Final 15mpe20 Thesis Hard Binding

“TREATMENT OF OIL WELL PRODUCED WATER BY
CONTINUOUS COLUMN ADSORPTION USING LOW COST

AND SYNTHESIZED ADSORBENT”
DISSERTATION
Submitted in partial fulfillment of the requirement of
MASTER OF TECHNOLOGY
IN
PETROLEUM ENGINEERING
By
APURV PATEL
Roll No. 15MPE20
Under the guidance of
DR. MADHAVAN P NATARAJAN
SCHOOL OF PETROLEUM TECHNOLOGY,

PANDIT DEENDAYAL PETROLEUM UNIVERSITY
GANDHINAGAR – 382007, GUJARAT- INDIA
MAY – 2017
APPROVAL SHEET
This thesis entitled “Treatment of oil well produced water by continuous column
adsorption using low cost and synthesized adsorbent” by Apurv patel is

recommended for the degree of M. Tech Petroleum Engineering.
Examiners
Supervisors
Chairman
Date: 25th May, 2017
Place:
STUDENT DECLARATION
I Apurv Patel hereby declare that this written submission represents my ideas in my
own words and where others’ idea or words have been included, I have adequately
cited and referenced the original sources. I also declare that I have adhered to all
principles of academic honestly and integrity and have not misrepresented or
fabricated or falsified any idea / data / fact / source in my submission. I understand
that any violation of the above will be cause for disciplinary action by the PANDIT
DEENDAYAL PETROLEUM UNIVERSITY and can also evoke penal action
from the sources which have thus not been properly cited or from whim proper
permission has not been taken when needed.
Apurv Patel
Roll No. 15MPE20
M.Tech Student, Petroleum Engineering
Date: 25th May, 2017

PREFACE
Oil and gas present in the Earth's sub-surface are required in abundant quantities to
satisfy the requirement of the ever growing society.
The whole tenure of my project will be approximately 10months and is divided in two
parts. I've completed the literature review and characterize the produced water
parameter in first five months and in next five months adsorbent analysis and column
adsorption study.
I started my project reading papers subjected on the very basics starting from adsorption
method .Various technique available for to treat the produced water in petroleum
industry.
Adsorption technique to treat the produced water in petroleum industry carried out in
cost-effective manner and revenue it'll earn in the future is also considered important.
I've tried my best to understand and reproduces the aspects of the valuation of the field
and have gained immense knowledge in the same.
Apurv J Patel (M.Tech)
SPT, PDPU, Gandhinagar

ACKNOWLEDGEMENT
I would like to express my special thanks of gratitude to Dr. Madhavan P

Natarajan, Assistant Professor, School of Petroleum Technology, PDPU,
Gandhinagar for allowing me to carry out my M.tech project under his guidance and
helping me to resolve my doubts. He was with me from day one guiding me from
very basics and also advised to me read as many research papers as possible so as to
get a crystal clear view of the concepts.
My warmest thanks to Dr. Syed Zaheer Hasan Director, Petroleum research lab in
Gujarat Energy Research Management Institute, Gandhinagar who had allowed me
to do my research work on there. I am also thankful to Dr. Mohammed Abdul
Rasheed and Dr. P L Srinivisa Rao, in-charge of petroleum research lab in GERMI
for helping me a lot in my project work.
I would like to thank Dr. Bhawanisingh G Desai for granted Permission in Institute
of Seismological Research, Gandhinagar. I am also thankful to Dr Siddharth
Prizomwala and Mr. Nisarg Patel for helping me in XRF.
I am also thankful to Mr Mustafa Vakharwala for helping me during project
analysis.
I also thank Pandit Deendayal Petroleum University for allowing me to complete my
master program.
Finally, I am indebted to my parents who have always supported me morally and
backed me all time.
i
ABSTRACT
Produced water is generated when oil and gas are produced either from onshore (land
drilling) or offshore wells (deep water/shallow water drilling). Produced water from
any oil well can be hazardous, if it is directly contact in to aquatic life as they are
subjected to pollute water and soil. The present research study is mainly focuses on the
treatment of produced water from Limbodara ONGC GGS II by adsorption process
using local soil and charcoal as an adsorbent.
Adsorption is a well-known method for high efficiency in treatment of water and

wastewater at low costs. It is a promising method that can compete strongly with
conventional purification methods. Carbon-based materials including activated carbon
and other nano materials have been investigated widely because of their outstanding
properties such as chemical permanence, low density and large scale production.
Activated carbon has been extensively used in the treatment of wastewater. In this
present study, activated carbon and soil was used as an adsorbent for the removal of
metals and heavy metals from the produced water.
The adsorption experiments were carried out in columns that were capable with a
stopper for controlling the column flow rate. This experiment is useful in understanding
and predicting the behaviour of the process. The sample solution was passed through
the adsorption column with a known amount of activated carbon and soil with 100mg/l
at a flow rate of 8 mL/min by gravity. Into the column study the flow rate was kept
constant by controlling the stopper valve.
An experimental work was carried out to determine the amount of dissolved chemical
element present in the produced water. The dissolved chemical elements present in the
produced water are sodium, potassium, calcium and lithium and it was analysed through
flame photometer and whereas rest of the chemical elements were analysed from xrf
analyser. The factors affecting chemical absorption are pH, Flow rate, adsorption and
amount of samples were considered during the part of experiment. An optimum
mechanism of 120 to 150 minutes was found to remove the highest amount of unwanted
metals present in the produced water. Then, the adsorbed material soil and charcoal was
analysed through xrf analyser. The xrf analyser result confirm adsorbed chemical
ii
elements from produce water such as, barium, lead, vanadium etc. The project main
aim was to achieve the disposal standard limit by low cost treatment.
Activated carbon and soil was able to treat a real sample of produced water with an
initial concentration of emulsified oil very high, and reduce it to some amount, which
is equivalent to 60 % removal efficiency of oil.
iii
TABLE OF CONTENTS
CHAPTER TITLE PAGE NO
ACKNOWLEDGEMENT .........................................................................................i
ABSTRACT................................................................................................................ii
LIST OF TABLES ...................................................................................................vii
LIST OF FIGURES ............................................................................................... viii
LIST OF GRAPHS ................................................................................................... ix
ABBREVIATIONS ...................................................................................................xi
CHAPTER 1 INTRODUCTION TO PRODUCED WATER ............................. 1
1.1 INTRODUCTION TO PRODUCED WATER ............................................. 1
1.1.1 The Origin of Produced Water ....................................................... 3
1.1.2 Overview of Produced Water Characteristics ................................ 4

1.1.2.1 Produced Water from Oil Production ......................................... 4
1.1.2.2 Produced Water from Gas Production ........................................ 5
1.2 Conventional Oil and Gas Production PW Constituents .......................... 5
1.2.1 Dispersed Oil .................................................................................. 5
1.2.2 Treatment Chemicals ...................................................................... 6
1.2.3 Produced Solids .............................................................................. 6
1.2.4 Dissolved Organic Components ..................................................... 6
1.2.5 Scales .............................................................................................. 8
iv
1.2.6 Bacteria ........................................................................................... 8
1.2.7 Metals ............................................................................................. 8
1.2.8 pH ................................................................................................... 9
1.2.9 Sulphates ........................................................................................ 9
1.2.10 Naturally Occurring Radioactive Material (NORM)...................... 9
1.3 Environmental Impact and Legislation ..................................................... 9
CHAPTER 2 LITERATURE SURVEY .............................................................. 11
2.1 Types of produced water treatment .............................................................. 11
2.1.1 Dispersed oil and grease ................................................................... 11

2.1.1.1 Gravity separation ..................................................................... 11
2.1.1.2 Gas flotation .............................................................................. 13
2.1.1.3 Hydrocyclones .......................................................................... 15
2.1.2 Physical Treatments: ........................................................................ 16
2.1.3 Chemical Treatment: ........................................................................ 20
2.1.4 Biological Treatment: ....................................................................... 21
2.2 Management of produced water:.................................................................. 22
2.3 Adsorption .................................................................................................... 23
CHAPTER 3 MATERIALS AND METHODS .................................................. 28
3.1 List of Instruments: ...................................................................................... 28
3.2 Experimental Procedure ............................................................................... 29
3.3 Characterization of Produced Water ............................................................ 30
3.3.1 Flame Photometer ............................................................................. 30
3.3.2 AAS/Atomic Absorption Spectroscopy ........................................... 32
3.3.3 Gravimetric ....................................................................................... 33
v
3.4 Adsorption process for produced water ....................................................... 34
3.4.1 Soil and Charcoal Analysis............................................................... 36
3.4.2 Procedure for making activated charcoal ......................................... 37
3.4.3 Analysis of adsorbent ....................................................................... 37
3.5 Adsorption Batch Study .............................................................................. 38
3.6 Column study ............................................................................................... 39
CHAPTER 4 RESULT ANALYSIS.................................................................... 41
4.1 Produced water parameter ............................................................................ 41
4.2 Adsorbent Analysis ........................................................................................ 42
4.3 Effects of various factor depends on adsorption process ............................... 44
4.3.1 Effect of contact time on soil and charcoal mix ................................. 44
4.3.2 Effect of adsorbent dosage ............................................................... 51
4.4 Langmuir adsorption isotherms ................................................................... 55
4.5 Adsorbent chemical properties through XRF .............................................. 61
CHAPTER 5 DISCUSSIONS, CONCLUSIONS AND

RECOMMENDATIONS ........................................................................................ 69
5.1 DISCUSSION .............................................................................................. 69
5.2 CONCLUSION AND RECOMMENDATION ........................................... 71
REFERENCES ........................................................................................................ 73
vi
LIST OF TABLES PAGE NO
Table 2-1 Types of water treatment method ............................................................16

Table 4-1 Physical parameter of produced water ....................................................41
Table 4-2 Ions measured in produced water ............................................................42
Table 4-3 Soil grain size analysis for oil well site at Limbodra ..............................43
Table 4-4 Effect of contact time on soil and charcoal versus produced water ........45
Table 4-5 Effect of contact time on activated charcoal versus produced water ......48
Table 4-6 Effect of adsorbent dosage on Calcium ion.............................................51
Table 4-7 Effect of adsorbent dosage on Lithium ion .............................................52
Table 4-8 Effect of adsorbent dosage on Potassium ion..........................................53
Table 4-9 Effect of adsorbent dosage on Sodium ion ..............................................54
Table 4-10 Amount of calcium adsorbed per unit mass of soil and charcoal ..........56
Table 4-11 Amount of lithium adsorbed per unit mass of soil and charcoal ...........57
Table 4-12 Amount of potassium adsorbed per unit mass of soil and charcoal ......58
Table 4-13 Amount of sodium adsorbed per unit mass of soil and charcoal...........59
Table 4-14 Langmuir isotherm data.........................................................................60
Table 4-15 Amount of chemical elements found in soil and charcoal through XRF
analysis ......................................................................................................................62
Table 4-16 Estimated metal present in produced water data ...................................68
vii
LIST OF FIGURES PAGE NO
Figure 1.1 A Typical oilfield reservoir ......................................................................3

Figure 2.1 Skim Pile ...............................................................................................13
Figure 2.2 Gas flotation method ..............................................................................14
Figure 2.3 Hydrocyclone .........................................................................................15
Figure 3.1 Sample Collection from ONGC limbodra on 30-9-2016 ........................29
Figure 3.2 Sample Collection from ONGC Limbodra on 24-11-2016 ....................29
Figure 3.3 Flame Photometer ...................................................................................30
Figure 3.4 Flame Photometer Analysis ...................................................................31
Figure 3.5 Sieve Analysis ..........................................................................................36
Figure 3.6 Column adsorption method ....................................................................40
viii
LIST OF GRAPHS PAGE NO
Graph 4-1 Physical properties of soil at Limbodra ..................................................43

Graph 4-2 Cumulative soil weight percentage vs Phi Value ...................................44
Graph 4-3 Effect of contact time on soil and charcoal versus calcium concentration
in produced water ......................................................................................................45
Graph 4-4 Effect of contact time on soil and charcoal versus lithium concentration
Graph 4-5 Effect of contact time on soil and charcoal versus potassium
concentration in produced water ................................................................................47
Graph 4-6 Effect of contact time on soil and charcoal versus sodium concentration
Graph 4-7 Effect of contact time on activated charcoal versus calcium
Graph 4-8 Effect of contact time on activated charcoal versus lithium concentration
Graph 4-9 Effect of contact time on activated charcoal versus potassium
Graph 4-10 Effect of contact time on activated charcoal versus sodium
Graph 4-11 Adsorbent dosage vs Material removal for Calcium ion ......................52
Graph 4-12 Adsorbent dosage vs Material removal for Lithium ion ......................53
Graph 4-13 Adsorbent dosage vs Material removal for Potassium ion ...................54
Graph 4-14 Adsorbent dosage vs Material removal for Sodium ion .......................55
Graph 4-15 Equilibrium concentration of calcium ion vs .......................................56
Graph 4-16 Equilibrium concentration of lithium ion vs Specific adsorption.........57
Graph 4-17 Equilibrium concentration of potassium ion vs Specific adsorption ....58
Graph 4-18 Equilibrium concentration of sodium ion vs ........................................59
Graph 4-19 Estimated isotherm parameters for adsorption of metal ions onto soil
and charcoal ...............................................................................................................60
Graph 4-20 Estimated isotherm parameters for adsorption rate of metal ions onto
soil and charcoal ........................................................................................................61
ix
Graph 4-21 Difference of magnesium concentration in adsorbent found before and
after passing through produced water ........................................................................63
Graph 4-22 Difference of iron concentration in adsorbent found before and after
passing through produced water ................................................................................63
Graph 4-23 Difference of potassium concentration in adsorbent found before and
Graph 4-24 Difference of sodium concentration in adsorbent found before and after
Graph 4-25 Difference of zinc concentration in adsorbent found before and after
Graph 4-26 Difference of vanadium concentration in adsorbent found before and
Graph 4-27 Difference of barium concentration in adsorbent found before and after
Graph 4-28 Difference of radium concentration in adsorbent found before and after
Graph 4-29 Difference of lead concentration in adsorbent found before and after
Graph 4-30 Difference of thorium concentration in adsorbent found before and
Graph 4-31 Year vs Metal generated in produced water .........................................68
Graph 4-32 Year vs Metal generated in produced water ..........................................68
x
ABBREVIATIONS
PW – Produced Water
API - American Petroleum Institute
ONGC – Oil and Natural Gas Corporation
USPEA – United States Environmental Protection Agency
TDS – Total Dissolve Solids
PAHs – Polycyclic aromatic hydrocarbons
BTEX – Benzene, Toluene, Ethylbenzene and Xylene

