B.tech final report (1)

[1]
TECHNIQUES OF TREATMENT OF OIL
FIELD PRODUCED WATER
Project Report
Submitted in requirements of
B. Tech. degree in Petroleum Engineering
By
Kunj Parmar (14BPE073)
Darshil Patel (14BPE081)
Ravi Patel (14BPE091)
Shubham Satani (14BPE106)
Kushal Shah (14BPE108)
Madhuram Sharma (14BPE110)
Under the Guidance of
Dr. Madhavan P Natarajan
SCHOOL OF PETROLEUM TECHNOLOGY
PANDIT DEENDAYAL PETROLEUM UNIVERSIY
GANDHINAGAR
May-2018

TECHNIQUES OF TREATMENT
OF OIL FIELD PRODUCED WATER
Project Report
Submitted in requirements of
B. Tech. degree in Petroleum Engineering
By
Under the Guidance of
Dr. Madhavan P Natarajan
SCHOOL OF PETROLEUM TECHNOLOGY
PANDIT DEENDAYAL PETROLEUM UNIVERSIY
GANDHINAGAR
May-2018

Approval Sheet
This report entitled “TECHNIQUES OF TREATMENT OF OIL FIELD
PRODUCED WATER” is recommended for the degree of Bachelor of Technology
in Petroleum Engineering submitted by following students:
Examiners
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Supervisors
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Chairman
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Date: _______________
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Student Declaration
We hereby declare that this written submission represents our ideas in our own
words and where others’ idea or words have been included, we have adequately
cited and referenced the original sources. We also declare that we have adhered to
all principles of academic honestly and integrity and have not misrepresented or
fabricated or falsified any idea / data / fact / source in our submission. We
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
whom proper permission has not been taken when needed.
NAME ROLL NUMBER SIGNATURE
KUNJ PARMAR 14BPE073
DARSHIL PATEL 14BPE081
RAVI PATEL 14BPE091
SHUBHAM SATANI 14BPE106
KUSHAL SHAH 14BPE108
MADHURAM SHARMA 14BPE110
Date: ________________
Place: ________________

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Acknowledgement
We express our sincere gratitude to School of Petroleum Technology (SPT), Pandit
Deendayal Petroleum University (PDPU) for facilitating the instrumentation of the
project undertaken by us. Our special thanks to our project guide Dr. N. Madhvan,
industrial mentor Dr. Anantha Singh and project co-guides Dr. Bhavanisingh
Desai for guiding and facilitating us technically in every aspect of the project and
also in solving every qualm in regards to the project.
We are also obliged to officials of Gujarat Energy and Management Institute
(GERMI) for assisting us in technical procedures and providing us the required
technical instruments and materials. We are greatly thankful to Ms. Sushila Rathod,
lab technician of Drilling Fluids and Cementation lab (DFC) for associating himself
in our project Last but not the least, we are thankful to all team members for
participating and associating themselves for performing and sharing the
responsibilities on their parts individually and collectively for successful completion
of the project.

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Abstract
Produced water is water that is returned to the surface through an oil or gas well. It
is made up of natural formation water as well as the up hole return of water injected
into the formation (flow back water) that was sent down hole as part of a fracture
stimulation (frac) process or an enhanced recovery operation. Produced water is
typically generated for the lifespan of a well.
Another important water category is known as flow backwater. It is water that was a
large component of fluids injected into a well at high pressure as part of a hydraulic
fracturing (frac) operation. Within a few hours to a few weeks after the frac job is
completed, a portion of the water returns to the surface. It typically contains much
higher levels of chemical constituents, including dissolved salts, than did the
original frac fluid.
Although produced water varies significantly among wells and fields, several groups
of constituents are present in most types of produced water. The major constituents
of concern in produced water are:
 Salt content (expressed as salinity, total dissolved solids, or electrical
conductivity).
• Oil and grease (identified by an analytical test that measures the presence of
families of organic chemical compounds).
• Various natural inorganic and organic compounds (e.g., chemicals that cause
hardness and scaling such as calcium, magnesium, sulfates, and barium).
• Chemical additives used in drilling, fracturing, and operating the well that may
have some toxic properties (e.g., biocides, corrosion inhibitors) – typically at very
concentrations.
• Naturally occurring radioactive material (NORM). Technologies and strategies
applied to produce water comprise a three-tiered water hierarchy: (1) Minimization;
(2) Recycle / Re-use; and (3) Disposal. Techniques to minimize produced water
volumes are tailored as is feasible for individual locations but disposal must
ultimately be addressed. Most onshore produced water is re-injected to underground
formations, either to provide additional oil and gas recovery or for disposal, under

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permits issued by State Pollution Control Board. Most offshore produced water is
disposed as discharge to the ocean following treatment according to requirements of
the State Pollution Control Board Techniques to minimize produced-water volumes
are tailored as is feasible for individual locations. Recycling or re-use of produced
water is an ongoing area of focused research and development that has equipped the
oil and gas industries with numerous technological solutions which can be tailored
for individual applications.

