0.02 Cataracts Runoff from
herbicide use
Endothall 0.01 0.01 Stomach and Runoff from
intestinal herbicide
problems
Endrin 0.002 0.002 Nervous Residue of banned
system effects insecticide
Epichlorohydirn Zero TT9 Stomach Discharge from
problems; industrial
reproductive chemical
difficulties; factories; added to
increased risk water during
of cancer treatment process
Ethylbenzene 0.7 0.7 Liver or Discharge from
kidney petroleum
problems refineries
Ethelyene Zero 0.00005 Stomach Discharge from
dibromiden problems; petroleum
reproductive refineries
difficulties;
increased; risk
of cancer
Glyphosate 0.7 0.7 Kidney Runoff herbicide
problems; use
reproductive
difficulties
Heptachlor Zero 0.0004 Liver damage; Residue of banned
risk of cancer termiticide
Heptachlor epoxide Zero 0.0002 Liver damage; Breakdown of
risk of cancer hepatachlor
Hexachlorbezene Zero 0.001 Liver or Discharge from
kidney metal refineries
problems; and agricultural
reproductive chemical factories
difficulties;
risk of cancer
Hexachlorocyclope 0.05 0.05 Kidney or Discharge from
n tadiane stomach chemical factories
problems
Lindane 0.0002 0.0002 Liver or Runoff/leaching
kidney from insecticide
problems used on cattle,
lumber, gardens
Methoxychlor 0.04 0.04 Reproductive Runoff/leaching
difficulties from insecticide
used on fruits,
vegetables,
alfalfa, livestock
Oxamyl (Vydate) 0.2 0.2 Slight nervous Runoff/leaching
system effects from insecticide
used on apples,
potatoes, and
tomatoes
Polychlorinated Zero 0.0005 Skin changes; Runoff from
biphenyls (PCBs) thymus gland landfills;
problems; discharge of waste
immune chemicals
deficiencies;
reproductive
or nervous
system
difficulties;
increased risk
of cancer
Pentachlorophenol Zero 0.001 Liver or Discharge from
kidney wood preserving
problems; factories
increased risk
cancer
Picloram 0.5 0.5 Liver Herbicide runoff
problems
Simazine 0.004 0.004 Problems with Herbicide runoff
blood
Styrene 0.1 0.1 Liver, kidney, Discharge from
and rubber and plastic
circulatory factories; leaching
problems from landfills
Tetrachlorethylene Zero 0.005 Liver Discharge from
 problems; factories and dry
increased risk cleaners
of cancer
Toluene 1 1 Nervous Discharge from
system, petroleum
kidney, or factories
liver problems
Toxaphene Zero 0.003 Kidney, liver, Runoff/leaching
or thyroid from insecticide
problems; used on cotton
increased risk and cattle
of cancer
2,4,5-TP (Silvex) 0.05 0.05 Liver Residue of banned
problems herbicide
1,2,4- 0.07 0.07 Changes in Discharge from
Trichlorobenzene adrenal glands textile finishing
factories
1,1,1- 0.20 0.2 Liver, nervous Discharge from
Trichloroethane system, or metal degreasing
circulatory site and other
problems factories
1,1,2- Zero 0.005 Liver, kidney, Discharge from
Trichloroethane or immune industrial
system chemical factories
problems
Trichloroethylene Zero 0.005 Liver, kidney, Discharge from
or increased petroleum
risk of cancer refineries
Vinyl chloride Zero 0.002 Increased risk Leaching from
of cancer PVC pipes;
discharge from
plastic factories
Xylenes (total) 10 10 Nervous Discharges from
system petroleum and
damage chemical plants
Table 5: NPDW Regulations for Radionuclides
Radionuclides MCLG1 MCL or Potential Sources of
2 1 2
(mg/L) TT (mg/L) Health Contaminant
Effects from in drinking
Ingestion of Water
Water
Alpha None ……… 15 picocuries Increased risk
7
Erosion of
particles as of per Liter of cancer natural
12/08/03: (pCi/L) deposits
zero