COD – Chemical oxygen demand
BOD – Biochemical Oxygen Demand
NORM – Natural Occurring Radioactive Material
MF – Membrane Filtration
RO – Reverse Osmosis
NF – Nano Filtration
UF – Ultra Filtration
BAF – Biological Aerated Filter
AAS – Atomic Adsorption Spectroscopy
XRF – X-Ray Fluorescence
MR – Material Removal
xi
CHAPTER 1 INTRODUCTION TO PRODUCED WATER
1.1 INTRODUCTION TO PRODUCED WATER
In subsurface formation, naturally occurring rocks are generally permeated with fluid
as water, oil, or gas (or some mixture of these fluids). Thus, reservoir rocks normally
contain both petroleum hydrocarbons (liquid and gas) and water. Sources of this water
may include flow from above or below the hydrocarbon zone, flow from within the
hydrocarbon zone, or flow from injected fluids and additives resulting from
production activities. This water is frequently referred to as “connate water” or
“formation water” and becomes produced water when the reservoir is produced and
the fluids are brought to the outside (Argonne National Laboratory et al, 2004)
Petroleum is a major source of energy and revenue for many countries today, and its
production has been described as one of the most important industrial activities in the
twenty-first century (Oliveira EP et al, 2005). Since late 1850s when Edwin Drake
drilled the first oil well, demand for petroleum has continued to rise. It is estimated
that world daily petroleum consumption would increase from 85 million barrels in
2006 to 106.6 million barrels by 2030. Despite its significance, petroleum is produced
with large volumes of waste, with wastewater accounting for more than 80% of liquid
waste (Azetsu-Scott K et al,2007) and as high as 95% in ageing oil fields (Kaur G et
al, 2009)
Communities across the world face water challenges due to increasing demand,
drought, depletion and contamination of groundwater, and dependence on only
sources of supply. Water generated during oil and gas extraction activities, known as
‘produced water’ (Fakhru'l-Razi A et al,2009).Even with its various sources and
supplies, water will become scarce with time due to poor management of water
infrastructure, increase in human population, change of climate, and lack of economic
and physical aids to care for this precious resource. As well, the paucity of fresh water
worldwide is coupled with lack of accessibility to this water; 1.2 billion people suffer
from this problem (F. R. Rijsbermanet al, 2006). As per Colorado School of Mines a
1
public research university “Approximately 21 billion bbl of produced water are
generated each year in the United States from about 900,000 wells”
Produced water includes formation water, injection water and process water that is
extracted along with oil and gas during petroleum production. In addition, a portion
of the chemicals added during processing of reservoir fluids may partition to the
produced water. Produced water contains both soluble and insoluble (oil droplets not
removed prior to physical separation) petroleum fractions, and are found at variable
concentrations. This petroleum fraction consists of a complex mixture of organic
compounds similar to those found in crude oils and natural gases.
This is one of the main waste water produced in the oil and gas industries, and hence,
water pollution due to the discharge of these wastes back to streams and lakes without
treatment or without meeting the minimum treatment required will continue to
increase and cause an environmental concern (Yeats P et al, 2007). Oil water
contamination can be hazardous to humankind and aquatic life as they are subjected
to polluted water and soil. Adverse effects have been reported on people’s
contamination with oil and organic compounds. It is therefore necessary to treat
produced water from the oil and gas companies in order to protect the local
environment as well as wetland creatures (Mandal AK et al, 2009).
At most offshore production installations, produced water are separated from the
petroleum process stream and after treatment are discharged to the marine
environment or disposed of in a subsurface formation. Treatment of produced water
may be required in order to meet disposal regulatory limits or to meet beneficial use
specifications (e.g. for recreational purposes, drinking water for stock and wild life
etc.). If the oil and gas operator aims to utilize a low-cost disposal option such as
discharge to surface waters, the produced water must meet or exceed limits set by
regulators for key parameters.
The measurement of oil in produced water is important for both process control and
reporting to regulatory authorities. Oil in produced water is a method-dependent
parameter, a point which cannot be emphasised enough. Without the specification of
a method, reported concentrations of oil in produced water can mean little, as there
are many techniques and methods available for making this measurement, but not all
are suitable in a specific application (Miller GE et al, 2006).
2
1.1.1 The Origin of Produced Water
Water is very often found together with petroleum in the reservoir where the water as
a consequence of higher density than oil, lays in vast layers below the hydrocarbons
in the porous reservoir media. This water, which occurs naturally in the reservoir, is
commonly known as formation water. At a particular time in an oil and gas
production, the formation water will reach the production wells and water production
will begin to initiate. The well water-cut will normally increase throughout the whole
oil and gas field lifetime, such that when the oil production from the field is shut down
and the oil content can be as low as a couple of percent 98 % water.
Also in order to maintain the hydraulic pressure in the petroleum reservoir which is
reduced as soon as production is initiated, seawater is commonly pumped into the
reservoir water layer below the hydrocarbons .This process, as a way of pressure
maintenance due to water injection, causes high extensions in recoverable
hydrocarbons but simultaneously contributes to increased water production.
Figure 1.1 A Typical oilfield reservoir
(https://www.researchgate.net/figure/235971711_fig2_Figure-2-Typical-production-profile-
for-an-oilfield-17)
3
1.1.2 Overview of Produced Water Characteristics
Produced water properties and volumes can vary considerably depending on the
geographical location of the oil field and the geological formation throughout the
lifetime of a reservoir. However, having a good understanding of produced water
characteristics can facilitate operators to increase production. For instance, parameters
such as total dissolved solids (TDS) can help define pay zone when coupled with
resistivity measurements. Also, by knowing produced water constituents, producers
can determine the proper application of scale inhibitors and well treatment chemicals
as well as identify potential well-bore or reservoir problem areas.
Knowledge of the constituents of specific produced water is needed for regulatory

compliance and for selecting management/disposal options such as secondary
recovery and disposal. Oil and grease are the main constituents of produced water that
has received the most attention in both onshore and offshore operations while salt
content (expressed as salinity, conductivity or TDS) is a primary constituent of
concern in onshore operations. In addition, produced water contains many organic and
inorganic compounds that vary greatly from location to location and even over time
in the same well.
1.1.2.1 Produced Water from Oil Production

The organic and inorganic components of produced water discharged from offshore
wells can be in a variety of physical states including solution, suspension, emulsion,
adsorbed particles and particulates. In addition to its natural components, produced
water from oil production may also contain groundwater or seawater (generally called
“source” water) injected to maintain the reservoir pressure as well as miscellaneous
solids and bacteria. Most produced waters are more saline than seawater and may
include chemical additives used in drilling and production operations in the oil/water
separation processes. In produced water, these chemicals can affect the oil/water
partition coefficient, toxicity, bioavailability and biodegradability.
The treatment chemicals are typically complex mixtures of various molecular

compounds and may include the following (Argonne National Laboratory et al, 2004):
1. Corrosion inhibitors and oxygen scavengers used to reduce equipment corrosion.
4
2. Scale inhibitors used to limit mineral scale deposits; biocides to mitigate bacterial
fouling.
3. Emulsion breakers and clarifiers to break water-in-oil emulsion and reverse

breakers to break oil-in-water emulsion.
4. Coagulants, flocculants and clarifiers to remove solids.
5. Solvents to reduce paraffin deposits.
1.1.2.2 Produced Water from Gas Production

Produced water from gas production have higher contents of low molecular-weight
aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene (BTEX)
than those from oil operations: hence they are relatively more toxic than produced
waters from oil production.
Studies have indicated that produced water discharged from gas/condensate platforms
are about 10 times more toxic than produced water discharged from the oil platforms.
However, for produced water discharged offshore, the volumes from gas production
are much lower and so the total impact may be less (Argonne National Laboratory et
al 2004).
1.2 Conventional Oil and Gas Production PW Constituents
Organic constituents are normally either dispersed or dissolved in produced water and
include oil and grease and a number of dissolved compounds.
1.2.1 Dispersed Oil
Dispersed oil consists of small droplets suspended in the aqueous phase and if the
dispersed oil gets in contact with the ocean flow, contamination and accumulation of
oil on the ocean sediments may occur, which could disturb the benthic community.
5
The less dense dispersed oils can also rise to the surface and spread. Causing sheening
and increases the biological oxygen demand (BOD) near the mixing zone.
1.2.2 Treatment Chemicals
Treatment chemicals such as biocides, reverse emulsion breakers and corrosion

inhibitors pose the greatest concerns for aquatic toxicity. However, these substances
may undergo reactions that reduce their toxicities before they are discharged or re-
injected. For example, biocides react chemically to lose their toxicity, and some
corrosion inhibitors may partition into the oil phase so that they never reach the final
discharge stream. Nonetheless, some of these treatment chemicals can be lethal at
levels as low as 0.1 ppm. In addition, corrosion inhibitors can form more stable
emulsions, thus making oil/water separation less efficient.
1.2.3 Produced Solids
Produced water can contain precipitated solids, sand and silt, carbonates, clay,
propant, corrosion products and other suspended solids derived from the producing
formation and from well bore operations. Quantities can range from insignificant to a
solids slurry, which can cause the well or the produced water treatment system to shut
down. The solids can influence produced water fate and effects. Fine-grained solids
can reduce the removal efficiency of oil/water separators, leading to excedances of oil
and grease limits in discharged produced water.
1.2.4 Dissolved Organic Components
Hydrocarbons that occur naturally in produced water include organic acids, polycyclic
aromatic hydrocarbons (PAHs), phenols and volatiles. These hydrocarbons are likely
contributors to produced water toxicity (and their toxicities are additive) although
individually the toxicities may be insignificant when combined aquatic toxicity can
occur.
6
Soluble organics are not easily removed from produced water and therefore are
typically discharged to the ocean or re-injected at onshore location. Generally, the
concentration of organic compounds in produced water increases as the molecular
weight of the compound decreases. The lighter weight compounds (BTEX and
naphthalene) are less influenced by the efficiency of the oil/water separation process
than the higher molecular weight PAHs and are not measured by the oil and grease
analytical method.
Organic components that are very soluble in produced water consist of low molecular
weight (C2-C5) carboxylic acids (fatty acids), ketones and alcohols. They include
acetic and propionic acid, acetone and methanol. In some produced waters, the
concentration of these components is greater than 5000 ppm. Due to their high
solubility, the organic solvent used in oil and grease analysis extracts virtually none
of them and therefore, despite their large concentrations in produced water they do
not contribute significantly to the oil and grease measurements.
Partially soluble components include medium to higher molecular weight

hydrocarbons (C6C15). They are soluble in water at low concentrations but are not as
soluble as lower molecular weight hydrocarbons. They are not easily removed from
produced water and are generally discharged directly to the sea. They contribute to
the formation of sheen but the primarily concern involves toxicity. These components
include aliphatic and aromatic carboxylic acids, phenols and aliphatic and aromatic
hydrocarbons.
Naphthalene is the most simple PAH, with two interconnected benzene rings and is
normally present in crude oil at higher concentrations than other PAHs (In Norwegian
fields, for example naphthalene comprises 95 % or more of the total PAHs in offshore
produced water). PAHs range from relatively “light” substances with average water
solubility to “heavy” substances with high liposolubility and poor water solubility.
They increase biological oxygen demand (BOD), are highly toxic to aquatic
organisms and can be carcinogenic to man and animals. All are mutagenic and harmful
to reproduction. Heavy PAHs bind strongly to organic matter (e.g. on the seabed)
contributing to their persistency. Higher molecular weight PAHs are less water
soluble and will be present mainly associated with dispersed oil. Aromatic
hydrocarbons and alkylated phenols are perhaps the most important contributors to
7
toxicity. Alkylated phenols are considered to be endocrine disruptors and hence have
the potential for reproductive effects. However, phenols and alkyl phenols can be
readily degraded by bacterial and photo-oxidation in seawater and marine sediments.
1.2.5 Scales
Scales can form when ions in supersaturated produced water react to form precipitates
when pressure and temperatures are decreased during production. Common scales
include calcium carbonate, calcium sulfate, barium sulfate, strontium sulfate and iron
sulfate. They can clog flow lines from oily sludge that must be removed and form
emulsions that are difficult to break.
1.2.6 Bacteria
One of the major concerns in the Oil & Gas sector is corrosion. This is often linked to
sulfate reducing bacteria (SRB) and the acid producing bacteria (APB). One reason
for this is that the very reductive conditions encourage the SRB to generate hydrogen
sulfide (H2S) gas. This gas has not only a foul odor (“rotten egg”) but also start off
process of electrolytic corrosion which can rapidly corrode steel. Bacteria can clog
equipment and pipeline and can form difficult-tobreak emulsion and hydrogen sulfide
that are corrosive.
1.2.7 Metals
The concentration of metals in produced water depends on the field particularly with
respect to the age and geology of the formation from which the oil and gas are
produced. Metals typically found in produced waters include zinc, lead, manganese,
iron and barium.
Metals concentrations in produced water are often higher than those in seawater.
However, potential impacts on marine organisms may be low because dilution reduces
8
the concentration and because the form of the metals adsorbed onto sediments is less
bioavailable to marine animals than metal ions in solution. Besides toxicity, metals
can cause production problems such as by reacting with oxygen in the air to produce
solids, which can interfere with processing equipment such as hydrocyclones and can
plug formations during injection or cause staining or deposits at onshore discharge
sites.
1.2.8 pH
Reduced pH can disturb the oil/water separation process and can impact receiving
water when discharged. Many chemicals used in scale removal are acidic.
1.2.9 Sulphates
Sulphate concentration controls the solubility of several other elements in solution