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Table of Contents
Acknowledgement ........................................................................................................i
Abstract....................................................................................................................... ii
Table of Contents........................................................................................................iv
List of Figure: .............................................................................................................vi
List of Table:............................................................................................................. vii
CHAPTER 1: INTRODUCTION TO PROUCED WATER.......................................1
1.1 Origin of produced water.............................................................................................. 3
1.2 Overview of Produced Water Characteristics............................................................... 4
1.3 Produced Water from Oil Production ........................................................................... 4
1.4 Produced Water from Gas Production.......................................................................... 5
1.5 Conventional Oil and Gas Production PW Constituents ............................................... 5
1.5.1 Dispersed Oil .......................................................................................................... 6
1.5.1.1 Treatment Chemicals ...................................................................................... 6
1.5.1.2 Produced Solids............................................................................................... 6
1.5.2 Dissolved Organic Components ............................................................................. 7
1.5.2.1 Scales............................................................................................................... 8
1.5.2.2 Bacteria ........................................................................................................... 8
1.5.2.3 Metals.............................................................................................................. 9
1.5.2.4 Sulphates......................................................................................................... 9
1.5.3 Naturally Occurring material (NORM).................................................................... 9
1.6 Environmental Impact and Legislation........................................................................ 10
CHAPTER 2: LITERATURE SURVEY ..................................................................11
2.1 List of literature survey ............................................................................................... 11
2.2 Produced water management .................................................................................... 18
2.3 Adsorption................................................................................................................... 19
2.3.1 Factors Affecting Adsorption ............................................................................... 20
2.3.2 Adsorbents ........................................................................................................... 21
2.4 Industrial Treatments for Produced Water................................................................. 22
CHAPTER 3: RESRARCH METHODOLOGY.......................................................23
3.1 Water Sampling Method and Analysis........................................................................ 23
3.1.1 Location of water sampling................................................................................ 23
3.2 Adsorption process for produced water..................................................................... 24
3.3 Material and methods................................................................................................. 26
3.3.1 List of Instruments: .............................................................................................. 26

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3.3.2 List of Glassware: ................................................................................................. 27
3.3.3 Tests ..................................................................................................................... 27
3.3.3.1 PH meter ....................................................................................................... 27
3.3.3.2 Salinity........................................................................................................... 29
3.3.3.3 Flame Photometer: ....................................................................................... 31
3.3.3.4 Conductivity .................................................................................................. 33
CHAPTER 4: RESULTS AND ANALYSIS ............................................................35
4.1 PRODUCED WATER PARAMETERS .............................................................................. 35
4.2 EFFECT OF VARIOUS FACTORS DEPENDS ON ADSORPTION PROCESS:....................... 36
4.2.1 EFFECT OF TOTAL SURFACE AREA ON ADSORPTION: .......................................... 36
4.2.1.1 Gray Shale: .................................................................................................... 36
4.2.1.2 White Clay:.................................................................................................... 41
4.2.1.3 Laterite Rock ................................................................................................. 45
4.2.2 EFFECT OF CONTACT TIME ON ADSORPTION ...................................................... 49
4.2.2.1 Gray shale...................................................................................................... 49
4.2.2.2 White clay...................................................................................................... 53
4.2.2.3 Late rite ......................................................................................................... 57
4.2.3 Effect of adsorbent dosage .................................................................................. 61
4.2.3.1 Langmuir adsorption isotherms.................................................................... 61
4.2.3.2 Gray Shale ..................................................................................................... 62
4.2.3.3 White clay...................................................................................................... 66
4.2.3.4 Literate.......................................................................................................... 70
4.3 PH results and analysis................................................................................................ 74
CHAPTER 5: DISCUSSION AND CONCLUSION................................................76
5.1 DISCUSSION................................................................................................................. 76
5.2 CONCLUSION............................................................................................................... 78
CHAPTER 6: RECOMMEDATION ........................................................................80
REFERENCES ..........................................................................................................81

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List of Figure:
Figure 1: Graph of Produced Water Volume v/s Operating time for typical oil field ........................... 3
Figure 3- 1: Sample of Produced Water...............................................................................................23
Figure 3- 2: Experiment setup Figure 3- 3: Rock sample of different size .....................................26
Figure 3- 4: Sieve Analysis..................................................................................................................26
Figure 3- 5: PH meter..........................................................................................................................29
Figure 3- 6: Salinity meter ...................................................................................................................31
Figure 3- 7: Flame Photometer ...........................................................................................................33
Figure 3- 8: Conductivity meter used for the experiment ....................................................................34
Figure 4- 1: Effect of grain size of gray shale on adsorption of Lithium from produced water...........37
Figure 4- 2: Effect of grain size of gray shale on adsorption of Sodium from produced water ...........38
Figure 4- 3: Effect of grain size of gray shale on adsorption of Calcium from produced water ..........39
Figure 4- 4: Effect of grain size of gray shale on adsorption of Potassium from produced water .......40
Figure 4- 5: Effect of grain size of White clay on adsorption of Lithium from produced water..........41
Figure 4- 6: Effect of grain size of White clay on adsorption of Sodium from produced water ..........42
Figure 4- 7: Effect of grain size of White clay on adsorption of Calcium from produced water .........43
Figure 4- 8: Effect of grain size of White clay on adsorption of Potassium from produced water ......44
Figure 4- 9: Effect of grain size of laterite on adsorption of Lithium from produced water ................45
Figure 4- 10: Effect of grain size of laterite on adsorption of Sodium from produced water ..............46
Figure 4- 11: Effect of grain size of laterite on adsorption of Calcium from produced water .............47
Figure 4- 12: Effect of grain size of laterite on adsorption of Lithium from produced water ..............48
Figure 4- 13: Concentration Lithium v/s contact time for gray shale ..................................................49
Figure 4- 14: Concentration Sodium v/s contact time for gray shale...................................................50
Figure 4- 15: Concentration Sodium v/s contact time for gray shale...................................................51
Figure 4- 16: Concentration Potassium v/s contact time for gray shale ...............................................52
Figure 4- 17: Concentration Lithium v/s contact time for white clay ..................................................53
Figure 4- 18: Concentration Sodium v/s contact time for white clay...................................................54
Figure 4- 19: Concentration Calcium v/s contact time for white clay..................................................55
Figure 4- 20: Concentration Potassium v/s contact time for white clay...............................................56
Figure 4- 21: Concentration Lithium v/s contact time for laterite........................................................57
Figure 4- 22: Concentration Sodium v/s contact time for laterite ........................................................58
Figure 4- 23: Concentration Calcium v/s contact time for laterite.......................................................59
Figure 4- 24: Concentration Potassium v/s contact time for laterite ....................................................60
Figure 4- 25: Equilibrium concentration of Li v/s Specific adsorption for gray shale .........................62
Figure 4- 26: Equilibrium concentration of Na v/s Specific adsorption for gray shale........................63
Figure 4- 27: Equilibrium concentration of Ca v/s Specific adsorption for gray shale ........................64
Figure 4- 28: Equilibrium concentration of K v/s Specific adsorption for gray shale..........................65
Figure 4- 29: Equilibrium concentration of Li v/s Specific adsorption for white clay.........................66
Figure 4- 30: Equilibrium concentration of Na v/s Specific adsorption for white clay........................67
Figure 4- 31: Equilibrium concentration of Ca v/s Specific adsorption for white clay........................68
Figure 4- 32: Equilibrium concentration of K v/s Specific adsorption for white clay .........................69
Figure 4- 33: Equilibrium concentration of Li v/s Specific adsorption for Laterite.............................70
Figure 4- 34: Equilibrium concentration of Na v/s Specific adsorption for Laterite............................71
Figure 4- 35: Equilibrium concentration of Ca v/s Specific adsorption for Laterite............................72
Figure 4- 36: Equilibrium concentration of K v/s Specific adsorption for Laterite .............................73