WASTE WATER QUALITY INDICATOR

Any oxidized material present in natural water way or in industrial waste will be
oxidized both y chemical or biochemical processes.
The result is that the oxygen content of H2O will be decreased, basically, the
reaction for bio chemical oxidation can be written as:
Oxidized material + bacterial + nutrient + O2→CO2 + H20 + oxidized inorganic
such as NO3 or SO3
Oxygen consumption by reducing chemical such as sulfides and nitrate is
typified as follows:
S + 2O2→SO4
NO2 + 1/2O2→NO3
Since all natural water way contains bacterial and nutrients, almost, any
water compound introduced into water way will initiate bio-chemical reactions.
This biochemical reaction create what is measured in the laboratory as the
biochemical oxygen demands (BOD)
Such chemicals are also liable to be broken down using strong oxidizing agents
and these chemicals reactions create what is measured in the laboratory as the
chemical oxygen demands (COD)
Both the BOD and COD test are measure of the relative oxygen depletion
effects of waste contaminant. Both have been widely adopted as a measure of
pollution effects. The BOD test measure the oxygen demanded of biodegradable
pollutants, whereas the COD test, measure the oxygen demand of oxidized
pollutant.
The BOD measures the amount of oxygen consumed by biochemical oxidation
of waste contaminant in a 5-days period.
Drinking water and wastewater treatment plants are essentially no
different. There are individual unit processes that comprise each of these types
of plants that are applied in a succession of operations, with each stage aimed at
improving the quality of the water as established by a set of product-
performance criteria. The criteria focuses on the quality of the final water,
which in the case of drinking water is established based upon legal criteria (e.g.,
the Safe Drinking Water Act, SDWA), and if non- potable or process plant
water, may be operational criteria (e.g., non-brackish waters to prevent scaling
of heat exchange equipment).
The number and complexity of unit processes and in turn unit operations
comprising a water purification or wastewater treatment facility are functions of
the legal and operational requirements of the treated water, the nature and
degree of contamination of the incoming water (raw water to the plant), and the
quantities of water to be processed. This means then, that water treatment
facilities from a design and operational standpoints vary, but they do rely on
overlapping and even identical unit processes.
If we start with the first technology group, then filtration should be thought of as
both a unit process and a unit operation within a water treatment facility. As a
separate unit process, its objective is quite clear: namely, to remove suspended
solids. When we combine this technology with chemical methods and apply
sedimentation and clarification (other physical separation methods), we can
extend the technology to removing dissolved particulate matter as well. The
particulate matter may be biological, microbial or chemical in nature. As such,
the operation stands alone within its own block within the overall manufacturing
train of the plant. Examples of this would be the roughening and polishing
stages of water treatment. In turn, we may select or specify specific pieces of
filtration equipment for these unit processes.
The above gives us somewhat of an idea of the potential complexity of choosing
the optimum group of technologies and hardware needed in treating water. To
develop a cost- effective design, we need to understand not only what each of
the unit processes are, but obtain a working knowledge of the operating basis
and ranges for the individual hardware. That, indeed, is the objective of this
work, namely to take a close look at the equipment options available to us in
each technology group, but not individually. Rather, to achieve an integrated
and well thought out design, we need to understand how unit processes and unit
operations compliment each other in the overall design, for waste water
analysis.
This chapter is for orientation purposes. Its objectives are to provide an
overview of water treatment and purification roles and technologies, and to
introduce terminology that will assist you in understanding the relation of the
various technologies to the schemes employed in waster treatment applications.

Characteristics Method of Analytics Determination

Physical parameters Photometric
Color Physiological
Temperature Thermometric
Turbidity Nephelometric
Total suspended solids Gravimetric
Specific conductance Conductivity meter
Biological parameters
Total coliform bacteria Fermentation tube or membrane filter
Fecal coliform bacteria Fermentation tube or membrane filter
Inorganic Chemical parameters:
Alkalinity Potentiometric or colorimetric titration
Ammonia nitrogen Spectrophotometric, or titratmetric
Arsenic AA spectroscopy
Boron Colorimetric
Cadmium AA spectroscopy
Chloride Titrametric
Chloride residual Colorimetric or potentiometric titration
Haxavalent chromium AA spectroscopy
Copper AA spectroscopy
Fluoride Colorimetric or ion selective probe
Hardness Titrametric
Iron Colorimetric or AA spectroscopy
Lead AA spectroscopy
Manganese Colorimetric
Mercury AA spectroscopy
Nitrates Colorimetric or ion selective probe
Nitrates Spectrophotometric
pH Electrometric
Phosphorous Colorimetric
Selenium AA spectroscopy
Silver AA spectroscopy
Sulfate Gravimetric or Nephelometric
Sulfide Colorimetric
Total dissolved solids Gravimetric
Zinc AA spectroscopy
Organic Chemical parameters:
Cyanide Colorimetric
Methylene blue active substances Spectrophotometric
Oil and grease Hexane extraction
Biochemical oxygen demand Chemical oxidation
Chemical oxygen demand Chemical oxidation