particularly barium and calcium.
1.2.10 Naturally Occurring Radioactive Material (NORM)
The most abundant NORM compounds in produced water are radium-226 and
radium-228 which are derived from the radioactive decay of uranium and thorium
associated with certain rocks and clays in the hydrocarbon reservoir. As the water
approaches the surface, temperature changes cause radioactive elements to precipitate.
The resulting scales and sludge may accumulate in water separation systems (Argonne
National Laboratory et al, 2004).
1.3 Environmental Impact and Legislation
Produced water can have different potential impacts depending on where it is

discharged. For example, discharges to small streams are likely to have a larger
9
environmental impact than discharges made to the open ocean by virtue of the dilution
that takes place following discharge.
Numerous variables determine the actual impacts of produced water discharge. These
include the physical and chemical properties of the constituents, temperature, content
of dissolved organic material, humic acids, presence of other organic contaminants
and internal factors such as metabolism, fat content, reproductive state and feeding
behaviour (Nicholas Owens, et al 2007).
The general practice in use for produced water treatment is gravity-based separation
and discharge into the environment, which can pollute soil, surface water and
underground water. For a long time, only non-polar oil in water (OIW) was regulated
by government, while little attention was given to dissolved organics in produced
water. Current researches are paying more attention to the consequence of dissolved
organic components, heavy metals and production chemicals on living organisms,
since their long-term effects on the environment are not fully documented and
understood. It has been reported that metals and hydrocarbons from oil platforms are
very toxic to the ecosystem and fish exposed to alkyl phenols have disturbances in
both organs and fertility (Cline JT et al, 1998).
A general legislation for discharging produced water into sea has been 40 ppm OIW,
but an increase in environmental concerns has made many countries to implement
more stringent regulatory standards. The United States Environmental Protection
Agency (USEPA) sets a daily maximum for oil and grease at 42 ppm.
10
CHAPTER 2 LITERATURE SURVEY
2.1 Types of produced water treatment
The general objectives for operators treating produced water are: de-oiling (removal
of dispersed oil and grease), desalination, removal of suspended particles and sand,
removal of soluble organics, removal of dissolved gases, removal of naturally
occurring radioactive materials (NORM), disinfection and softening (to remove
excess water hardness) (Daniel Arthur J, et al 2005). To meet up with these objectives,
operators have applied many standalone and combined physical, biological and
chemical treatment processes for produced water management. Some of these
technologies are reviewed in this section.
2.1.1 Dispersed oil and grease
This oil mixture of dispersed oil, free oil, and emulsified oil. Due to strict regulations for oil
discharge in the produced water, the latter must be treated accordingly. Which is depending
on the oil composition in the produced water before treatment and the target use of the treated
water, the treatment choice is selected. The treatment technologies often include American
Petroleum institute (API) gravity separator, gas flotation, induced gas flotation, hydro
cyclones, centrifuges and macro porous polymer extraction. The level required for removal is
based on the imposed regulations. Certain methods are employed to remove the dispersed oil
and grease. These methods are described below:
2.1.1.1 Gravity separation

Equipment that separates the dispersed oil from produced water that is based on
gravity includes:
1. Skim Tanks
11
2. API separators
3. Plate coalescers
4. Skim piles
These pieces of equipment are usually cost-effective, but may require large storage
space due to their high residence time. They can be used offshore or onshore for
treatment. A brief description of each is given below:
Skim tanks: These tanks have a large residence time which is sufficient for gravity
separation to happen. They also can be pressure vessels or atmospheric tanks.
API separators: An API separator is an oil skimmer that could be horizontal and have
a rectangular cross-section. They are used rarely offshore due to their large size
(Arnold et al, 1991). American Petroleum Institute (API) is used for oil classification,
where it represents the ratio of density of oil to the density of a reference substance
(water). It is always calculated at 60 degrees Fahrenheit. The equation used to
calculate API is shown below.
API = 141.5/specific gravity - 131.5
The classification of oil based on API is as follows: API > 31.1 is light oil, API
between 22.3 and 31.1 is medium oil, API < 22.3 is heavy oil and API < 10.0 is very
heavy.
Plate coalescers: These could be in three different configurations:
i. Parallel plate interceptors (PPI).
ii. Corrugated plate interceptors (CPI).
iii. Cross flow separators.
The basic principles of these plates are that they allow the oil droplets to rise upwards
to the plate surface and form coalescers.
Skim pile: Skim pile are gravity water treating device used in offshore As shown in
fig flow through the multiple series of baffle plates creates quiescent zones that
reduces the distance given oil droplets must rise to be separated from the main flow.
It is usually used offshore at which the flow through baffle plates results in inactive
12
areas. This helps to minimize the distance for which an oil droplet will need to rise in
order to be strained from the main flow.
Figure 2.1 Skim Pile

(http://envirotechsystems.com/produced-water-equipment/sumperator-skim-pile/)
2.1.1.2 Gas flotation

Flotation technology is widely used for the treatment of conventional oilfield
produced water. This process uses fine gas bubbles to separate suspended particles
that are not easily separated by sedimentation. When gas is injected into produced
water, suspended particulates and oil droplets are attached to the air bubbles as it rises.
This results into the formation of foam on the surface of the water which is skimmed
off as froth (Cassidy et al, 1993)
13
Figure 2.2 Gas flotation method
(http://en.citizendium.org/wiki/Induced_gas_flotation)
There are two types of gas flotation technology (dissolved gas flotation and induced
gas flotation) based on the method of gas bubble generation and resultant bubble sizes.
In dissolved gas floatation units, gas is introduced into the flotation chamber by a
vacuum or by creating a pressure drop, but mechanical shear or propellers are used to
create bubbles in induced gas flotation units. Gas floatation can remove particles as
small as 25 µm and can even remove contaminants up to 3 µm in size if coagulation
is added as pre-treatment, but it cannot remove soluble oil constituents from water.
Flotation is most effective when gas bubbles size is less than oil droplet size and it is
expected to work best at low temperature since it involves dissolving gas into water
stream.
Flotation can be used to remove grease and oil, natural organic matter, volatile
organics and small particles from produced water. It does not require chemical use,
except coagulation chemicals are added to enhance removal of target contaminants.
Solid disposal will be necessary for the sludge generated from this process and the
estimated cost for flotation treatment is $0.60/m of produced water (Çakmakce M et
al, 2008).
14
2.1.1.3 Hydrocyclones
Hydrocyclones use physical method to separate solids from liquids based on the
density of the solids to be separated. They are made from metals, plastics or ceramic,
and usually have a cylindrical top and a conical base with no moving parts. The
performance of the hydrocyclone is determined by the angle of its conical section.
Hydrocyclones can remove particles in the range of 5–15 µm and have been widely
used for the treatment of produced water Jain hydro cyclone filter 2010).
Figure 2.3 Hydrocyclone
(http://www.ogj.com/articles/print/volume-113/issue-4/processing/hydrocyclone-study-
enables-gosp-debottlenecking.html)
15
Adsorption
Sand filters
Evaporation
Media filtration
Ion exchange technology
Membrane Treatment
Physical Treatment Reverse Osmosis
Ultrafiltration
Microfiltration
Nano filtration
Chemical Precipitation
Electrochemical Process
Fenton Process
Chemical Treatment
Photo electrolysis
Activated Sludge
Biological Treatment Biological aerated filter

Sequencing Batch Reactors
Table 2-1 Types of water treatment method
2.1.2 Physical Treatments:
Adsorption:
Adsorption is a surface phenomenon with common mechanism for organic and
inorganic pollutants removal from the waste water and produced water from oil and
gas industries. When a solution mixture of absorbable solute comes into contact with
solid with highly porous surface structure, liquid-solid intermolecular forces of
attraction cause some of the solute molecules from the solution to be deposited at the
solid surface or adsorbent. Some of the contaminated impurities which retained (on
the solid surface) in adsorption process is called adsorbate, whereas, the solid on
which it's retained is called as an adsorbent. This surface accumulation of adsorbate
on adsorbent process which it's called adsorption process.
16
An adsorption column is usually used, where it is packed with a certain adsorbent like
activated carbon, silica gel, bentonite etc. Soluble hydrocarbons will adsorb to the
surface of the adsorbent and eventually get engaged within the porous structure.
Common adsorbents used include activated carbon, nutshell media, zeolites, modified
organoclay, silica gel etc. where the surface area is a major factor in determining the
adsorption performance of these adsorbents. The major concern of adsorption
operation is the requirement of retention time which limits the throughput capacity.
Activated carbon can remove soluble BTEX, whereas organoclay can remove
insoluble hydrocarbons which are part of TPHs. Advantages include high efficiency
and no corrosion of equipment as well as no scale decomposition. Disadvantages
include high operating costs and disposal of spent material, as well as the possibility
to foul the bed of material. Zeolites have been used as one example of these
adsorbents, where they are introduced as pellets in a fixed bed. On the other hand,
Means et al. one column filled with resin which is capable of removing soluble organic
compounds based on this adsorbent. Nevertheless, to regenerate the adsorbent, the
used of solvents or acid backwash is proposed. The adsorption process it may be
affected by factors such as temperature, pH, salinity, dispersed/suspended oil,
dissolved organic chemicals, and heavy metals.
Sand filters: This method is purely physical method for treatment of waste water.
Sand filter provides efficient removal of large suspended solids particles. Sand filter
are mainly three types.
1) Rapid sand filter 2) Upward flow sand filter 3) Slow sand filter
In rapid sand filter and upward flow sand filter method require the use of flocculants
chemicals to work effectively while slow sand filters can produce very high quality
water free from taste and odour without the need for chemical aids. Sand filters can,
apart from being used in water treatment plants, that can be used for water purification
in particular households application.
A sand bed filter is like depth filter. Mainly there are two types of filter for
separating particulate solids from fluids:
 Surface filters: where particulates are captured on a permeable surface

 Depth filters: where particulates are captured within a porous body of material.
17
In addition, there are passive and active devices for causing solid-liquid separation
such as settling tanks, self-cleaning screen filters, hydro cyclones and centrifuges.
Evaporation: Evaporation is another method that can be used to remove oil

components from saline produced water. It can be vertical tubes, falling film, or
vapour compression evaporators. In this method, no chemical or physical treatment is
needed. Less maintenance is required for this method compared to the other methods
used in treating produced water.
Media filtration: Filtration technology is extensively used for the removal of oil and
grease and TOC from produced water. Filtration can be accomplished by the use of
various types of media such as sand, gravel, anthracite, walnut shell and others.
Walnut shell filters are commonly used for produced water treatment. This process is
not affected by water salinity and may be applied to any type of produced water.
Media filtration technology is highly efficient for the removal of oil and grease, and
efficiency of more than 90% has been reported. Efficiency can be further enhanced if
coagulants are added to the feed water prior to filtration. Media regeneration and solid
waste disposal are setbacks to this process (Colorado School of Mines, 2009).
Ion exchange technology: Ion exchange is a widely applied technology in industrial

operations for various purposes, including utilization for the treatment of CBM
produced water. It is especially useful in the removal of monovalent and divalent ions
and metals by resins from produced water(Clifford DA et al, 1999) Nadav suggested
that ion exchange has the potential to remove boron from RO permeate of produced
water. Ion exchange technology has a lifespan of ∼8 years and will require pre-
treatment options for solid removal. It also requires the use of chemicals for resin
regeneration and disinfection. The operating cost accounts for more than 70% of the
overall cost of this technology.
Membrane treatment: This is a physical treatment method based on separation of

the molecules depending on the pore size of the membrane. Membranes are micro
porous films with specific pore ratings, which selectively separate a fluid from its
components. There are four established membrane separation processes, including
microfiltration (MF), ultra-filtration (UF), reverse osmosis (RO) and nano filtration
(NF). RO separates dissolved and ionic components, MF separates suspended
18
particles, UF separates macromolecules (Madaeni SS et al, 1999) and NF is selective
for multivalent ions. MF and UF can be used as an individual technology for treating
industrial wastewater, but RO and NF are usually employed in water desalination
Microfiltration/ultra-filtration.
MF has the largest pore size (0.1–3 µm) and is typically used for the removal of
suspended solids and turbidity reduction. It can operate in either cross-flow or dead
end filtration. UF pore sizes are between 0.01 and 0.1 µm. They are employed in the
removal of colour, odour, viruses and colloidal organic matter (Han R, et al, 2010).
UF is the most effective method for oil removal from produced water in comparison
with traditional separation methods (He Y, Jianget al.2008), and it is more efficient
than MF for the removal of hydrocarbons, suspended solids and dissolved constituents
from oilfield produced water(Bilstad T et al,1996). Both MF and UF operate at low
Trans membrane pressure (1–30 psi) and can serve as a pre-treatment to desalination
but cannot remove salt from water.
Reverse osmosis and nano filtration: RO and NF are pressure-driven membrane

processes. Osmotic pressure of the feed solution is suppressed by applying hydraulic
pressure which forces permeate (clean water) to diffuse through a dense, non-porous
membrane (Spiegler KS et al, 1966). Seawater RO can remove contaminants as small
as 0.0001 µm, but its major disadvantage is membrane fouling and scaling (Mark W.et
al.2007). Early studies on using RO to treat produced water failed due to insufficient
process integration and poor treatment (Doran G et al ,2000). Nicolaisen and Lien
however reported a successful RO treatment of oilfield produced water in Bakersfield,
California. The pilot system which was operated for over 1700 h in 6 months produced
20 gpm of clean water. Bench-scale studies have shown the potential of brackish water
RO membranes to successfully treat oil and gas produced water. Experiments
indicated that RO membrane technology would be excellent for oilfield produced
water treatment with appropriate pre-treatment technology (Mondal S et al, 2008).
Capital costs of RO membrane systems vary depending on the size of rejection