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List of Table:
Table 4- 1: Physical parameter of produced water...............................................................................35
Table 4- 2: Ions measured in produced water ......................................................................................35
Table 4- 3: Lithium concentration analysis for treated produced water for different grain size of grey
shale .....................................................................................................................................................37
Table 4- 4: Sodium concentration analysis for treated produced water for different grain size of grey
shale .....................................................................................................................................................38
Table 4- 5: Calcium concentration analysis for treated produced water for different grain size of grey
shale .....................................................................................................................................................39
Table 4- 6: Potassium concentration analysis for treated produced water for different grain size of
grey shale .............................................................................................................................................40
Table 4- 7: Lithium concentration analysis for treated produced water for different grain size of
White clay............................................................................................................................................41
Table 4- 8: Sodium concentration analysis for treated produced water for different grain size of White
clay.......................................................................................................................................................42
Table 4- 9: Calcium concentration analysis for treated produced water for different grain size of
White clay............................................................................................................................................43
White clay............................................................................................................................................44
Table 4- 11: Lithium concentration analysis for treated produced water for different grain size of
laterite ..................................................................................................................................................45
Table 4- 12: Sodium concentration analysis for treated produced water for different grain size of
laterite ..................................................................................................................................................46
Table 4- 13: Calcium concentration analysis for treated produced water for different grain size of
laterite ..................................................................................................................................................47
laterite ..................................................................................................................................................48
Table 4- 15: Effect of contact time on adsorption of Lithium from produced water for gray shale ....49
Table 4- 16: effect of contact time on adsorption of Sodium from produced water for gray shale......50
Table 4- 17: Effect of contact time on adsorption of Calcium from produced water for gray shale ....51
Table 4- 18: Effect of contact time on adsorption of Potassium from produced water for gray shale .52
Table 4- 19: Effect of contact time on adsorption of Lithium from produced water for white clay ....53
Table 4- 20: Effect of contact time on adsorption of Sodium from produced water for white clay.....54
Table 4- 21: effect of contact time on adsorption of Calcium from produced water for white clay ....55
Table 4- 22: Effect of contact time on adsorption of Potassium from produced water for white clay.56
Table 4- 23: Effect of contact time on adsorption of Lithium from produced water for laterite..........57
Table 4- 24: effect of contact time on adsorption of Sodium from produced water for laterite ...........58
Table 4- 25: Effect of contact time on adsorption of Calcium from produced water for laterite .........59
Table 4- 26: effect of contact time on adsorption of Potassium from produced water for laterite .......60
Table 4- 27: Effect of adsorbent dosage on adsorption of Li from produced water for gray shale ......62
Table 4- 28: Effect of adsorbent dosage on adsorption of Na from produced water for gray shale.....63
Table 4- 29: Effect of adsorbent dosage on adsorption of Ca from produced water for gray shale .....64
Table 4- 30: Effect of adsorbent dosage on adsorption of K from produced water for gray shale.......65
Table 4- 31: Effect of adsorbent dosage on adsorption of Li from produced water for white clay......66
Table 4- 32: Effect of adsorbent dosage on adsorption of Na from produced water for white clay.....67
Table 4- 33: Effect of adsorbent dosage on adsorption of Ca from produced water for white clay.....68
Table 4- 34: Effect of adsorbent dosage on adsorption of K from produced water for white clay ......69
Table 4- 35: Effect of adsorbent dosage on adsorption of Li from produced water for Laterite..........70
Table 4- 36: Effect of adsorbent dosage on adsorption of Na from produced water for Laterite.........71
Table 4- 37: Effect of adsorbent dosage on adsorption of Ca from produced water for Laterite .........72
Table 4- 38: Effect of adsorbent dosage on adsorption of K from produced water for Laterite ..........73
Table 4- 39: pH analysis ......................................................................................................................74

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CHAPTER 1: INTRODUCTION TO PROUCED WATER
In subterraneous formation, sedimentary rocks are usually penetrated with
fluid as water, oil, or gas (or some mixture of those fluids). Thus, reservoir rocks
unremarkably contain each oil hydrocarbons (liquid and gas) and water. Sources of
this water could embody ensue on top of or below the organic compound zone,
ensue at intervals the organic compound zone, or ensue injected fluids and additives
ensuing from production activities. This water is usually brought up as "connate
water" or formation water" and becomes produced water once the reservoir is
produced and therefore the fluids are delivered to the skin.
Petroleum may be a major supply of energy and revenue for several
countries these days, and its production has been delineated mutually of the foremost
vital industrial activities within the ordinal century. Since late decennium once
Edwin Drake drilled the primary well, demand for oil has continued to rise. It's
calculable that world daily oil consumption would increase from eighty five million
barrels in 2006 to 106.6 million barrels by 2030. Despite its significance, oil is
produced with giant volumes of waste, with effluent accounting for over eightieth of
liquid waste and as high as ninety fifth in ageing oil fields.
Communities across the globe face water challenges owing to increasing
demand, drought, depletion and contamination of groundwater, and dependence on
solely sources of provide. Water generated throughout oil and gas extraction
activities, called ‘Produced water'. Even with its numerous sources and provides,
water can become scarce with time owing to poor management of water
infrastructure, increase in human population, modification of climate, and lack of
economic and physical aids to worry for this precious resource. As well, the
scarceness of H2O worldwide is let alone lack of accessibility to the current water:
1.2 billion individuals suffer from this drawback. As per Colorado faculty of Mines
a public analysis university close to more or less twenty one billion British capacity
unit of produced water are generated every year within the US from about 900,000
wells".