PRINCIPLES OF THE ADSORPTION PROCESS

Surface Interaction:

Adsorption at a surface is the result of binding forces between the individual

atoms, ions, or molecules of an adsorbate and the surface. The force originated
from electro-magnetic interactions, ion exchange, physical, chemical and
specific are the four major types of adsorption.

Ion exchange adsorption is electrostatic attachment of ionic species to sites of

opposite charge at the surface of an adsorbent. Physical adsorption results from
the action of Vander Waals force.

Chemical adsorption involves a reaction between an adsorbate and an adsorbent

resulting in a change in the chemical form of the adsorbate.

The chemiosorptive bond is usually strong than that derived from the
physical Vander Waals force. When attachment of adsorbate molecules at
functional group , adsorbent surface result from specific interactions which do
not result adsorbate transformation is designated as specific adsorption.
Adsorption from emulsion unto a solid can take place as a result of one or both
of two characteristic properties for a given solvent adsorbate - adsorbent system.
Solvophobic or lyphobic character or a particular affinity of the adsorbate for
the surface of the adsorbent of the asdsorbate is the primary driving force.
Adsorbate and adsorbent properties have a great impact on the adsorption
process.

ADSORBATE - SOLVENT PROPERTIES

An inverse relationship between the extent of adsorption of a substance

from a solvent and its solubility in that solvent can be generally anticipated.

For example; the water solubility of organic compounds within a particular

chemical class decrease with increasing molecular size or weight because the
compound becomes more hydrocarbon-like as the number of carbon atoms
increase. Thus, as the molecular weight increases, adsorption from aqueous
emulsion increases. Molecular size can also affect adsorption rayed if these are
controlled by intraparticles diffuse mass transport within porous of the
adsorbent, which generally is more rapid the smaller, the molecule. Certain
chemical and physical properties of a compound change upon ionization and
this can affect adsorbability. Most observations for amphoteric substances point
to generalization that as long as the adsorbing compound are structurally simple
and electrostatic or exchange reactions are not significant adsorption from polar
solutes such as water is greater for neutral species that for the corresponding
ionic forms. Adsorption reactions are normally exothermic. the equilibrium
extent or the capacity of adsorption in a given system is found to increase with
decreasing temperature conversely, because adsorption kinetics is generally
controlled by diffusive mass transfer , rate of approach to equilibrium normally
increase with increasing temperature.

ADSORBENT PROPERTIES

Adsorption is a surface phenomenon therefore practical and commercial

adsorbent are characterized by large surface areas, the majority of which is
comprised of internal surface bonding the extensive pores and capillaries of
highly porous solids. Activated carbon is one of the most widely used porous
adsorbent, because of its capability for efficiently adsorbing a broad range of
different types of adsorbate while activated carbon’s wide spectrum adsorption
capability is unmatched by any other material, certain synthetic adsorbent such
as organoclay may offer distinct advantage in specifically defined cases. The
performance characteristic of Adsorbent Relate in a Large Measure to there
intraparticle properties, surface area and the distribution of area with respect to
pore size generally are primarily determinant of adsorption capacity.

ADSORPTION IN WASTE WATER TREATMENT

Adsorption is typically used in waste water treatment to remove toxic or

recalcitrant organic pollutants (especially halogenated and also non-
halogenated) and to a lesser extent, inorganic contaminants from the waste
water.

Adsorption finds application in tertiary waste water treatment as a polishing step

before final discharge.

Adsorption is commonly used in the treatment of industrial waste water

containing organic compounds not easily bio-degradable during secondary
treatment or toxic.