required, materials of construction and site location. Operating costs depend on energy
price and total dissolved solid (TDS) level in the feed water. RO membrane systems
generally have a life expectancy of 3–7 years. NF is a robust technology for water
softening and metals removal and is designed to remove contaminants as small as
19
0.001 µm. It is applicable for treating water containing TDS in the range of 500– 25
000 ppm. This technology is similar to RO (T. C. Frankiewicz et al, 2000). NF
membranes were employed for produced water treatment on both bench and pilot
scales. Mondal and Wickramasinghe studied the effectiveness of NF membranes for
the treatment of oilfield produced water. Results showed a minimal improvement
when compared with the effectiveness of brackish water RO treatment of the same
feed water.
Membrane technology operates two types of filtration processes, cross flow filtration
or dead-end filtration, that can be a pressure (or vacuum) driven system. This method
is good compare to chemical and biological treatments used in produced water
because it does not require the use of chemicals. Also this method does not need much
space for installation. They are suitable for water with high oil content, particles with
small sizes, and flow rates which are greater than 150 (m3/hr), and, hence, they also
work effectively for medium and large offshore platforms.
2.1.3 Chemical Treatment:
Chemical oxidation: Chemical oxidation is an established and reliable technology

for the removal of colour, odour, COD, BOD, organics and some inorganic
compounds from produced water (Barratt PA et al 1997). Chemical oxidation
treatment depends on oxidation/reduction reactions occurring together in produced
water because free electrons cannot exist in solution. Oxidants commonly used
include ozone, peroxide, permanganate, oxygen and chlorine. The oxidant mixes with
contaminants and causes them to break down. The oxidation rate of this technology
depends on chemical dose, type of the oxidant used, raw water quality and contact
time between oxidants and water. Chemical cost during this process may be high
(Awwa et al, 1998. Energy consumption accounts for ∼18% of the total cost of
operations and maintenance. It requires minimal equipment and has a life expectancy
of 10 years or greater and solid separation post-treatment may be employed to remove
oxidized particles.
Electrochemical process: A pilot-scale experiment was conducted using double

anodes with active metal and graphite, and iron as a cathode. This configuration can
20
oxidize hydrocarbons and dissolved organic compounds to carbon dioxide and water
and other oxidation by-products. It was reported that the Biochemical Oxygen
Demand (BOD) as well as the Chemical Oxygen Demand (COD) were minimized by
more than 90 % in 6 minutes using this method.
Photo catalytic treatment: Honda and Fujishima have illustrated the use of this
method to decompose water on TiO2 electrodes. In addition, this method is applicable
for different contaminants. The organic treatment follows this process by the photo
catalytic:
In this method was tried in an open reactor at fixed pH followed by flocculation and
settlement. The filtrate was removed, and then TiO2 was used as a catalyst at high
pressure conditions and ambient temperature. It was found that this method can
minimize the toxicity of produced water (EPA 1980)
2.1.4 Biological Treatment:
Biological aerated filter (BAF) is a class of biological technologies which consists of

permeable media that uses aerobic conditions to facilitate biochemical oxidation and
removal of organic constituents in polluted water. Media is not more than 4 in in
diameter to prevent clogging of pore spaces when sloughing occur (Su D et al, 2007).
BAF can remove oil, ammonia, suspended solids, nitrogen, chemical oxygen demand
(COD), biological oxygen demand (BOD), heavy metals, iron, soluble organics, trace
organics and hydrogen sulphide from produced water (Ball HL.et al, 1995). It is most
effective for produced water with chloride levels below 6600 mg/l.
This process requires upstream and downstream sedimentation to allow the full bed
of the filter to be used. Removal efficiencies of up to 70% nitrogen, 80% oil, 60%
COD, 95% BOD and 85% suspended solids have been achieved with BAF treatment
(Ball HL et al, 1994).
Water recovery from this process is nearly 100% since waste generated is removed in
solid form. BAF usually have a long lifespan. It does not require any chemicals or
cleaning during normal operations. Its power requirement is 1–4 kWh/day, and capital
accounts for the biggest cost of this technology. Solids disposal is required for
21
accumulated sludge in sedimentation basins and can account for up to 40% of the total
cost of this technology.
2.2 Management of produced water:
Some of the options available to oil and gas operators for PW management Water
reduction: Water reduction is an essential option to minimize costs for operators, and
it can be done by several ways including the following:
1. Reduce the volume of water incoming the wells by adding mechanical blocking
devices or water shut-off chemicals.
2. Reduce the amount of water injected during the fracturing process by material
substitution. For example, consider the use of nitrogen or carbon dioxide as an
alternative to water.
3. De-oiling: Removing dispersed oil and grease
4. Removal of suspended solids and soluble organics
5. Removing naturally occurring radioactive minerals
Recycle/Re-use: If water reduction is not a feasible option, then one should consider
recycling or re-using produced water. Commonly, re-injection of produced water into
a producing formation is employed in order to augment production. Almost all
produced water is injected underground. The remainder is treated for reuse or
discharged on the surface (Mark W, et al 2007). Several ways are used to recycle/re-
use produced water including injection of water for future purposes, injection for
hydrological uses such as subsidence control, agriculture uses (wetlands, livestock
and irrigation), industrial uses (power plants, oil/gas industries) and others like
firefighting, dust control, etc. Usually, if the water quality is acceptable for certain
uses, then it would be considered beneficial, especially water with a low TDS (less
than 10000 ppm).
22
2.3 Adsorption
In adsorption that is mass transfer process which involves the accumulation of

substances at the interface of two phases, such as liquid-liquid, gas-liquid, gas-solid,
liquid-solid interface. The substance being adsorbed is the adsorbate and adsorbing
material termed as adsorbent. The properties of the adsorbate and adsorbent are quite
specific and depend upon their constituents. The constituents of adsorbents are mainly
responsible for removal of any particular pollutants from wastewater (Khattri SD et
al 2009).
In adsorption process if the interaction between the solid surface and the adsorbed
molecules has a physical nature, the process is called physisorption. In this case, the
attraction interactions are van der Waals forces and, as they are weak the process
results are reversible. Also, it occurs lower or close to the critical temperature of the
adsorbed substance. On the other hand, if the attraction forces between adsorbed
molecules and the solid surface are due to chemical bonding, the adsorption process
is called chemisorption.
In adsorption process if the interaction between in a solid–liquid system adsorption

results in the removal of solutes from solution and their accumulation at solid surface.
The solute remaining in the solution reaches a dynamic equilibrium with that adsorbed
on the solid phase. The quantity of adsorbate that can be taken up by an adsorbent as
a function of both temperature and concentration of adsorbate, and the process, at
constant temperature, can be described by an adsorption isotherm according to the
general
Qt = (C0-Ct) V/m
Where Qt (mg/g) is the amount of adsorbate per mass unit of adsorbent at time t, C0
and Ct (mg/L) is the initial and at time t concentration of adsorbate, respectively, V is
the volume of the solution (L), and m is the mass of adsorbent (g).
The process of adsorption is usually studied throw graphs know as adsorption

isotherm. Taking into account that adsorption process can be more complex, several
adsorption isotherms were proposed. Among these the most used models to describe
23
the process in water and wastewater applications were developed by (i) Langmuir, (ii)
Brunauer, Emmet, and Teller (BET), and (iii) Freundlich.
Adsorption process generally used isotherms for the application of activated carbon
in water and wastewater treatment are the Freundlich and Langmuir isotherms.
Freundlich isotherm is an empirical equation. Langmuir isotherm has a rational basis.
Factors Affecting Adsorption
The factors affecting the adsorption process are:
(i) Surface area,
(ii) Nature and initial concentration of adsorbate,
(iii) Solution pH,
(iv) Temperature,
(v) Interfering substances, and
(vi) Nature and dose of adsorbent.
Since adsorption is a surface phenomenon, the extent of adsorption is proportional to

the specific surface area which is defined as that portion of the total surface area that
is available for adsorption. Thus more finely divided and more porous is the solid
greater is the amount of adsorption accomplished per unit weight of a solid adsorbent
(Weber WJJr et al, 1972). The major contribution to surface area is located in the
pores of molecular dimensions.
Another important parameter is the temperature. In adsorption method reactions are

normally exothermic; thus the extent of adsorption generally increases with
decreasing temperature.
Finally, the adsorption can be affected by the concentration of organic and inorganic
compounds. The adsorption process is strongly influenced by a mixture of many
compounds which are typically present in water and wastewater. The compounds can
mutually enhance adsorption, may act relatively independently, or may interfere with
one other. In most cases, as also shown hereinafter, natural organic matter (NOM)
negatively affects the adsorption of emerging compounds in surface waters and
wastewaters (Yoon Y et al, 2005).
24
Adsorbents: Adsorbents and adsorbents used in produced water. In Adsorption
process widely used to remove the oil present in produced water, and activated carbon
is an adsorbent that is commonly used in the removal of a wide variety of organic
compounds one of which is oil. It has been found to be technically feasible. As per
United states environmental protection agency recommended activated carbon is good
adsorbent in adsorption and one of the best available technologies for treating organic
compounds, but it still may be expensive, especially for developing countries.
Okiel in 2011 conducted a study to remove emulsified oil from produced water using
three different adsorbents, namely powdered activated carbon, deposited carbon, and
bentonite. The oil-water emulsion samples were allowed to stabilize and then were
divided into 200 mL portions where different doses of the adsorbents were added.
Contact time was varied, after which the samples were filtered and extracted using
1,1,2-trichloro-1,2,2-trifluoroethane solvent. Then the extracted oil was diluted and
tested by infrared spectroscopy. As per results showed that adsorbents were able to
remove oil, where the oil recovery ranged from 20 to 90 %. This recovery depended
on the amount of adsorbents used, their weight, and the contact time.
Nwabanne, J. T in 2012 studied the adsorption performance of packed bed column

using activated carbon prepared from oil palm fibre for the removal of lead from
aqueous solution was investigated. The influence of important parameters like inlet
ion concentration, flow rate and bed height on the breakthrough curves and adsorption
performance was studied. Into the result showed that adsorption efficiency increased
with increase in the inlet ion concentration and bed height and decreased with increase
in flow rate. Increasing the flow rate resulted to a shorter time for saturation. As per
result indicated that the throughput volume of the aqueous solution increased with
increase in bed height, due to the availability of more number of sorption sites. The
adsorption kinetics was analysed using Thomas and Yoon and Nelson kinetic models.
Kinetic data were well described by in Thomas and Yoon and Nelson kinetic model.
The maximum adsorption capacity, calculated from both models, increased with
increase in flow rate and initial ion concentration but decreased with increase in bed
height. For Yoon and Nelson model, the rate constant increased with increase in flow
rate, initial ion concentration and bed height. The time required for 50% breakthrough
decreased with increase in flow rate, bed height and initial ion concentration. The
kinetic data correlated well with both models. The relationship between the
25
experimental breakthrough curve to the breakthrough profile obtained from Yoon and
Nelson method showed a satisfactory fit for activated carbon derived from oil palm
empty fruit bunch.
Anantha Singh investigated described adsorption of Crystal Violet (CV) by bottom