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Produced water includes formation water, injection water and method water
that's extracted in conjunction with oil and gas throughout oil production.
Additionally, some of the chemicals value-added throughout process of reservoir
fluids could partition to the produced water. Produced water contains both soluble
and insoluble (oil droplets not removed before physical separation) oil fractions, and
are found at variable concentrations. This oil fraction consists of a posh mixture of
organic compounds almost like those found in crude oils and natural gases.
This is one in all the most waste water produced within the oil and gas
industries, and hence, pollution owing to the discharge of those wastes back to
streams Associate in Nursing lakes while not treatment or while not meeting the
minimum treatment needed can still increase cause an environmental concern. Oil
water contamination is risky to humanity and aquatic life as they're subjected to
impure water and soil. Adverse effects are reported on people's contamination with
oil and organic compounds. It's thus necessary to treat produced water from the oil
and gas corporations so as to shield the native atmosphere further as land creatures.
At most offshore production installations, produced water are separated from
the oil method stream and when treatment are discharged to the marine atmosphere
or disposed of during a subterraneous formation. Treatment of produced water could
also be needed so as to fulfil disposal restrictive limits or to fulfil useful use
specifications (e.g. for recreational functions, water for stock and wild life etc.). If
the oil and gas operator aims to utilize an inexpensive disposal choice like discharge
to surface waters, the produced water should meet or exceed limits set by regulators
for key parameters.
The mensuration of oil in produced water is vital for each method
management and coverage to restrictive authorities. Oil in produced water may be a
method-dependent parameter, some extent that cannot be emphatic enough. Without
the specification of a technique, reported concentrations of oil in produced water
will mean very little, as there are several techniques and ways obtainable for
creating this mensuration, however not all are appropriate during a specific
application.

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1.1 Origin of produced water
Water is incredibly typically found alongside fossil fuel within the reservoir
wherever the water as a consequence of upper density than oil, lays in immense
layers below the hydrocarbons within the porous reservoir media. This water that
occurs naturally within the reservoir is often referred to as formation water. At a
specific time in Associate in producing oil and gas production, the formation water
can reach the assembly wells and water production can begin to initiate. The well
water-cut can ordinarily increase throughout the complete oil and gas field lifespan,
specified once the drilling from the sphere is stop working and therefore the oil
content are often as low as a handful of 98% in serious trouble.
Also so as to take care of the hydraulic pressure within the fossil fuel reservoir that
is reduced as before long as production is initiated, brine is often pumped-up into the
reservoir water layer below the hydrocarbons This method, as the way of pressure
maintenance thanks to water injection, causes high extensions in retrievable
hydrocarbons however at the same time contributes to exaggerated water production.
Figure 1: Graph of Produced Water Volume v/s Operating time for typical oil field

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1.2 Overview of Produced Water Characteristics
Produced water properties and volumes will vary significantly reckoning on
the geographical location of the oil field and therefore the natural object throughout
the life span of a reservoir. However, having a decent understanding of produced
water characteristics will facilitate operators to extend production. For example,
parameters like total dissolved solids (TDS) will facilitate outline pay zone once as
well as resistance measurements. Also, by calculating produced water constituents,
producers will confirm the correct application of scale inhibitors and well treatment
chemicals moreover as establish potential well-bore or reservoir drawback areas.
Knowledge of the constituents of specific produced water is required for
restrictive compliance and for choosing management/disposal choices like
secondary recovery and disposal. Oil and grease are the important constituents of
produced water that has received the foremost attention in each onshore and offshore
operation whereas salt content (expressed as salinity, conduction or TDS) could be a
primary constituent of concern in onshore operations. Additionally, produced water
contains several organic and inorganic compounds that adjust greatly from location
to location and even over time within the same well.
1.3 Produced Water from Oil Production
The organic and inorganic parts of produced water discharged from offshore
wells is in an exceedingly type of physical states as well as resolution, suspension,
emulsion, adsorbed particles and particulates. additionally to its natural parts,
produced water from drilling might also contain groundwater or brine (generally
known as "source" water) injected to keep up the reservoir pressure moreover as
miscellaneous solids and microorganism. Most produced waters contains a lot of
saline than brine and will embody chemical additives utilized in drilling and
production operations within the oil/water separation processes. In produced water,
these chemicals will have an effect on the oil/water partition constant, toxicity,
bioavailability and biodegradability.

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The treatment chemicals are generally complicated mixtures of varied molecular
compounds and will embody the following:
1. Corrosion inhibitors and Oxygen scavengers accustomed cut back instrumentality
corrosion.
2. Scale inhibitors accustomed limit mineral scale deposits, biocides to mitigate
microorganism fouling.
3. Emulsion breakers and clarifiers to interrupt water-in-oil emulsion and reverse
breakers to interrupt oil-in-water emulsion.
4. Coagulants, flocculants and clarifiers to get rid of solids
5. Solvents to reduce paraffin deposits.
1.4 Produced Water from Gas Production
Produced water from gas production have higher contents of low molecular-weight
aromatic hydrocarbons like aromatic hydrocarbon, toluene, ethylbenzene and xylene
(BTEX) than those from oil operations: therefore they're comparatively additional
unhealthful than produced waters from production.
Studies have indicated that produced water discharged from gas/condensate
platforms are concerning ten times additional unhealthful than produced water
discharged from the oil platforms but, for produced water discharged offshore, the
volumes from gas production are abundant and lower than the total impact is also
less.
1.5 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.