ADSORPTION EQUILIBRIA

The adsorption of a substance from one phase to the surface of another in

a specific system leads to a thermodynamically defined distribution of that
substance between the phases when the system reaches equilibrium; that is
when no further net adsorption occurs .the common manner in which depict this
distribution is to express the amount of substance adsorbed per unit weight of
adsorbent "qe" , as a function of the residual equilibrium concentration "c e" of
the substance remaining in the solution phase. an expression of this type termed
an adsorption isotherm, defines the functional distribution of adsorption with
concentration of adsorbed in solution at constant temperature typically, the
amount of adsorbed material per unit weight of adsorbent increases with
increasing concentration but not in direct proportion.

Several equilibrium models have been developed to describe adsorption

isotherm relationships. To follow equilibrium models

LANGMUIR MODEL

This model originally developed for adsorption of gasses unto solids assumes
that adsorption energy, express as joule/mole is constant and independent of
surface coverage’s; that adsorption occurs on localized sits with no interaction
between adsorbate molecules, and that maximum adsorption occurs when the
surface is covered by a mono layer of adsorbents. The relationship can be
derived by considering the kinetics of condensation and evaporation of gas
molecules of a unit solid surface. So at equilibrium, rate of evaporation and rate
of condensation become equal

Kd = KaP(l- Ө)
Where Ө= fraction of surface coverage
P= absolute pressure of gas (psi)
Kd= rate constant for evaporation (no. of molecules evaporate/time)
Ka= rate constant for condensation (no. of molecules condensate/time) Again,
 θ = kap + kap ………………. (2)
Kd

= bp

1 +bp …………………… (3)

Where, b= ka/kd, is related to the enthalpy of adsorption.

For solid-liquid system the equation is written as:
Qe= Q*bCe
1+bCe ...............……… (4)
Where qe=amount of solute adsorbed per unit weight of adsorbent
(mg/gm)
Q*=solid phase concentration- corresponding to complete coverage of
available sites (mg/gm)
Ce= residual liquid phase concentration (Mg/L)
So, after re arranging the equation becomes
Qe= Q*-qe
bCe ………………………(5)

It is to be noted that the parameters in the above equation (i.e., b and Q*)
vary with temperature and the specific chemistry of the solution or gas
and the surface. For example, in liquid-solid systems Q* and b
determined for a certain adsorbent and adsorbent will generally be a
function of temperature, PH, ionic strength, and so forth.

BET MODEL

Limitations of Langmuir isotherm model were reduced by the BET

(Brunauer, Emmet and Teller) model. The essential assumption of this model
are that any given layer need be complete before subsequent layers can form,
that the first layer of molecules adhere to the first layer of molecules adhere to
the surface with energy to the surface with energy comparable to the heat of
adsorption. For monolayer attachment, and that subsequently layers are
essentially condensation reactions. If the layers beyond the first assumed to
have equal energies of adsorption the BET equation takes the form: 28
 qe = BCeQ*
(Ce – Cs )[1+(B – 1) Ce ] .........................(6)
Cs
Where, Cs = Saturation concentration of the solute (mg/l)
B = BET isotherm constant.
Q* = solid phase concentration corresponding to complete coverage of
available sites (mg/gm).

FREUNDLISCH MODEL:
Despite the sound theoretical bases of the Langmuir, model, these
isotherms often fail to describe experimental data adequately, freudlich(1926)
found that adsorption equilibrium data were often better described by the
relationship

Qe=kf Ce1/n ……………………………… (7)

Where, kf and 1/n are the characteristics constants. freunlich attempted to

attach rigorous physical significance to the parameter k f and 1/n. the value of kf
can be taken as a relative indicator of adsorption capacity, while n is indicative
of the affinity of the adsorbate for the surface (adsorbent).