ash in fixed-bed column mode. Adsorption was studied in batch mode for finding
adsorption capacity of bottom ash. In fixed bed column adsorption, the effects of bed
height, feed flow rate, and initial concentration were studied by assessing
breakthrough curve. In result show that CV adsorption onto bottom ash was
investigated. Adsorption capacity of bottom ash was found to be 5.24 mg/g from batch
isotherm study. Removal efficiency of dyes from wastewater strongly depends on
flow rate, initial CV concentration and bed depth. The slope of the breakthrough curve
decreased with increasing bed height. The breakthrough time and exhaustion time
were decreased with increasing influent CV concentration and flow rates.
Anantha Singh also investigated the removal of crystal violet from wastewater, by
means of bottom ash, was investigated in a packed bed down-flow column. The bed
depth service time (BDST) model was used to analyse the experimental data up to
breakthrough time. A mass transfer model was used to analyse the mass transfer zone.
The breakthrough curve was analysed by the Thomas, Yoon–Nelson, and Clark
models. Result shows that adsorption capacity is inversely proportional to flow rate,
concentration and bed depth. The Thomas rate constant decreases with corresponding
decreases in flow rate. The value of s is decreased with corresponding increases in
flow rate, initial CV concentration, and bed depth. The values of r increase with
corresponding increases in concentration and flow rate.
I. M. Muhammad in 2012 showed that eggshells have the ability to adsorb oil
providing almost 100 % oil removal by using just 1.8 g/L of the eggshell. So that
preparing adsorbent as eggshells was crushed, washed, and dried -- after which they
were added to samples of produced water. Different dosages of eggshells were used
to find the optimum dosage, which was found to be 1.8 g to remove 194 mg of oil, i.e.
100 % of oil. Nonetheless, the adsorption was found to follow pseudo second order
kinetics, whereas the Temkin-Pyzhev isotherm was the most favourable isotherm that
has the highest correlation coefficient.
26
U. A. El-Nafaty in 2013 also studies by using natural adsorbents such as banana peel.
The adsorbent was chosen based on its low cost, abundance, and flexibility. It was
presented that banana peels can contribute to a 100 % oil removal by just using 50
mg/L of the adsorbent. The contact time is 35 minutes. The kinetics was described by
pseudo second order kinetics, and the Langmuir isotherm favours the adsorption
process.
27
CHAPTER 3 MATERIALS AND METHODS
3.1 List of Instruments:
1) Atomic Adsorption Spectrophotometer
2) Flame Photometer
3) Gravimetric
4) pH meter
5) Salinity meter
6) Conductivity meter
7) Orbital Shaker
8) Hot gas oven
9) Sieve Analyser
10) X –Ray fluorescence
List of Glasswares:
1) Measuring cylinders
2) Test tubes
3) Separating funnel
4) Conical flask
5) Beakers
6) Funnel
28
3.2 Experimental Procedure:
Figure 3.1 Sample Collection from ONGC limbodra on 30-9-2016
Figure 3.2 Sample Collection from ONGC Limbodra on 24-11-2016
Sample of produced water and soil collected from ONGC Limbodra GGS II. After
collect the sample than I started to measure its parameter into petroleum research lab
in GERMI.
29
3.3 Characterization of Produced Water:
After collecting produced water sample, parameters of produced water measured using Flame
photometer, Gravimetric, Atomic absorption spectroscopy (AAS) etc.
3.3.1 Flame Photometer:
It is device which used for inorganic chemical analysis to determine the concentration
of certain metal ions, among them sodium, potassium, lithium, and calcium.
Figure 3.3 Flame Photometer
(http://www.systronicsindia.com/Product.aspx?QF1=3&Qf2=Flame%20Photometers&Qf5=
*MFG*)
As per principle, it is a controlled flame test with the intensity of the flame colour
quantified by photoelectric circuitry. In flame photometer the intensity of the flame
colour will depend on the energy that had been absorbed by the atoms that was
sufficient to vaporise them. A sample is introduced to the flame at a constant rate.
Then Filters select which colours the photometer detects and exclude the influence of
other ions. Before use, the device requires calibration with a series of standard
solutions of the ion to be tested Click and drags each of the standard solution below
the Capillary tube and click on the "Aspirate" button to calibrate the machine.
30
Figure 3.4 Flame Photometer Analysis
(GERMI, Gandhinagar)
1) Select the Test
2) Drag the standard solution to place it in the original position.
3) After calibration select the sample solution from the list.
4) Click and drag the fruit juice sample below the Capillary tube and click on the
"Start Test” button to measure the concentration.
These are the standard solution:
Na: Standard solution of Na with 10, 50,100ppm
Ca: Standard solution of Ca with 10, 50,100,300ppm
Li: Standard solution of Li with 2, 5, 10, 50ppm
K: Standard solution of K with 1, 10, 25, 50,100ppm
General procedure for preparation of stock standard solution for flame photometer
31
1) Sodium
i) 1000ppm
Dissolve 2.5416 g Nacl in one litre of glass distilled water
ii) 1000ppm (asNa2O)
Dissolve 1.886g Nacl in one litre of glass distilled water
2) Potassium
i) 1000ppm
Dissolve 1.9070 g KCL or 2.5869 g KNO3 in one litre of glass distilled water
ii) 100ppm (as K2O)
Dissolve 1.5830 g KCL in one litre of glass distilled water
3) Calcium
i) 1000ppm
Dissolve 2.497 g CaCO3 in approx. 300ml glass distilled water and add 10ml conc.
HCL
Dilute to 1 litre .The same solution is 1400ppm as CaO
4) Lithium
i) 2000ppm (as Li2O)
Dissolve 4.945 g Li2CO3 in approx. 300ml glass distilled water and add 15ml conc.
HCL. After release of Co2 dilute to 1 litre.
3.3.2 AAS/Atomic Absorption Spectroscopy
Atomic Absorption Spectroscopy is an instrumental analysis technique for rapid trace

metal analysis. It is based on element specific wavelength light absorption by ground
state atoms in the flame or electro thermal graphite furnace. AAS finds immense of
applications in the analysis for trace metals in soils, lakes, rivers, oceans, and drinking
water, pharmaceuticals, foods and beverages, geological and mineralogical samples,
petroleum products, biological fluids and specimens and forensic analysis. In
32
generally the results get in ppm levels and a higher sensitivity of ppb levels when we
using graphite furnace atomisation.
The atoms of different elements absorb characteristic wavelengths of light. Analysing
a sample to see if it contains a particular element means using light from that element.
For example with lead, a lamp containing lead emits light from excited lead atoms
that produce the right mix of wavelengths to be absorbed by any lead atoms from the
sample. In AAS, the sample is atomised – i.e. to convert into the ground state free
atoms in the vapour state – and a beam of electromagnetic radiation emitted from
excited lead atoms is passed through the vaporised sample. Some of the radiation is
absorbed by the lead atoms in the sample. The more the number of atoms there is in
the vapour, the more radiation is absorbed. The amount of light absorbed is
proportional to the number of lead atoms. As per the calibration curve is constructed
by running several samples of known lead concentration under the same conditions as
the unknown. The amount the standard absorbs is compared with the calibration curve
and this enables the calculation of the lead concentration in the unknown sample. As
per an atomic absorption spectrometer needs the following three components: a light
source; a sample cell to produce gaseous atoms; and a means of measuring the specific
light absorbed.
3.3.3 Gravimetric
In this method requires that the extracted sample will be put in a flask with a known
weight, after which the temperature is controlled in a water bath, and the solvent is
evaporated, condensed, and then recovered. Then, the oil left in the flask is dried and
weighed, from which the weight of the flask is subtracted. Thus, the amount of the
left over (residual) PW is calculated.
Advantages include ease of determinations since gravimetric does not require any
calibration curve and normally it does not provide instrumental errors, and it can read
the atomic mass of any element up to six significant figures. However, it is time
consuming and it can only read one element or a limited number of elements at the
same time. This tool has been used to identify crude oil presence in samples, but
mostly to study the bacterial degradation of crude oil/organic matter.
33
pH: Before measuring ph of produced water prepared standard buffers solution it's ph
4.0 and 10.01 prepared using standard methods. Ref: Durst, R A 1975 Standard
methods.
Salinity: Dissolve 32.4356grams of kcl in 1kg of solution for 35ppt salinity.

Conductivity is very dependent on temperature.
Conductivity: Before measuring conductivity prepared standard solution. For making

standard solution dissolve 0.7459grams of potassium chloride in distilled water made
up to one litre solution. At 25̊ C this has conductivity of 1413µs/cm.
3.4 Adsorption process for produced water
The term adsorption refers to the accumulation of substance at the interface between
two phase (liquid - solid interface or gas - solid interfaces) the substance that
accumulates at the interface is called adsorbate and the solid on which adsorption
occurs is adsorbent.
Adsorbent: The substance on whose surface the adsorption process occurs is known
as adsorbent.
Adsorbate: The substance whose molecules get adsorbed on the surface of the
adsorbent is known as adosrbate.
Adsorption is different from absorption. In absorption the molecules of substance are

equally spread in the bulk of the other, whereas in adsorption molecules of one
substance are present in higher concentration on the surface of the other substance.
Adsorption can be classified in two types;
1) Chemical adsorption
2) Physical adsorption
In chemical adsorption is illustrated by the formation of strong chemical association

between molecules or ions of adsorbate to adsorbent surface .Which is generally due
to exchange of electrons and thus chemical sorption generally irreversible. In
34
chemisorption the force of attraction is very strong; therefore adsorption can't be
easily reversed.
In Physical adsorption is characterized by weak vanderwaals intra particle bonds

between adsorbate and adsorbent therefore this type of adsorption can be easily
reversible by heating or by decreasing the pressure in most cases.
In adsorption mainly adsorbent including agriculture by products is controlled by

physical forces with some exception of chemisorption. The main physical forces
controlling adsorption are vanderwaals forces, hydrogen bonds, polarity, and dipole-
dipole interaction.etc. Adsorption process provides an attractive alternative for the
treatment of chemical contaminated waters, waste water, produced water (o&g)
especially if the sorbent is inexpensive and does not require an additional pre-
treatment step before its application. As for environmental remediation purpose,
adsorption techniques are commonly used to remove certain classes of chemical
contaminants from waters, especially those that are practically unaffected by
conventional biological wastewater treatments. Adsorption has been found to be
superior to other techniques in terms of flexibility and simplicity of design, initial cost,
insensitivity to toxic pollutants and ease of operation. Adsorption also does not
produce harmful substances.
Adsorption depends upon following factors.
1) Nature of adsorbate and adsorbent
2) The surface area of adsorbent
3) Experimental condition
4) Contact time
5) Adsorbent dosage
35
3.4.1 Soil and Charcoal Analysis
A sieve analysis (or gradation test) is a procedure used to assess the particle size
distribution (also called gradation) of a granular material. The size distribution is often
of critical importance to the way the material performs in use.
The size distribution is often of crucial importance to the way the adsorbent performs
in use. A sieve analysis can be performed on any type of non-organic or organic
granular materials including sands, crushed rock, clays, granite, feldspars, coal, soil,
a wide range of manufactured powders, grain and seeds, down to a minimum size
depending on the exact method.
Figure 3.5 Sieve Analysis
(Civil lab, PDPU)
A representative weighed sample is poured into the top sieve which has the largest
screen openings. Each lower sieve in the column has smaller openings than the one
above. At the base is a round pan, called the receiver.
The column is typically placed in a mechanical shaker. The shaker shakes the column,
usually for some fixed amount of time. After the shaking is complete the material on
36
each sieve is weighed. The weight of the sample of each sieve is then divided by the
total weight to give a percentage retained on each sieve. The size of the average
particle on each sieve is then analysed to get a cut-off point or specific size range,
which is then captured on a screen.
3.4.2 Procedure for making activated charcoal
1) Take charcoal and powdered it.
2) To make 25% of solution by weight for calcium chloride. Examples for 9ml of
distilled water add into 3gram of calcium chloride and make solution.
3) Than take 5gram of charcoal powder and make paste.
4) Than put paste for 24 hours in atmosphere temperature.
5) Now we have to filter that paste using distilled water
6) Dry that paste at 250 c for 30 minutes
3.4.3 Analysis of adsorbent
Analysis of adsorbent chemical properties using X-ray Fluorescence in Institute of

seismological research at Gandhinagar.
XRF (X-ray fluorescence) is a non-destructive analytical technique used to determine

the elemental composition of materials. XRF analysers determine the chemistry of a
sample by measuring the fluorescent (or secondary) X-ray emitted from a sample
when it is excited by a primary X-ray source. Each of the elements present in a sample
produces a set of characteristic fluorescent X-rays ("a fingerprint") that is unique for
that specific element.
X-ray Fluorescence spectrometry is an elemental technique with broad application in

science and industry. XRF is based on the principle that individual atoms, when
excited by an external energy source, emit x-ray photons of a characteristic energy or
wavelength. That is widely used for elemental analysis and chemical analysis,
37
particularly in the investigation of metals, glass, ceramics and building materials, and
for research in geochemistry etc.
3.5 Adsorption Batch Study
Adsorption tests were performed in set of 3 Erlenmeyer flasks (250ml) where 150ml
of produced water with initial concentration very high. Equal mass of adsorbent
100mg/l added into the flasks. but here adsorbent uses different like mixture soil and
activated charcoal in 1st flask ,soil as adsorbent in 2nd flask, activated carbon as
adsorbent in 3rd flask.
Each flask kept in orbital shaker of 120rpm and at 300c for 6 hours to reach
equilibrium. All samples were filtered using whatman filter paper 125mm. The
concentration of produced water measured by flame photometer.
Take 3 conical flasks of 250ml and fill each flask 100ml of formation water.
1st flask: 150ml of formation water and 100mg/l activated charcoal.
2nd flask: 150ml of formation water and 100mg/l soil.
3rd flask: 150ml of formation water and 100mg/l activated charcoal and soil.
Here soil which I used from around oil well. And size of both adsorbent 300micron.
Then put this 3 flask on orbital shaker and shake. All flasks were shaken at a constant
rate, allowing sufficient time for adsorption equilibrium. In this practical assumed that
the applied shaking speed allows all the surface area to come in contact with metal
ions over the course of the experiments. This study was performed at room
temperature to be representative of environmentally relevant condition. It for 3 hours.
From each flask take 10ml regular interval time like 5, 10, 15, 30, 45, 60, 90,
120,150,180,240,360minutes.
After completing this process I measured the concentration of formation water like
potassium, sodium, lithium, and calcium. So it decreased some amount because some
impurities adsorbed in adsorbent onto the activated charcoal and soil.
38
Now draw graph of concentration of cation versus time so we know about that which
time concentration it would be constant.
So now take that time constant and change only adsorbent dosage so we know that
which adsorbent dosage is more suitable for that water. After that draw graph of
adsorbent dosage versus concentration of formation water like sodium, potassium,
lithium and calcium.
The solution volume (V) was kept constant. The amount of metal adsorbed per
unit mass is calculated as
Qe = (Ci - Ce) V/ m
Where Ci and Ce are the initial and equilibrium concentration (mg/L), m is the
mass of the adsorbent (g) and V is the volume of the solution (mL). And as per
the equation the percentage of metal ion removal (%MR) calculated using the
equation
%MR = (Ci - Ce)/Ci × 100
3.6 Column study
The adsorption experiments were carried out in columns that were capable with a
stopper for controlling the column flow rate. This experiment is useful in
understanding and predicting the behaviour of the process. The sample solution was
passed through the adsorption column with a known amount of activated carbon and
soil at a flow rate of 8 mL/min by gravity. Into the column study the flow rate was
kept constant by controlling the stopper valve.
39
Figure 3.6 Column adsorption method
(ADEMILUYI et al, J. Appl. Sci. Environ. Manage. September, 2009 Vol. 13(3) 39 – 47)
In column studies were conducted using columns, 2.5 cm in diameter and 30 cm in

length. The column was packed with Activated carbon and soil between supporting
layers of pre-equilibrated glass wool. The particle size of adsorbent which was 300–
600µm; produced water was fed into the column in a down flow mode. Before
operation, the column was rinsed with distilled water and left overnight. The produced
water samples were collected at specified time intervals of 1hr and measured for
different ion concentration by flame photometer. (Mulu Berhe Desta, 2013)
The concentration of metal was measured in flame photometer as per American public
health association method.
After complete the whole process i collect all used adsorbent and put it normal
atmospheric temperature for dry. So that i analysis of that adsorbent using XRF. So I
can know how many impurities or chemical contamination adsorbed onto adsorbent.
40
CHAPTER 4 RESULT ANALYSIS
4.1 Produced water parameter
Following are the parameter of the produced water which I measured using flame
photometer and atomic adsorption spectrophotometer. All parameter measured as per
Bureau of Indian standard and American public health association standard method.
Parameter Value Standard Method