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1.5.1 Dispersed Oil
Dispersed oil consists of little droplets suspended within the liquid part and if the
spread oil gets in grips with the ocean flow, contamination and accumulation of oil
on the ocean sediments could occur, that might disturb the benthonic community.
The less dense spread oils may rise to the surface and unfold. Inflicting sheening and
will increase the biological gas demand (BOD) close to the blending zone.
1.5.1.1 Treatment Chemicals
Treatment chemicals like biocides, reverse emulsion breakers and corrosion
inhibitors create the best considerations for aquatic toxicity. However, these
substances might endure reactions that cut back their toxicities before they're
discharged or re-injected. As an example, biocides react with chemicals to lose their
toxicity, and a few corrosion inhibitors might partition into the oil part so they never
reach the ultimate discharge stream. Still, a number of these treatment chemicals
will be fatal at levels as low as zero-1 ppm. Additionally, corrosion inhibitors will
type additional stable emulsions, therefore creating oil/water separation less
economical.
1.5.1.2 Produced Solids
Produced water will contain precipitated solids, sand and silt, carbonates clay,
propant, corrosion merchandise and different suspended solids derived from the
manufacturing formation and from well bore operations Quantities can vary from
insignificant to solids suspension, which might cause the well or the produced water
treatment system to pack up. The solids will influence produced water fate and
effects. Fine-grained solids will cut back the removal potency of oil water
separators, resulting in excedances of oil and grease limits in discharged produced
water.

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1.5.2 Dissolved Organic Components
Hydrocarbons that occur naturally in produced water embody organic acids,
polycyclic aromatic hydrocarbons (PAHs), phenols and volatiles. These
hydrocarbons are possible contributors to produced water toxicity (and their
toxicities are additive) though on an individual basis the toxicities could also be
insignificant once combined aquatic toxicity will occur.
Soluble organics aren't simply aloof from produced water and thus are usually
discharged to the ocean or re-injected at onshore location. Generally, the
concentration of organic compounds in produced water will increase because the
mass of the compound decreases. The lighter weight compounds (BTEX and
naphthalene) are less influenced by the potency of the oil/water separation method
than the upper mass PAHs and aren't measured by the oil and grease analytical
technique.
Organics aren't simply aloof from produced water and thus are Organic parts that are
terribly soluble in produced water include low mass (C2-C5) group acids (fatty
acids), ketones and alcohols. They embody carboxylic acid and carboxylic acid,
ketone and fuel. In some produced waters, the concentration of those parts is larger
than 5000 ppm. as a result of their high solubility, the organic solvent utilized in oil
and grease analysis extracts just about none of them and thus, despite their massive
concentrations in produced water they are doing not contribute considerably to the
oil and grease measurements.
Partially soluble pares embody medium to higher mass hydrocarbons (C6-C15).
They are soluble in water at low concentrations however are not any soluble as
lower mass hydrocarbons. They are not simply aloof from produced water and are
typically discharged on to the ocean. They contribute to the formation of sheen
however the primarily concern involves toxicity. These parts embody open-chain
and aromatic group acids, phenols and open-chain and aromatic hydrocarbons.
Naphthalene is that the most straightforward PAH, with 2 interconnected benzene
rings and is often gift in fossil fuel at higher concentrations than different PAHs (In
Norwegian fields, as an example hydrocarbon includes ninety five the concerns or a
lot of of the entire PAHs in off home produced water). PAHs vary from
comparatively "light" substances with average water solubility to "heavy"

8
substances with high liposolubility and poor water solubility. They increase
biological atomic number 8 demand (BOD), are extremely poisonous to aquatic
organisms and might be malignant neoplastic disease to man and animals. All are
agent and harmful to copy. Significant PAHs bind powerfully to organic matter
(e.g., on the seabed) contributing to their purpose. Higher mass PAHs are less water
soluble and can be gift chiefly related to spread oil. Aromatic hydrocarbons and
alkylated phenols are maybe the foremost vital contributors to toxicity. Alkylated
phenols are thought-about to be endocrine disruptors and therefore have the potential
for procreative effects. However, phenols and chemical group phenols will be
promptly degraded by microorganism and photo-oxidation in H2O and marine
sediments.
1.5.2.1 Scales
Scales will occur once ions in concentrated produced water react to make
precipitates once pressure and temperatures are reduced throughout production.
Common scales embody carbonate, salt, barium sulphate, metallic element salt and
iron salt. They will clog flow lines from oily sludge that has to be removed and kind
emulsions that are troublesome to interrupt.
1.5.2.2 Bacteria
One of the foremost issues within the Oil & Gas sector is corrosion. This can be
often connected to salt reducing microorganism (SRB) and therefore the acid
manufacturing microorganism (APB). One reason for this can be that the terribly
subtractive conditions encourage the SRB to come up with sulfide (H2S) gas. This
gas has not solely a foul odour ("rotten egg") however conjointly embark method of
electrolytic corrosion which may apace corrode steel. Micro-organism will clog
instrumentality and pipeline and may kind difficult to break emulsion and sulfide
that are corrosive.

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1.5.2.3 Metals
The concentration of metals in produced water depends on the sector significantly
with reference to the age and earth science of the formation from that the oil and gas
are produced. Metals generally found in produced waters embody metal, lead,
manganese, iron and Barium. Metals concentrations in produced water are usually
over those in saltwater but, potential impacts on marine organisms is also low as a
result of dilution reduces the concentration and since the shape of the metals
adsorbed onto sediments is a smaller amount bio available to marine animals than
metal ions in resolution. Besides toxicity, metals will cause production issues like by
reacting with oxygen within the air to provide solids, which may interfere with
process instrumentality like hydro cyclones and may plug formations throughout
injection or cause staining or deposits at onshore discharge sites.
1.5.2.4 Sulphates
Sulphate concentration controls the solubility of many different components in
resolution significantly Barium and metallic element.
1.5.3 Naturally Occurring material (NORM)
The most bumper NORM compounds in produced water are radium-226 and
radium-228 that are derived from the decay of atomic number U92 and Th related to
sure rocks and clays within the organic compound reservoir. Because the water
approaches the surface, temperature changes cause radioactive components to
precipitate. The ensuing scales and sludge might accumulate in water separation.