THE ADSORPTION ISOTHERM

The adsorption isotherm is the initial experiment test step in an evolution
to determines feasibility of adsorption treatment and whether further test work
should be conducted. The adsorption isotherm is constructed with data obtained
from the equilibrium test which provides data on adsorbent per unit provides
data on adsorbent per unit weight of adsorbent to the amount of adsorbent
remaining in solution. The equation that expresses the equilibrium between the
adsorbent adsorbed per unit weight of carbon and the concentration of adsorbate
remaining unabsorbed in freundlich equation can be stated as:
Qe = x
m = kf Ce 1/n……………………………….. (8)
 Where, x is the amount of organic adsorbed (mg/gm), m the unit weight
of organoclay, Ce the equilibrium concentration remaining in the solution, and
Kf and n are the constants specific to the adsorbate of concern.
Log x = log Kf + 1 log Ce ........................................ (9)
m n
This expresses the equation for straight line when x/m is plotted vs. Ce.
The resulting line has a slope of l/n and an intercept of Kf when Ce = 1. The x/m
and Ce values are measured and calculated from the isotherm test while plotting
the test data allows determination of l/n and Kf.28

FACTORS AFFECTING THE ISOTHERM

ADSORBENT PREPARATION AND DOSAGE

The adsorbent to be tested should be of same mesh size, while any
particle size of the same adsorbent should reach the sure equilibrium capacity
the rate at which the particle size, smaller particle simply reach equilibrium
faster than larger ones.

HYDROGEN ION CONCENTRATION (PH):

Adsorption from solution can be highly PH dependent from economically

and practical standpoint, fluid should always be evaluated at the ambient PH.

TEMPERATURE
Temperature affects the adsorption process. Isotherms generally are
conducted at the temperature which is expected in the treatment which is
expected in the treatment process. It is recognized that an elevated temperature
generally provides a faster rate of diffusion of the impurities into the adsorbent
pores while simultaneous potentially changing the equilibrium capacity of the
adsorbent for the adsorbate.

CONTACT TIME
To approach equilibrium with the adsorbate, sufficient contact time
between the adsorbent and the fluid is necessary to allow the adsorption. Each
adsorbent particles has to purify volume of liquid, so that the higher adsorbent
dosage with less volume to treat per unit weight may reach equilibrium
somewhat faster than the low dosages. 23 consequently, enough time must be
permitted for the critical low carbon dosage to yield valid data points. Generally
4-5 hrs constant time with vigorous agitation is sufficient for approaching
equilibrium, but this can vary with the sample, measuring the concentration
change over time in a particular system will show the effect of contact time. The
equilibrium concentration can be achieved by plotting change of concentration
vs. time graph

TYPES OF ADSORBENT
Adsorption can be carried out using many types of adsorbents. The extent of
adsorption depends on the nature of adsorbent especially its porosity and surface
area.
A fundamental important characteristic of good adsorbent is their high porosity
and consequent large surface area with more specific adsorption site. A better
adsorbent is the one with large surface area and which requires less time for
adsorption equilibrium

SILICA GEL

Silica gel is the most widely used desiccant (adsorbent for moisture)
because of it large adsorption capacity for water, further, its ease in
regeneration make silica gel most widely used desiccant, gel is considered a
good adsorbent and is use in many industries for drying of gases and liquids,
purification of hydrocarbon.

ORGANOCLAYS
Organoclay can be used to used to remove mechanically emulsified oil
from water to desire of discharged water. Although organoclays can be used in
cleaning up of storm waters, boiler steam condensate, ground water, landfill
leachate, oiler feed water wood treating water and produced water from oil
production well. Organoclay has emerged as a better substitute for GAC that in
comparism between GAC and organoclay, organoclay has several advantage
over GAC as an adsorbent. Organoclay is used as a pre-polisher for removing
small amount of oils from industrial processing water; it shows better
performance as far as the removal of hydrocarbons is concerned.
Organoclay has higher adsorption capacity than GAC (granular activated
carbon) and can adsorb 60-70% hydrocarbon by weight.
It is very effective in removing insoluble and dispersed hydrocarbon.
It does not desorb the adsored hydrocarbon.

ACTIVATED CARBON
Activated carbon has undoughted been the most popular and widely used
adsorbent in waste water treatment throughout the world, charcoal, that is
recognized as the oldest adsorbent known in waste water treatment.
Activated carbon generally exist in two forms:
1 powdered activated carbon (PAC)
2 Granular activated carbon (GAC)

Granular activated carbon adapts to continuous contacting and there is no

need to separate the carbon from the bulk fluid most of the work on the removal
of pollutants from has been on GAC. Therefore, activated carbon has becomes
the standard adsorbent for the reclamation of municipal and industrial waste
water to pottable water quality, due to its low capital cost and lesser contact
time requirement.