pH 7.5 - 8.5 (at 28O IS-3025(part 11) 1983- clause -RA
C) 2012
Electrical conductivity 15.6 ms/cm APHA-22nd ed. 2510B
Salinity 19.2 ppt APHA 22nd ed. 2520- B Electrical
Conductivity method
Total suspended solids 210-240 ppm APHA 22nd ed. 2540 D
Total dissolved solids 12400-14000 -
Chemical oxygen 820 mg/l IS - 3025 (part 58) 2006 RA 2012
demand
Hardness 140-160 APHA 2340- EDTA Titrimetric
method
Total Alkalinity 812.8 - 1024 ppm IS -3025 (Part 23) 1986 - cluse 8.1
RA 2014
Chloride 3500 - 4000 ppm APHA 22nd ed. 4500 B
Argentometric method
Table 4-1 Physical parameter of produced water
41
Metal Value(mg/L) Standard Method
Pb 0.037 IS - 3025 (Part 47)
V 2.601 APHA 22ne ed. 3500 B
AS 0.015 Is - 3025 (Part 37)
Mg 1467 APHA 22nd ed. 3500 Mg –B
Na 2029 APHA 22nd ed. 3500 Na- B Flame
photometry
Ca 1200-1360 APHA 22nd ed. 3500 Ca- B
EDTA Titrimetric method
Li 2.3-2.7 APHA 22nd ed. 3500 Li B- Flame
photometry
K 460 APHA 22nd ed. 3500 K - B Flame
photometry
Table 4-2 Ions measured in produced water
4.2 Adsorbent Analysis
Here, Adsorbent as mixture of soil and charcoal. Soil which collected from around oil well
at Limobdra.
This is the results of the soil analysis measure through sieve analysis. (Simon J.
Blott, et al 2001)
42
Individual Cumulative
Size in Weight in
Description weight in weight in Φ
micron grams
percentage percentage
4000 25.84 13.03 13.03 -2
2000 13.82 6.97 20.01 -1
Sand 1400 5.52 2.78 22.80 0.25
Coarse grained 600 11.94 6.02 28.82 0.7
250 28.49 14.37 43.19 2
Fine grained
125 54.44 27.46 70.66 2.99
Very Fine
grained 65 47.12 23.77 94.43 4.1
45 4.29 2.164 96.60 4.47
Coarse silt 40 4.41 2.22 98.83 4.7
Clay <40 2.31 1.165 100 5
198.22
Table 4-3 Soil grain size analysis for oil well site at Limbodra
75
Weight in grams
50
25
0
-2 -1 0.25 0.7 2 2.99 4.1 4.47 4.7 5
Phi value
Graph 4-1 Physical properties of soil at Limbodra
43
6
5
4
Phi value 3
2
1
0
-1
-2
-3
0 20 40 60 80 100
Soil Weight (%)
Graph 4-2 Cumulative soil weight percentage vs Phi Value
4.3 Effects of various factor depends on adsorption process
4.3.1 Effect of contact time on soil and charcoal mix
Here, Adsorbent use as mixture of soil and charcoal with size 300micron.
As can be seen from below table no 4.4 the amount of ion concentration adsorbed on
the mixture of soil and charcoal increase with time and at some point in time, it reaches
a constant value beyond which no more ions are removed from the produced water.
At this point, the amount of ion concentration desorbing from soil and activated
carbon is in state of dynamic equilibrium time reflects the maximum adsorption
capacity of the adsorbent under those operating condition.
44
Time in Ca+2 (mg/l) Li+ (mg/l) K+(mg/l) Na+(mg/l)
minutes
5 1149.0 2.2 456 1956.0
10 934.2 2.1 389 1803.0
15 808.6 2.1 377 1788.0
30 745.4 1.8 344 1594.0
45 725.0 1.7 330 1491.0
60 712.3 1.7 327 1273.0
90 704.4 1.5 298 1118.0
120 649.3 1.4 276 1093.0
150 618.8 1.4 254 830.2
180 598.1 1.3 241 763.8
240 596.7 1.2 234 755.5
360 596.1 1.1 232 750.3
Table 4-4 Effect of contact time on soil and charcoal versus produced water
Here as per graph no 4.3, calcium concentration versus time is shown that
concentration decreases with time. But after some time it is constant. In this practical
adsorbent used as mixture of soil and activated charcoal. As per this study the
adsorption capacity at equilibrium from 1149 to 596.1 mg/g with in the initial ion
concentration from 1200mg/l.
1200
Calcium concetration (mg/l)
1100
1000
900
800
700
600
500
0 50 100 150 200 250 300 350 400
Time in minutes
Graph 4-3 Effect of contact time on soil and charcoal versus calcium concentration in
produced water
45
Here as per graph no 4.4, lithium concentration versus time is shown that
adsorption capacity at equilibrium from 2.2 to 1.1 mg/g with in the initial ion
concentration from 2.3mg/l.
2.4
2.2
Lithium concetration(mg/l)
1.8
1.6
1.4
1.2
1
0 50 100 150 200 250 300 350 400
Time in minutes
Graph 4-4 Effect of contact time on soil and charcoal versus lithium concentration in
produced water
Here as per graph no 4.5, potassium concentration versus time is shown that
46
500
Potassium concetration(mg/l)
450
400
350
300
250
200
0 50 100 150 200 250 300 350 400
Time in minutes
Graph 4-5 Effect of contact time on soil and charcoal versus potassium concentration
in produced water
Here as per graph no 4.6, sodium concentration versus time is shown that
2100
Sodium concetration(mg/l)
1900
1700
1500
1300
1100
900
700
500
0 50 100 150 200 250 300 350 400
Time in minutes
Graph 4-6 Effect of contact time on soil and charcoal versus sodium concentration in
produced water
47
Here, Adsorbent use as only activated charcoal with size 300 micron
As can be seen from below table no 4.5 the amount of ion concentration adsorbed on
the Activated charcoal increase with time and at some point in time, it reaches a
constant value beyond which no more ions are removed from the produced water. At
this point, the amount of ion concentration desorbing from activated carbon is in state
of dynamic equilibrium time reflects the maximum adsorption capacity of the
adsorbent under those operating condition.
Time in Ca+2 Li+ K+ Na+

minutes (mg/l) (mg/l) (mg/l) (mg/l)
5 1180.0 2.2 450.0 1990
10 992.8 2.1 442.8 1860
15 893.2 2.1 421.3 1750
30 805.0 2.1 401.8 1570
45 774.0 1.8 394.6 1486
60 767.5 1.8 370.2 1389
90 757.2 1.7 360.4 1291
120 749.1 1.7 358.3 1233
150 735.8 1.7 351.2 1210
180 716.9 1.6 341.0 1120
240 710.3 1.6 341.2 1116
360 701.6 1.4 340.0 1100
Table 4-5 Effect of contact time on activated charcoal versus produced water
Here as per graph no 4.7 to 4.10, ion concentration versus time is shown that
activated charcoal used as a single adsorbent.
48
1200
1100

1000
900
800
700
600
500
0 50 100 150 200 250 300 350 400
Time in minutes
Graph 4-7 Effect of contact time on activated charcoal versus calcium

concentration in produced water
2.4
2.2
Lithium concetration(mg/l)
1.8
1.6
1.4
1.2
1
0 50 100 150 200 250 300 350 400
Time in minutes
Graph 4-8 Effect of contact time on activated charcoal versus lithium concentration
in produced water
49
460
440
Potassium concetration (mg/l)
420
400
380
360
340
320
300
0 50 100 150 200 250 300 350 400
Time in minutes
Graph 4-9 Effect of contact time on activated charcoal versus potassium

2200
2000
Sodium concetration(mg/l)
1800
1600
1400
1200
1000
0 50 100 150 200 250 300 350 400
Time in minutes
Graph 4-10 Effect of contact time on activated charcoal versus sodium

50
4.3.2 Effect of adsorbent dosage
Adsorbent dosage is important process parameters to determine the capacity of an

adsorbent for given amount of the adsorbent at operating conditions. Generally the
percentage of ion removal from produced water increase with increasing adsorbent
dosage, where the quantity of sorption sites at the surface of adsorbent will increase
by increasing the amount of adsorbent. The effect of adsorbent dosage gives an idea
for the ability of an ion adsorption to adsorb with the smallest amount of adsorbent,
so as recognise the capability of an ion from an economical point of view. The
reported studies on the effect of adsorbent dosage on the percentage of ion removal in
below table. Here I take adsorbent dosage (soil + Activated charcoal) as 25, 50, 75,
100,125mg/l and with constant time 360 min. and result which I got is below.
1) Calcium
Here as shown in table no 4.6 when we increase adsorbent dosage 25mg/l to 125mg/l
than calcium concentration continuously decrease with adsorbent dosage but after
100mg/l adsorbent dosage the removal efficiency and calcium concentration it
decreasing low rate and after that it would be constant. In below table shown that
calcium concentration and removal efficiency. And I also as draw graph of calcium
concentration and material removal to the adsorbent dosage so we can better
understand.
Adsorbent Dosage (mg) Calcium Concentration Calcium Removal (%)

(mg/l)
25 876.3 32.37
50 748.6 37.61
75 659.1 45.05
100 596.1 50.32
125 548.1 54.32
Table 4-6 Effect of adsorbent dosage on Calcium ion
51
950 60
Calcium concetration in produced water
Calcium removal by adsorbent

850 50
750
40
650
(%)
(mg/l) 30
550
20
450
350 10
250 0
0 25 50 75 100 125 150
Amount of adsorbent in mg
Calcium concentration in produced water(mg/l) Calcium removal by adsorbent (%)
Graph 4-11 Adsorbent dosage vs Material removal for Calcium ion
2) Lithium
Here as shown in table when we increase adsorbent dosage 25mg/l to 125mg/l than
calcium concentration continuously decrease with adsorbent dosage but after 100mg/l
adsorbent dosage the removal efficiency and lithium concentration it decreasing low
rate and after that it would be constant. In below table shown that calcium
concentration and removal efficiency. And I also draw graph of lithium concentration
and material removal to the adsorbent dosage so we can better understand.
Adsorbent Dosage (mg) Lithium Concentration Lithium Removal (%)

(mg/l)
25 2.1 8.60
50 1.9 17.39
75 1.5 34.78
100 1.1 52.17
125 1.0 56.52
Table 4-7 Effect of adsorbent dosage on Lithium ion
52
2.5 60
Lithium removal by adsorbent (%)

Lithium concteration (mg/l)
2 50
40
1.5
30
1
20
0.5
10
0 0
0 25 50 75 100 125 150
Lithium Concentration in produced water (mg/l)

Lithium Removal by adsorbent (%)
Graph 4-12 Adsorbent dosage vs Material removal for Lithium ion
3) Potassium
adsorbent dosage the removal efficiency and potassium concentration it decreasing
low rate and after that it would be constant. In below table shown that calcium
concentration and removal efficiency. And I also draw graph of potassium
concentration and material removal to the adsorbent dosage so we can better
understand.
Adsorbent dosage (mg) Potassium Concentration Potassium Removal (%)

(mg/l)
25 410.0 10.86
50 350.5 23.80
75 290.0 36.95
100 232.5 49.45
125 215.0 53.26
Table 4-8 Effect of adsorbent dosage on Potassium ion
53
500 60
Potassium concteration in produced
Potassium removal by adsorbent (%)

400 50
40
300
water (mg/l)
30
200
20
100 10
0 0
0 25 50 75 100 125 150
Potassium concentration in produced water (mg/l)

Potassium removal by adsorbent (%)
Graph 4-13 Adsorbent dosage vs Material removal for Potassium ion
4) Sodium
adsorbent dosage the removal efficiency and sodium concentration it decreasing low
rate and after that it would be constant. In below table shown that calcium
concentration and removal efficiency. And I also draw graph of sodium concentration
and material removal to the adsorbent dosage so we can better understand.
Adsorbent Dosage (mg) Sodium Concentration Sodium Removal (%)

(mg/l)
25 1710 15.72
50 1435 29.27
75 1089 46.32
100 750 63.03
125 732 63.92
Table 4-9 Effect of adsorbent dosage on Sodium ion
54
2000 70
Sodium removal by adsorbent (%)

Sodium concetration in produced water
60
1500 50
40
1000
(mg/l) 30
500 20
10
0 0
0 25 50 75 100 125 150
Sodium Concentration in produced water (mg/l)

Sodium Removal by adsorbent (%)
Graph 4-14 Adsorbent dosage vs Material removal for Sodium ion
4.4 Langmuir adsorption isotherms
Langmuir isotherm assumes monolayer adsorption onto a surface containing a finite

number of adsorption sites of uniform strategies of adsorption with no transmigration
of adsorbate in the plane of surface. Langmuir equation is given below;
Ce/Qe = 1/Q0b + Ce/Q0
Where Ce is the equilibrium concentration of the adsorbate (mg/l)
qe is the amount of adsorbate adsorbed per unit mass of adsorbent(mg/g)
Q0 and b are Langmuir constants related to adsorption capacity and rate of adsorption
respectively.
As per Langmuir isotherm I drawn graph Ce/Qe Vs Ce for calcium, lithium, potassium
and sodium ions
55
1) Calcium
Adsorbent Calcium Amount of Specific

dosage (mg) concentration, Ce adsorbate Adsorption,
(mg/l) adsorbed Ce/Qe (mg/l)
per unit
mass of
adsorbent,
Qe (mg/g)
25 876.1 5.43 161.30
50 748.6 6.03 123.96
75 659.1 7.21 91.38
100 596.1 9.02 66.02
125 546.1 12.94 42.35
Table 4-10 Amount of calcium adsorbed per unit mass of soil and charcoal
180
Specific Adsorption ,Ce/Qe (mg/l)
160 y = 0.359x - 149.15