10
1.6 Environmental Impact and Legislation
Produced water will have completely different potential impacts betting on wherever
it's discharged. For instance, discharges to little streams are doubtless to own a
bigger environmental impact than discharges produced to the open ocean by virtue
of the dilution that takes place following discharge.
Numerous variables confirm the particular impacts of produced water discharge.
These embody the physical and chemical properties of the constituents, temperature,
content of dissolved organic material, soil acids, presence of different organic
contaminants and internal factors like metabolism, fat content, generative state and
feeding behavior.
The general follow in use for produced water treatment is gravity-based separation
and discharge into the surroundings, which may dirty soil, surface water and
underground water. For an extended time, solely non-polar oil in water (OIW) was
regulated by government, whereas very little attention was given to dissolved
organics in produced water. Current researches are paying a lot of attention to the
consequence of dissolved organic elements, significant metals and production
chemicals on living organisms, since their semi-permanent effects on the
surroundings don't seem to be absolutely documented and understood. It's been
according that metals and hydrocarbons from oil are terribly toxic to the system and
fish exposed to alkyl radical phenols have disturbances in each organs and fertility.
A general legislation for discharging produced water into ocean has been forty ppm
however a rise in environmental issues has produced several countries to implement
a lot of tight restrictive standards. The US Environmental Protection Agency
(USEPA) sets a daily most for oil and grease at forty two ppm.

11
CHAPTER 2: LITERATURE SURVEY
The most relevant publication revised till 2018 which studied the techniques of
treatment of oil field produced water from different field and Environmental impacts
of produced water.
2.1 List of literature survey
1) Dr. J. Daniel Arthur (2011) studied about the different technologies that can be
used to make the produced water disposable recyclable and re-injected. They mainly
focused on the five contents to be removed.1) slat.2) Oil and grease.3) organic and
in-organic compounds.4) chemical additives.5) naturally occurring radioactive
material. They mainly focused on three criteria for a technology to be stated
sustainable.1) Economic cost 2) Efficiency 3) availability.
Based on this parameter they concluded different technologies for removal of
different components.
e.g.:1) for slat: Membrane separation, Thermal treatment, Ion exchange, capacitive
deionization.
2) For oil and grease: Physical Separation, coalescence, adsorption, solvent
extraction.
Different processes have different pros. and cons. Based on the three parameters
stated above they categorised the potential use of different technology in different
premises and different G.As in North America.
2) 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
using1, 1, 2-trichloro-1, 2, 2-trifluoroethane solvent. Then the extracted oil was

12
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.
3) Petroleum Development Oman (PDO) studied on Treatment and Utilization of
oil containing Produced-water in Oman. Its major objective was identification of
critical environmental problems associated with the petroleum industry in Oman.
Environmental problems in Oman were investigated; tank sludge and oil-containing
wastewater were chosen as major problems associated with the petroleum industry,
and current situations were studied. Survey of environmental problems in the
petroleum industry in Oman (FY 1996 survey)
The environmental problems that have surfaced are a few because the industry is
still not matured in Oman, and its population density is low. Although sewage and
waste loom as major potential problems, these are problems of the social system
rather than technological problems.
In the petroleum industry, which supports Omani economy, the problems of oil-
containing produced water and sludge involve technological issues, and it was found
that the solving the problem of the produced water, in particular, would have much
greater impact overall.
Problem of oil containing Produced-water is in the oil fields of Oman, the
underground water (oil-containing water) drawn up associated with oil production
amounts to more than three times the volume of the produced oil. The total volume
of produced water at present is approximately 500,000 tons per day, and it is
forecasted that the volume will increase to 750,000 tons per day by the year 2005. In
the oil fields of the southern district, underground water does not have to be re-
injected to maintain pressure of reservoirs. In the northern region, on the other hand,
it is discharged to a shallow aquifer at 100~200 m and a deep formation at
approximately 1000 m. Since there is a danger that the oily-water discharged to the
shallow layer could contaminate underground water sources, the discharge is
scheduled to be prohibited in the near future.
Main features of the oil-containing wastewater problem can be summarized as the

13
Followings:
(1) Volume of the oil-containing wastewater is extremely large.
(2) Material needs to be removed from the water can be specified to oil components.
(3) Treated water should be effectively used for irrigation.
And they concluded that our hope that the findings obtained through this research
project will be applied to the development of technology to treat oil-containing
produced water in Oman. It is also hoped earnestly that in the near future, a water
treatment plant on a practical scale.
4) Nwabanne, J. T in 2012 studied the adsorption performance of packed bed
column using activated carbon prepared from oil palm fiber 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 analyzed 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 initial 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
correlate well with both models. The relationship between the experimental
breakthrough curve to the breakthrough fit for activated carbon derived from oil
palm empty fruit bunch.

14
5) I. M.Muhamadn 2012 showed that eggshells have the ability to absorb 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 favorable
isotherm this highest correlation.
6) 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 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 analyses the experimental data up to
breakthrough time. A mass transfer model was used to analyses the mass transfer
zone. The breakthrough curve was analyzed 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.