CONDITIONS THAT IMPACT ON ACTIVATED CARBON

PERFORMANCE
Adsorption usually increases as pH and temperature decrease. Chemical
reactions and forms of chemicals are closely related to p H and temperature.
When pH and temperature are lowered many organic chemicals are in a more
adsorbable form.
The adsorption process is also influenced by the length of time that the AC is in
contact with the contaminant in the water. Increasing contact time allows
greater increasing the amount contaminant to be removed from the water.
Contact is improved by increasing the amount of AC in the filter and reducing
the flow rate of water through the filler.
AC filters can be a breeding ground for microorganisms. The organic chemicals
that are adsorbed to the AC are a source of food for various types of bacteria.
Pathogenic bacteria are those that cause human diseases such as typhoid,
cholera, and dysentery. AC filtration should only be used on water that has been
tested and found to be bacteria free or effectively treated for pathogenic
bacteria. Other types of non-pathogenic bacteria that do not cause diseases have
been regularly found in AC filters. There are times when high amounts of
bacteria (non-pathogenic) are found in water filtered through an AC unit.
Research shows little risk to healthy people that consume high amounts of non-
pathogenic bacteria. We regularly take in millions of bacteria every day from
other sources. However, there is some concern for certain segements of the
population, such as the very young or old and people weakened by illness. Some
types of non-pathogenic bacteria can cause illness in those whose natural
defenses are weak. Flushing out bacteria that have built up in the filter can be
accomplished by backflushing the AC filter prior to use. Water filtered after the
initial flushing will have been lower levels of bacteria and ingestion of a high
concentration of bacteria will have been avoided. Some compounds of silver
have been used as disinfectants, especially in European operations. Silver has
been added to certain AC filters as a solution to the bacteria problem.
Unfortunately, product testing has not shown silver impregnated AC to be
much more effective in controlling bacteria than normal AC filters. The areas
that require definition when specifying and sizing a carbon adsorption system
include:
Processing conditions:
 Concentration of adsorbate
 Temperature of liquid stream
 pH of liquid stream
 flow rates and operating frequency
 pressure drop in system

characteristics of the adsorbate:

 Relative molecular mass

 Solubility of the adsorbate
 Concentration relative to solubility limits
 Polarity of adsorbate
 Temperature of solution

Selection of adsorbent for optimum effectively

 Specific adsorption isotherm

 Selection of optimum activity level
  Cost sensitivity analysis
 Consideration of thermal reactivation

We will now touch upon some of these factors. First, what we mean by system
isotherm. Freundlich liquid phase isotherm studies can be used to establish the
adsorptive capacity of activated carbon over a range of different concentrations.
Under standard conditions, the adsorptive capacity activated carbon increases as
the concentration increases, until we reach a point of maximum saturation
capacity.

PRINCIPLE OF ABSORPTION

Due to the presence of some unwanted gases in the produced waste water, or
some excess gasses in the water, absorption is necessary in the waste water
treatment. It helps in maintaining the level of (COD). Chemical oxygen
demands and (BOD), biochemical oxygen demands.

Absorption is the removal of one or more selected component from a mixture

gas in liquid. Absorption processes are therefore, conveniently divided into two
groups these are: physical absorption process and chemical reaction absorption
process.

Physical absorption process is those whole whose process is soly physical, and
chemical reaction is occurring. In consideration the design of equipment to
achieve gas absorption, the main requirement is that gas should be brought into
intimate contact with the liquid.

In absorption, the feed is a gas introduced at the column, and unabsorbed

component leaves as gas from the top.

The proceding analysis of the process of adsorption is based on the two-film

theory WHITMAN which states, that material is transferred in the bulk of the
phase by convection currents and concentration difference are regarded as
negligible except in the vicinity of the interface between the phases.

Carbon (iv) oxide can be used as absorbent.

RATE OF ABSORPTION

In a steady state process of absorption, the rate of transfer of material

through gas- film will be as that through the liquid film and the equation for
mass transfer of the component A may be written as:

NA = Ka(PAG - PAi) = Kl(CAi – CAi) = …………………………..(9)

Where PAG = partial pressure in the bulk of the gas.