R² = 0.9909
140
120
100
80
60
40
20
0
0 200 400 600 800 1000
Graph 4-15 Equilibrium concentration of calcium ion vs
Specific adsorption
56
2) Lithium
Adsorbent Lithium Amount of Specific

Dosage(mg) concentration Ce adsorbate Adsorption
(mg/l) adsorbed per Ce/Qe(mg/l)
unit mass of
adsorbent, Qe
(mg/g)
25 2.1 0.008 262.5
50 1.9 0.006 250.0
75 1.5 0.010 140.6
100 1.1 0.011 100.0
125 1.0 0.010 96.1
Table 4-11 Amount of lithium adsorbed per unit mass of soil and charcoal
300
250
200
150
100
50 y = 164.26x - 79.822
R² = 0.9567
0
0 0.5 1 1.5 2 2.5
Lithium concetration ((mg/l)
Graph 4-16 Equilibrium concentration of lithium ion vs Specific adsorption
57
3) Potassium
Adsorbent Potassium Amount of Specific

Dosage(mg) concentration, Ce adsorbate Adsorption,
(mg/l) adsorbed per Ce/Qe (mg/l)
unit mass of
adsorbent, Qe
(mg/g) Specific
Adsorption
Specific
Adsorption
25 410.0 2.00 205.00
50 350.5 2.19 160.04
75 290.0 2.26 128.31
100 232.5 2.27 102.46
125 215.0 1.96 109.69
Table 4-12 Amount of potassium adsorbed per unit mass of soil and charcoal
250
200
150
100
50 y = 0.5048x - 10.124
R² = 0.954
0
0 100 200 300 400 500
Potassium concetration (mg/l)
Graph 4-17 Equilibrium concentration of potassium ion vs Specific adsorption
58
4) Sodium
Adsorbent Sodium Amount of Specific Adsorption

Dosage(mg) Concentration, adsorbate Ce/Qe (mg/l)
Ce(mg/l) adsorbed per
unit mass of
adsorbent, Qe
(mg/g) Specific
Adsorption
Specific
Adsorption
25 1710 12.76 134.01
50 1435 11.88 120.79
75 1089 12.53 86.91
100 750 12.79 58.63
125 732 10.37 70.54
Table 4-13 Amount of sodium adsorbed per unit mass of soil and charcoal
150
Specific Adsorption ,Ce/Qe
100
(mg/l)
50
y = 0.0743x + 9.285
R² = 0.9693
0
0 500 1000 1500 2000
Sodium concetration (mg/l)
Graph 4-18 Equilibrium concentration of sodium ion vs

Specific adsorption
59
Langmuir Isotherm parameters for adsorption of metal ions
Metal Maximum Adsorption rate, b R2

Adsorption (l/mg)
capacity, Q0 =Qmax
(mg/g)
K 2.268 1.980 0.9540
Li 1.653 0.006 0.9567
Na 12.790 13.450 0.9693
Ca 6.040 2.785 0.9909
Table 4-14 Langmuir isotherm data
16
Maximum Adsorption capacity, Q0
14
12
=Qmax (mg/g)
10
0
K Li Metal ion Na Ca
Graph 4-19 Estimated isotherm parameters for adsorption of metal ions onto soil
and charcoal
60
14
12
Adsorption rate, b (l/mg)

10
0
K Li Na Ca
Metal ion
Graph 4-20 Estimated isotherm parameters for adsorption rate of metal ions onto
soil and charcoal
4.5 Adsorbent chemical properties through XRF
Analysis of adsorbent chemical properties using X-ray Fluorescence in Institute of

seismological research at Gandhinagar.
XRF (X-ray fluorescence) is a non-destructive analytical technique used to determine

the elemental composition of materials. XRF analysers determine the chemistry of a
sample by measuring the fluorescent (or secondary) X-ray emitted from a sample
when it is excited by a primary X-ray source. Each of the elements present in a sample
produces a set of characteristic fluorescent X-rays ("a fingerprint") that is unique for
that specific element.
X-ray Fluorescence spectrometry is an elemental technique with broad application in

science and industry.XRF is based on the principle that individual atoms, when
excited by an external energy source, emit x-ray photons of a characteristic energy or
wavelength. That is widely used for elemental analysis and chemical analysis,
particularly in the investigation of metals, glass, ceramics and building materials, and
for research in geochemistry etc.
61
Elements Soil Activated Soil and Soil and
charcoal Activated Activated
charcoal in charcoal in
size 250 µm, size less than
after passing 250 µm, after
produced passing
water produced
water
Calcium 8.04% 3.33% 6.63% 3.96%
Silicon 2.37% 3.14% 22.15% 6.59%
Sodium 2.22% 9.02% 12.64% 6.59%
Aluminium 1.03% 1.96% 6.89% 3.74%
Potassium 0.97% 1.05% 1.26% 1.03%
Magnesium 0.95% 0.78% 1.92% 1.05%
Iron 0.19% 0.72% 2.59% 2.51%
Phosphorus 0.12% 0.53% 0.21% 0.23%
Strontium 299.1ppm 212.3ppm 303.6ppm 327ppm
Manganese 111.5ppm 209.4ppm 358.2ppm 339.5ppm
Zinc 30.2ppm 23.3ppm 72.5ppm 66.3ppm
Vanadium 15.8ppm 54ppm 69.1ppm 59.9ppm
Barium 12.8ppm 23.9ppm 601.5ppm 778.5ppm
Rubidium 6.6ppm 5.9ppm 48.6ppm 57.6ppm
Lead 5.5ppm 10ppm 26.3ppm 22.45ppm
Thorium 2.1ppm 1.9ppm 4.1ppm 4.2ppm
Gallium 2.0ppm 4.6ppm 9.9ppm 10.5ppm
Table 4-15 Amount of chemical elements found in soil and charcoal through XRF
analysis
62
2.50%
2.00%
Magnesium concentration
1.50%
1.00%
0.50%
0.00%
Soil Charcoal Soil+Char(>250µm) Soil+Char(<250µm)
Graph 4-21 Difference of magnesium concentration in adsorbent found before and

after passing through produced water
3.00%
2.50%
2.00%
Iron concentration
1.50%
1.00%
0.50%
0.00%
Graph 4-22 Difference of iron concentration in adsorbent found before and after
passing through produced water
63
1.50%
Potassium Concentration
1.00%
0.50%
0.00%
Graph 4-23 Difference of potassium concentration in adsorbent found before and

15.00%
Sodium Concentration
10.00%
5.00%
0.00%
Graph 4-24 Difference of sodium concentration in adsorbent found before and after
64
80.00
60.00
Zinc concetration in PPM
40.00
20.00
0.00
Graph 4-25 Difference of zinc concentration in adsorbent found before and after
75.00
Vanadium concentration in PPM
50.00
25.00
0.00
Graph 4-26 Difference of vanadium concentration in adsorbent found before and

65
1000.00
750.00
Barium concetration in PPM
500.00
250.00
0.00
Graph 4-27 Difference of barium concentration in adsorbent found before and after
75
Radium concetration in PPM
50
25
0
Graph 4-28 Difference of radium concentration in adsorbent found before and after
66
30
25
Lead concentration in PPM
20
15
10
0
Graph 4-29 Difference of lead concentration in adsorbent found before and after
4
Thorium concentration in PPM
0
Graph 4-30 Difference of thorium concentration in adsorbent found before and

67
Year 2013 2014 2015 2016
Produced water 20 22 25 26
per day (m3)
Produced water 7300000 8030000 9125000 9490000
per Year (litre)
Barium (gm) 5683 6251 7103 7387
Rubidium (gm) 420.4 462.5 525.6 546.0
Lead (gm) 163.8 180.2 204.8 213.0
Thorium (gm) 30.66 33.72 38.32 39.85
Manganese (gm) 2478 2726 3097 3221
Strontium (gm) 2387 2625 2983 3103
Table 4-16 Estimated metal present in produced water data
4000
Metal generated in grams
3000
2000
1000
0
2013 2014 2015 2016
Year
Manganege Strontium
Graph 4-31 Year vs Metal generated in produced water
750
Metal generated in grams
500
250
0
2013 2014 2015 2016
Year
Rubidium Lead Thorium
Graph 4-32 Year vs Metal generated in produced water
68
CHAPTER 5 DISCUSSIONS, CONCLUSIONS AND
RECOMMENDATIONS
5.1 DISCUSSION
Produced water is water trapped in underground formations that is brought to the

surface along with oil or gas. Produced water can be in contact with the hydrocarbon-
bearing formation for centuries and because of this reason, produced water contains
some of the chemical characteristics of the formation and the hydrocarbon itself. It
may include water from the reservoir, water injected into the formation to maintain
the reservoir pressure and any chemicals added during the production and treatment
processes. However the major constituents of concern in produced water are:
1. Salt content (salinity, total dissolved solids TDS, electrical conductivity)
2. Oil and grease (this is a measure of the organic chemical compounds)
3. Various natural inorganic and organic compounds or chemical additives used in

drilling and operating the well
4. Naturally occurring radioactive material (NORM)
This shows that produced water is not a single commodity and could contain a variety
of the following constituents mention above in various proportions. Also, the physical
and chemical properties of produced water vary considerably depending on the
geographic location of the field, the geological host formation and the type of
hydrocarbon product being produced. Produced water properties and volume can even
vary throughout the lifetime of a reservoir and hence a concern area in the oil and gas
industries to be fully understood to enhance higher oil recovery.
Produced water is by far the largest volume by product or waste stream associated
with oil and gas exploration and production. Today produced water is the largest
volume waste stream in oil and gas production with an estimated 240 million bbl/day
requiring treatment and disposal.
Approximately 21 billion bbl (barrels; 1 bbl = 42 U.S. gallons) of produced water are
generated each year in the United States from nearly a million wells representing
about 57 million bbl/day, 2.4 billion gallons/day, or 913 000 m3/day.
69
More than 50 billion bbl of produced water are generated each year at thousands of
wells in other countries. The oil production is high while water production is at a
lower rate in the early life of an oil well and over time, oil production decreases while
the water production goes up. One other way of considering this is to examine the
ratio of water-to-oil. For instance, worldwide estimate – 2:1 to 3:1 and U.S. estimate
– 5.1 to 8:1 because many U.S. fields are mature and past their peak production,
although the ratio may be even higher (such as > 50:1). (Clark et al, 2009)
As wells mature oil and gas volumes in the production stream are gradually replaced
by ever increasing volumes of water and sand. At some point the cost of managing
the produced water exceeds the profit from selling the oil and the well is shut down
when this point is reached. However, in contrast to this phenomenon, coal bed
methane well initially produces a large volume of water, which declines over time.
The methane production starts low, builds to a peak, and then decreases. In any of
these cases managing these waste streams efficiently and compliantly represents
major separation, treatment and disposal challenges for operators around the world,
especially those working offshore and in other environmentally sensitive regions.
Sand and water production can also damage vital production equipment through
corrosion, erosion and blockages. All of these processes, if left unaddressed could
create flow assurance, health and safety or environmental problems. As production
progresses, conditions change making the demands of each well different and the
requirements of every solution unique.
Produced water management typically differs between onshore and offshore facilities.
This is partly due to the space and weight restrictions at most offshore sites. Also the
primary contaminant of concern is typically different between onshore discharges
(salt content) and offshore discharges (oil and grease level).
Onshore produced water faces different options depending on where in the country
the well is located and whether the water comes from an oil or gas well or from coal
bed natural gas (CBNG – also known as coal bed methane or CBM) production. The
management technologies and practices used by various companies in managing
water can be grouped into three major categories: water minimization, recycle/reuse,
and treatment/disposal. However, the categories overlap somewhat, for example many
of the reuse opportunities require that the produced water is treated before it can be
70
used for another purpose. These issues of produced water and its problems associated
with the management process calls for more attention into a detail studies and research
of the impact of produced water. There are various technologies implored by many
companies in the management and handling of produced water.
However, this research work was aimed at considering adsorption as one of the
technologies used in the oil and gas industries for treating produced water.
5.2 CONCLUSION AND RECOMMENDATION
In this work, a thorough literature review was completed which highlighted the
importance of treating produced water, and some of the common techniques followed
in the process of treatment. Below are the important conclusions regarding the
treatment of produced water using adsorption technique with mixture of activated
charcoal and soil as adsorbent.
Flame photometer and AAS is the optimum analytical tool to quantify produced water.
Continuous column adsorption experiments for the adsorption of produced water were
studied by the use of adsorbent as mixture of activated charcoal and soil. Results
collected present the following: Optimum adsorbent dosage = 100mg/l, optimum
contact time = 180 minutes, and optimum temperature = 28.0.
Increasing the initial concentration of produced water decreases the removal

efficiency of produced water.
The experimental data obtained in this study best fits the Langmuir isotherm model,
The thermodynamics study conducted demonstrated that the adsorption process of

emulsified oil onto activated carbon and soils is rather physic sorption, and that higher
temperatures will decrease the removal efficiency of emulsified oil.
Activated carbon and soil was able to treat a real sample of industrial produced water
with an initial concentration of emulsified oil very high, and reduce it to some amount,
which is equivalent to 60 % removal efficiency of oil.
71
Maximum adsorption capacity of activated carbon and soil was found to be 100mg/l
was evaluated using the Langmuir isotherm model.
In this study, activated carbon and soil as an adsorbent is capable of treating produced
water efficiently and because it is economical to be employed in large scale
applications, it can be an alternative to other adsorbents that treat emulsified oil in
produced water.
In way to forward to increase adsorption capacity and removal rate of emulsified oil
from produced water using different adsorbent or add some chemicals or mixture of
good adsorbent which will help to increase the adsorption rate for produced water
.And also using as per suitable different adsorption isotherms which will helpful for
this study.
72
REFERENCES
REFERENCES
1) Argonne National Laboratory et al, A white paper Describing Produced Water from
Production of Crude Oil, Natural Gas and Coal Bed Methane, Prepared for: U.S.
Department of Energy National Energy Technology laboratory Under Contract W-
31-109-Eng-38. January 2004.
2) Oliveira EP, Santelli RE, Cassella RJ. Direct determination of lead in produced
waters from petroleum exploration by electro thermal atomic absorption spectrometry
X-ray fluorescence using Ir-W permanent modifier combined with hydrofluoric
acid, Anal Chim Acta , 2005, vol. 545 (pg. 85-91)
3) Energy Information Administration International energy outlook 2009, 2009US