15
7) 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 favors’ the
adsorption process.
8) ITF theme (2015) studied and summarised the key challenges facing ITF GCC
Members in deploying commercial down hole oil and water separation techniques
(DOWS).The report mainly focused on ITF methodology. They are mainly
characterised into six part and each part represented detailed information conform to
its title.
1) DOWS SYSTEM (Hydro cyclone separation, Machinery Separation.)
2) Systematic Problems. (Solid content, Too high water cut)
3) Key factors for deployment. (Suspended oil content, Solids content, Water
compatibilities)
4) Priority requirements. (e.g.: Retrofit capable in both vertical and horizontal wells)
5) Selected emerging technologies.(combined gravity separation and coalescence
separation, surface coated magnetic nano-particles, coupled hydro cyclone and
modified pumping system, Down hole water sink technology, Vane-type pipe
separator etc.)
The key deficiency identified from the currently available technology is the
deployment of the necessary equipment associated with oil-water separation, down
hole; a challenging environment with limited space. Overcoming this fundamental
challenge may represent the real turning point in applying conventional oil-water
separation technologies down hole.
9) J. Daniel Arthur, P.E. & Bruce G. Langhus, .studied oil and gas produced
water treatment include meeting discharge regulations (local, state and federal),
reusing treated produced water in oil and gas operations, developing agricultural

16
water uses. The oil and gas industry produces approximately 14 billion bbls of water
annually. They define that the options available to the oil and gas operator for
managing produced water might include the following:
1. Avoid production of water onto the surface
2. Inject produced water
3. Discharge produced water
4. Reuse in oil and gas operations
5. Consume in beneficial use
10) Katie Guerra, Katharine Dahm, Steve Dundorf(2010) studied about Oil and
Gas Produced Water Management and Beneficial Use in the Western United
States(Oklahoma, Kansas, Houston.).They first concluded their study on produced
water characterization. Salt Concentration and Composition, Inorganic Constituents,
Organic Constituents, Naturally Occurring Radioactive Materials, Chemical
Additives were the main composition got found in produced water in western United
States. To make the content fall under usable premises. They did Assessment of
Technologies for Treatment of Produced Water. They mainly focused on 4 types of
technology.
1) Organic, Particulate, and Microbial Inactivation/Removal Technologies (e.g.:
adsorption)
2) Desalination Technologies (e.g.: forward osmosis, softening.)
3) Commercial processes (e.g.: CDM produced water technology, Veolia OPUS).
4) GIS based approach to produced water management. (e.g.: Agriculture water
demand.)
From the use of those technological innovations, they reclaimed the potential use of
produced water as commercial and agriculture use.

17
11) Brian P. Dwyer (2016) studied about characterization and treatment procedures
for produced water in New Mexico in accordance to location, geography, production
method, H.C being used. The common method for handling the produced water from
well production was re-injection in regulatory permitted salt water disposal wells.
This is expensive (~$5/bbl.) and does not recycle water, an ever increasingly
valuable commodity Previously ,Sandia National laboratory tested pressure driven
membrane-filtration techniques to remove the high TDS (total dissolved solids) from
a Four Corners Coal Bed Methane produced water. Treatment effectiveness was less
than optimal due to problems with pre-treatment. Inadequate pre-treatment allowed
hydrocarbons, wax and biological growth to foul the membranes. This research was
mainly based on innovative pre-treatment scheme using ozone and hydrogen
peroxide was pilot tested. Results showed complete removal of hydrocarbons and
the majority of organic constituents from a gas well production water.
12) Colorado School of Mines did the Technical assessment of produced water
treatment technologies. This technical assessment includes stand-alone water
treatment processes, hybrid configurations, and commercial packages developed for
treatment of oil and gas produced water and zero liquid discharge (ZLD).
They assessed total of 54 technologies which are classified into stand-alone
technologies and combined treatment process. Stand-alone/ primary technology like
media filtration and adsorption is assessed below.
1 Media filtration:
In this process the Filtration can be accomplished using a variety of different types
of media: walnut shell, sand, anthracite, and others. Filtration is a widely used
technology for produced water, especially walnut shell filters for the removal of oil
and grease. Filtration does not remove dissolved ions and performance of filters is
not affected by high salt concentrations, therefore filtration can be used for all TDS
(Total dissolved solids) bins regardless of salt type.
Assessment of media filtration process: This process is applicable to all TDS bins,
independent of salt type and concentration. Product water quality is >90% removal
of oil and grease. In this process 100% water recovery is achieved. Chemicals like

18
Coagulant may be added to the feed water to increase particle size and enhance
separation. This process does not require pre and post treatment.
2 Adsorption process:
Adsorption can be accomplished using a variety of materials, including zeolites,
oregano clays, activated alumina, and activated carbon. Chemicals are not required
for normal operation of adsorptive processes. Chemicals may be used to regenerate
media when all active sites are occupied. Adsorbents are capable of removing iron,
manganese, total organic carbon, BTEX compounds, heavy metals, and oil from
produced water.
Assessment of Adsorption process: This process is applicable to all TDS bins,
independent of salt type and concentration. It can remove iron, manganese, TOC,
BTEX, and oil. Product water quality is > 80% removal of heavy metals. In this
process 100% water recovery is achieved. In this process chemicals are required for
media generation. As pre and post treatment adsorption is best used as a polishing
step to avoid rapid usage of adsorbent material.
2.2 Produced water management
PW is considered as a waste stream in oil and gas production processes and its
management which is usually done to decrease its environmental pollution issues, is
very expensive. For the PW management, three major successive manners can be
considered which could respectively be summarized as minimizing the production of
PW, reusing or recycling the PW and if none of them could be applied, discarding of
PW must be considered.
PW treatment process, which is used before recycling or discarding the PW, is very
important to decrease the harmfulness of the PW and valuable products would be
achieved through it.
The main objectives of this process could be stated as the removal of the following
contents of PW:
1. Free and dispersed oil
2. Dissolved organics

19
3. Microorganisms, algae and bacteria
4. Turbidity via elimination of suspended particles and colloids
5. Dissolved gases
6. Dissolved salts and minerals, excess water-hardness and possible radioactive
materials
Usually, selection of the PW treatment method is a challenging problem that is
steered by the overall treatment goal. The general plan is to choose the cheapest and
most efficient method. To meet up with mentioned objectives, operators usually
have applied many stands-alone in one combined technology: physical, biological
and chemical treatment methods for PW management and treatment.
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 re removal of any particular pollutants from wastewater.
In adsorption process if the interaction between the solid surface and the adsorbed
molecules has a physical nature, the process is called physical adsorption. 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 processes is called chemisorptions.
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

20
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 Q (mg/g) is the amount of adsorbate per mass unit of adsorbent at time, Co
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 the process in water and wastewater application were developed by ( i )
Langmuir, (ii) Brunauer, Emmet, ( 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.
2.3.1 Factors Affecting Adsorption
1. Surface area
2. Nature and initial concentration of adsorbate
3. Solution pH
4. Temperature
5. Interfering substances
6. 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

21
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. The major contribution to surface area is located in the pores of
molecular dimension.
Another important Parameter is the temperature. In adsorption Nielhod 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.
2.3.2 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.