CAL = the concentration in the bulk of the liquid.

PAI = partial pressure at the interface.

CAI = concentration at the interface where equilibrium conditions are

assumed to exist.
𝐾𝑎
= CAi - CAL÷ PAa - PAi
𝐾𝐿

RATE OF ABSORPTION IN TERMS OF MOLE FRACION

The mass transfer equation can be written as:

NAi = KiG(YA - YAi) = kiiG(YA – YAL)………………………………..(11)

NAi = KiL(YAi – YA) = KIIL(YAL – YA)……………………………….(12)

Where YA, YA are the mole fractions of the soluble component A in the liquid
and phase respectively.
 CHAPTER 3

METHODOLOGY

Material and apparatus: These are the apparatus used in produce wastewater
treatment.
 Equipments and Materials
 Screens-rack bar
 Grit chamber
 Pre-acration tank
 Chemical fed units
 Mixing devices
 Flocculation
 Clarifier
 Septic tank
 Trickling fitter with settling tank
 Activated sludge
 Intermittent sand fitters
 Stabilization ponds.
 Thermometer
 Nephelometer
 API Oil-water separator
 Gravimeters
 Spectrophotometer
 Colorimeter or potentiometer
 Electrometer
 Hexane Extractor/oil Skimmers
 Reagents;
 Chlorine
  Lime water
METHODS OF PRODUCED WASTEWATER TREATMENT
Primary Treatment: Plant preliminary treatment is as used to protect pumping
equipments and facilitate subsequent treatment processes.
Preliminary devices which were basically designed to remove the larger
suspended, and floating solids, the heavy inorganic solids and to remove
excessive amounts of oil and greases.
 Suspend Solids Removal: solid particles were removed using simple
sedimentation techniques with the solids recovered as slurry, then due to
very fine solids and with density of the water Flocculation Techniques
was also applied, using alum salts.
 Oil and Grease Removal: an API oil water separator was used to separate
the oil content (oil and grease) and suspended solid from their produced
wastewater; the API separator has been designed according to the
standard published by the American Petroleum Institute (API).
The API separator is a gravity separation device/equipment designed by
using stokes-law to define the rise velocity of oil droplets based on their density
and size, it equally based on specific gravity difference between oil and the
wastewater because that difference is much smaller than the specific gravity
difference between the suspended solids and water. Therefore, the suspended
solid settled in the bottom of the separator as a sediment layer, the oil raised to
the top of the separator and the cleaned wastewater was in the middle layer
between the oil layer and the solids.
The oil layer was skimmed off for re-processes and the bottom sediment layer
was removed by chain and flight scraper and a sludge pump.
Secondary Treatment: secondary treatment depends on primary treatment upon
anerobic organism which biochemically decompose the organic solids to
inorganic or stable organic solids. The equipment used in secondary treatment is
divided into two.
 Activated Sludge: it is biochemical process for treating produced waste
water that uses oxygen and microorganism to biological oxidize organic
pollutants producing a waste sludge containing the oxidized material.
Procedures:
1. An aeration tank colour air (oxygen) was injected and thorough moved
into the wastewater.
2. A clarifier was used to allow the waste sludge settle, past of the waste
sludge was recycled to the aeration tank and the remaining waste sludge
was removal for further treatment.
 Trickling filter processes: this is a fixed bed filter, in which the granular
activated carbon remains stationary to a cylindrical tank while the water
flows downwards through the granular medium under the force of gravity
and is removed from the bottom. This is adsorption process, which
adsorption of organic compounds in the produced wastewater by microbioal-
slime layer, diffusion of air into the slime layer to provide the oxygen require
for the biochemical oxidation of the organic compound. The end product
includes carbon dioxide (Co2), water and other product of the oxidation.
 Procedures:
The produced wastewater gotten from primary treatment was pump into a
fixed bed filter in which granular activated carbon (adsorbent) remained
stationary in a cylindrical tank. The water flowed downward through the
granular medium under the force gravity, and it was removed at the bottom.
 SUMMARY OF METHODOLOGY

tank

Absorber

Gas

Wastewater

Adsorber

Activated carbon

Treatedwater (BOD,COD, phenol

level, Turbidity test)