Department of Energy DOE/EIA-0484(2009) www.eia.doe.gov/oiaf/ieo/index.html
4) Azetsu-Scott K, Yeats P, Wohlgeschaffen G, et al. . Precipitation of heavy metals

in produced water: influence on contaminant transport and toxicity, Mar Environ
Res, 2007, vol. 63 (pg. 14667)
5) Kaur G, Mandal AK, Nihlani MC, et al. . Control of sulfidogenic bacteria in

produced water from the Kathloni oilfield in northeast India, Int Biodeterior
Biodegrad, 2009, vol. 63 (pg. 151-5)
6) Fakhru'l-Razi A, Pendashteh A, Abdullah LC, et al. . Review of technologies for

oil and gas produced water treatment, J Hazard Mater, 2009, vol. 170 (pg. 530-51)
7) Miller GE (2006) Integrated concepts in water reuse: Managing global water needs:
Desalination 187:65-75
8) F. R. Rijsberman, "Water scarcity: Fact or fiction?" Agricultural Water

Management, vol. 80, pp. 5-22, 2006
9) Nicholas Owens, G.S.L. and G.S.L. Douglas W. Lee, The Use of Micro Bubble
Flotation Technology in Secondary &Tertiary Produced Water Treatment - A
Technical Comparison With Other Separation Technologies. 30th – 31st May 2007.
10) Nature Technology Group, Introduction to Produced Water

Treatment, 2005Nature Technology Solutions (pg. 2-18) Retrieved 13 March 2010.
73
REFERENCES
11) Cline JT. Treatment and discharge of produced water for deep offshore
disposal, 1998API Produced Water Management Technical Forum and
Exhibition Lafayette, LA
12) Daniel Arthur J, Langhus BG, Patel C, Technical Summary of Oil & Gas Produced
Water Treatment Technologies, 2005NET
13) Removing hydrocarbon from water "Petrowiki.org. Available:

http://petrowiki.org/Removing_ hydrocarbon_ from water.
14) "API Gravity," Petroleum.co.uk. Available: http://www.petroleum.co.uk/api.
15 ) Technology Subgroup of the Operations & Environment Task Group,

"Management of Produced water from oil and gas wells," National Petroleum
Council, Washington, DC, September 2011.
16) Colorado School of Mines Technical Assessment of produced water treatment

technologies, 2009(pg. 8-128) An Integrated Framework for Treatment and
Management of Produced Water. RPSEA Project 07122-12, Colorado
17) Clifford DA. Letterman RD. Ion exchange and inorganic adsorption, Water
Quality and Treatment, 1999McGraw-Hill
18) Nadav N. Boron removal from seawater reverse osmosis permeate utilizing
selective ion exchange resin, Desalination , 1999, vol. 124 (pg. 131-5)
19) Xu P, Drewes JE. Viability of nano filtration and ultra-low pressure reverse
osmosis membranes for multi-beneficial use of methane produced water, Sep Purif
Technol, 2006, vol. 52 (pg. 67-76)
20) Madaeni SS. The application of membrane technology for water

disinfection, Water Res, 1999, vol. 33 (pg. 301-8)
21) Judd S, Jefferson B, Membranes for Industrial Wastewater Recovery and Re-use
Oxford, 2003Elsevier Ltd (pg. 14-169)
22) Han R, Zhang S, Xing D, et al. Desalination of dye utilizing copoly (phthalazinone
biphenyl ether sulfone) ultrafiltration membrane with low molecular weight cut-off J
Membr Sci , 2010, vol. 358 (pg. 1-6)
74
REFERENCES
23) He Y, Jiang ZW. Technology review: treating oilfield wastewater, Filtr

Sep, 2008, vol. 45 (pg. 14-6)
24) Bilstad T, Espedal E. Membrane separation of produced water, Water Sci

Technol, 1996, vol. 34 (pg. 239-46)
25) Spiegler KS, Kedem O. Thermodynamics of hyper filtration (reverse osmosis):

criteria for efficient membranes, Desalination, 1966, vol. 1 (pg. 311-26)
26) Mark W, The Guidebook to Membrane Desalination Technology: Reverse

Osmosis, Nano filtration and Hybrid Systems Process, Design, Applications and
Economic, 20071st ednL'Aquila Desalination Publications (pg. 160-80)
27) Doran G, Leong LYC. Developing a cost effective solution for produced water
and creating a ‘new’ water resource, 2000United Sates Department of
Energy DOE/MT/95008-4
28) Nicolaisen B, Lien L. Treating oil and gas produced water using membrane
filtration technology, 2003Produced Water Workshop Aberdeen, Scotland
29) Mondal S, Wickramasinghe SR. Produced water treatment by nano filtration and
reverse osmosis membranes, J Membr Sci , 2008, vol. 322 (pg. 162-70)
30) Barratt PA, Xiong F, Baumgartl A, et al. . Eckenfelder WW, Bowers AR, Roth
JA. , Chemical Oxidation: Technologies for the Nineties, 1997, vol. Vol. 6 Technomic
Publishing Co. Inc (pg. 112)
31) T. C. Frankiewicz and J. Gerlach, "Removal of hydrocarbons, mercury and arsenic

from oil-field produced water," US Patent 08,841,481, September 12, 2000.
32) AWWA, Water Treatment Plant Design, 19983rd ednMcGraw-Hill (pg. 221-80)
33) EPA, Onsite Wastewater Treatment and Disposal Systems Design

Manual, 1980US EPA
34) Su D, Wang J, Liu K, et al. . Kinetic performance of oil-field produced water

treatment by biological aerated filter, Chin J Chem Eng, 2007, vol. 15 (pg. 591-4)
35) Ball HL. Nitrogen reduction in an on-site trickling filter/up flow filters wastewater
treatment system, 1994Proceedings of the 7th International Symposium on Individual
75
REFERENCES
and Small Community Sewage Systems Atlanta, GA American Society of

Agricultural Engineers
36) A. Fujishima and K. Honda, "Electrochemical Photolysis of Water at a

Semiconductor Electrode", Nature, vol. 238, no. 5358, pp. 37-38, 1972.
37)"Produced Water R&D | Department of Energy," Energy.gov. Available:

http://energy.gov/fe/science-innovation/oil-gas/shale-gas-rd/produced-waterrd.
38) Interstate Oil and Gas Compact Comission, ALL Consulting (Firm), United States
Department of Energy, United States National Petroleum Technology Office,
Montana Board of Oil and Gas Conservation et al., "A Guide to Practical
Management of Produced Water from Onshore Oil and Gas operations in the United
States," Interstate Oil & Gas Compact Commission, Oklahoma, 2006.
39) Khattri SD, Singh MK (2009) Removal of malachite green from dye wastewater
using neem sawdust by adsorption. J Hazard Mater 167:1089–1094
40) El-Sheikh AH, Newman AP, Al-Daffaee H, Phull S, Cresswell N, York S (2004)
Deposition of anatase on the surface of activated carbon. Sur Coat Technol 187:284–
292
41) Naeem A, Westerhoff P, Mustafa S (2007) Vanadium removal by metal (hydr)

oxide adsorbents. Water Res 41:1596–1602
42) Weber WJJr (1972) Physicochemical processes for water quality control. Wiley,
New York
43) Yoon Y, Westerhoff P, Snyder SA (2005) Adsorption of 3H-labeled 17-bestradiol

on powdered activated carbon. Water Air Soil Pollut 166:343–351
44) K. Okiel, M. El-Sayed, and M. Y. El-Kady, "Treatment of oil–water emulsions

by adsorption onto activated carbon, bentonite and deposited carbon," Egyptian
Journal of Petroleum, vol. 20, pp. 9-15, 2011.
45) P. V. Nidheesh, R. Gandhimathi, S. T. Ramesh, T. S. Anantha Singh "Modelling

of Crystal Violet Adsorption by Bottom Ash Column" in 2013 Water Environment
Research, Volume 85, Number 6
76
REFERENCES
46) Puthiya Veetil NIDHEESH, Rajan GANDHIMATHI∗, Sreekrishnaperumal

Thanga RAMESH, Tangappan Sarasvathy ANANTHA SINGH "Kinetic analysis of
crystal violet adsorption on to bottom ash" in 2012
47) I. M. Muhammad, U. A. El-Nafaty, S. Abdul Salam, and Y. I. Makarfi, "Removal

of Oil from Oil Produced Water Using Eggshell," Civil and Environmental Research,
vol. 2, no. 8, 2012.
48) U. A. El-Nafaty, M. I.M, and S. Abdul Salam, "Bio sorption and Kinetic Studies
on Oil Removal from Produced Water Using Banana Peel," Civil and Environmental
Research, vol. 3, 2013.
49) Clark, C.E., and J.A. Veil, 2009, Produced Water Volumes and Management
Practice in the United States prepared by the Environmental Science Division,
Argonne National Laboratory for the U.S. Department of Energy, Office of Fossil
Energy, National Energy Technology Laboratory.
50) Simon J. Blott and Kenneth Pye, 2001, “A Grain Size distribution and statistics
package for the analysis of unconsolidated Sediments” Surface Processes and Modern
Environments Research Group.
51) Mulu Berhe Desta, 2013 “Batch Sorption Experiments: Langmuir and Freundlich
Isotherm Studies for the Adsorption of Textile Metal Ions onto Teff Straw (Eragrostis
tef) Agricultural Waste” Department of Chemistry, College of Natural and
Computational Sciences, Mekelle University, Ethiopia
77
REFERENCES
78

Final 15mpe20 Thesis Hard Binding

Diunggah oleh

Informasi Dokumen

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

Final 15mpe20 Thesis Hard Binding

Diunggah oleh

Hak Cipta:

Format Tersedia

“TREATMENT OF OIL WELL PRODUCED WATER BY

CONTINUOUS COLUMN ADSORPTION USING LOW COST

SCHOOL OF PETROLEUM TECHNOLOGY,

adsorption using low cost and synthesized adsorbent” by Apurv patel is

Date: 25th May, 2017

Roll No. 15MPE20

M.Tech Student, Petroleum Engineering

Date: 25th May, 2017

Apurv J Patel (M.Tech)

SPT, PDPU, Gandhinagar

I would like to express my special thanks of gratitude to Dr. Madhavan P

Adsorption is a well-known method for high efficiency in treatment of water and

CHAPTER TITLE PAGE NO

LIST OF TABLES ...................................................................................................vii

LIST OF FIGURES ............................................................................................... viii

LIST OF GRAPHS ................................................................................................... ix

CHAPTER 1 INTRODUCTION TO PRODUCED WATER ............................. 1

1.1 INTRODUCTION TO PRODUCED WATER ............................................. 1

1.1.1 The Origin of Produced Water ....................................................... 3

1.1.2 Overview of Produced Water Characteristics ................................ 4

1.2 Conventional Oil and Gas Production PW Constituents .......................... 5

1.2.1 Dispersed Oil .................................................................................. 5

1.2.2 Treatment Chemicals ...................................................................... 6

1.2.3 Produced Solids .............................................................................. 6

1.2.4 Dissolved Organic Components ..................................................... 6

1.2.5 Scales .............................................................................................. 8

1.2.7 Metals ............................................................................................. 8

1.2.9 Sulphates ........................................................................................ 9

1.2.10 Naturally Occurring Radioactive Material (NORM)...................... 9

1.3 Environmental Impact and Legislation ..................................................... 9

CHAPTER 2 LITERATURE SURVEY .............................................................. 11

2.1 Types of produced water treatment .............................................................. 11

2.1.1 Dispersed oil and grease ................................................................... 11

2.1.2 Physical Treatments: ........................................................................ 16

2.1.3 Chemical Treatment: ........................................................................ 20

2.1.4 Biological Treatment: ....................................................................... 21

2.2 Management of produced water:.................................................................. 22

2.3 Adsorption .................................................................................................... 23

CHAPTER 3 MATERIALS AND METHODS .................................................. 28

3.1 List of Instruments: ...................................................................................... 28

3.2 Experimental Procedure ............................................................................... 29

3.3 Characterization of Produced Water ............................................................ 30

3.3.1 Flame Photometer ............................................................................. 30

3.3.2 AAS/Atomic Absorption Spectroscopy ........................................... 32

3.3.3 Gravimetric ....................................................................................... 33

3.4.1 Soil and Charcoal Analysis............................................................... 36

3.4.2 Procedure for making activated charcoal ......................................... 37

3.4.3 Analysis of adsorbent ....................................................................... 37

3.5 Adsorption Batch Study .............................................................................. 38

3.6 Column study ............................................................................................... 39

CHAPTER 4 RESULT ANALYSIS.................................................................... 41

4.1 Produced water parameter ............................................................................ 41

4.2 Adsorbent Analysis ........................................................................................ 42

4.3 Effects of various factor depends on adsorption process ............................... 44

4.3.1 Effect of contact time on soil and charcoal mix ................................. 44

4.3.2 Effect of adsorbent dosage ............................................................... 51

4.4 Langmuir adsorption isotherms ................................................................... 55

4.5 Adsorbent chemical properties through XRF .............................................. 61

CHAPTER 5 DISCUSSIONS, CONCLUSIONS AND

5.1 DISCUSSION .............................................................................................. 69

5.2 CONCLUSION AND RECOMMENDATION ........................................... 71

Table 2-1 Types of water treatment method ............................................................16

Figure 1.1 A Typical oilfield reservoir ......................................................................3

Graph 4-1 Physical properties of soil at Limbodra ..................................................43