22
2.4 Industrial Treatments for Produced Water
General objectives for operators when they plan produced water treatment are
1. De-oiling – Removal of free and dispersed oil and grease present in produced
water.
2. Soluble organics removal – Removal of dissolved organics.
3. Disinfection – Removal of bacteria, microorganisms, algae, etc.
4. Suspended solids removal – Removal of suspended particles, sand, turbidity, etc.
5. Dissolved gas removal – Removal of light hydrocarbon gases, carbon dioxide,
hydrogen sulfide, etc.
6. Desalination or demineralization – Removal of dissolved salts, sulfates, nitrates,
contaminants, scaling agents, etc.
7. Softening – Removal of excess water hardness.
8. Sodium Adsorption Ratio (SAR) adjustment – Addition of calcium or magnesium
ions into the produced water to adjust sodicity levels prior to irrigation.
9. Miscellaneous – Naturally occurring radioactive materials (NORM) removal.
The effectiveness and performance of the various treatment technologies can also be
analyzed according to a new five-step ranking approach devised by the authors. This
ranking scheme can be applied to a range of technological options for treating
produced waters. The ranking can help the oil and gas operator choose between
options, but of course an important part of the decision will depend on the
requirements for the chosen end use for the water.

23
CHAPTER 3: RESRARCH METHODOLOGY
3.1 Water Sampling Method and Analysis
The water samples were analysed for various parameters in the laboratory of
Drilling fluids and cementation, Pandit Deendayal Petroleum University and in
Gujarat laboratory. Various physical and chemical parameters like, pH,
Conductivity, Total hardness, Biochemical Oxygen Demand (BOD), Chemical
oxygen demand (COD), Chloride, Oil and grease, Sulfide, Iron, Mercury,
Chromium, Aluminium, Carbonate and Lead have been monitored for the produced
water and water samples of different locations.
Plastic bottles of 1litters and 1.2 litters capacity were used for collecting
samples. Each bottle was washed and rinsed with distilled water. The bottles were
then preserved in a clean and dark place with optimum room temperature. The
bottles were filled leaving no air space, and then the bottle was sealed to prevent any
leakage. Each container was clearly marked with the name and date of sampling.
3.1.1 Location of water sampling
Water samples were collected from the following location.
Produced water from ONGC GGS 2,
Jhlora Field
Figure 3- 1: Sample of Produced Water

24
3.2 Adsorption process for produced water
The term adsorption refers to the accumulation of substance at the interface between
to 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 adsorbate.
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
Substances 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 exchange of electrons and thus chemical sorption generally
irreversible. In chemisorptions the force of attraction is very strong. Therefore
adsorption can’t be early reversed.
In Physical Adsorption is characterized by weak van der waals 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 chemisorptions. The main physical forces
controlling adsorption are van der waals 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-

25
treatment step before its application. As for environmental remediation purpose.
Adsorption techniques are commonly used to remove certain classes of chemical
contaminants from water, 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
We did the adsorption process to identify the change in concentration of ions in
produced water. To accomplished adsorption we used different types of rock
material and different rock sizes for experiment. To conduct the adsorption process
we used separator funnel, cotton, beaker, flask, and weighting machine. The used
adsorbent rocks were: 1) Gray shale 2) White clay 3) Laterite
Raw material: produced water form Jhalora Filed
Experiment Procedure
 First we sampled the three rocks into different mess sizes of 125 microns, 250
microns, 500 microns, 1000 microns, 2000 microns
 We set up the separator funnel in the stand and filled it with cotton as barrier to
avoid the chocking of the rock particles in the funnel.
 Took one rock sample and measured 10gm in weighing machine and took 100ml of
produced water in beaker.
 In the separator funnel we pour the 10gm of rock sample above the cotton.
 After that steadily we pour 100ml of produced water in to the separator funnel and
kept it for one hour to set.

26
 After one hour we slightly opened the chock to allow the water to pass it through
rock sample and cotton and collect it in the beaker and note the time.
 We followed the same procedure for other rock sample as well.
 After the experiment we collected the water sample and rock sample.
Figure 3- 2: Experiment setup Figure 3- 3: Rock sample of different size
3.3 Material and methods
3.3.1 List of Instruments:
1) Separator funnel
2) Flame Photometer
3) PH meter
4) Salinity meter
5) Sieve Analyzer
6) Weighting machine
Figure 3- 4: Sieve Analysis

27
3.3.2 List of Glassware:
1) Measuring cylinders
2) Separating funnel
3) Conical flask
4) Beakers
3.3.3 Tests
3.3.3.1 PH meter
3.3.3.1.1 PRINCIPLES
The pH of a solution is determined by electrochemical measurements with a device
known as a pH meter with a pH (proton)-sensitive electrode (usually glass) and a
reference electrode (usually silver chloride or calomel). Ideally, the electrode
potential, E, for the proton can be written as
Where E is a measured potential, E0 is the standard electrode potential at an H+= 1
mol/L, R is the gas constant, T is the temperature in Kelvin, F is the Faraday
constant.
The pH electrode is specially formulated, pH-sensitive glass in contact with the
solution, which develops the potential (E) proportional to the pH of the solution. The
reference electrode is designed to maintain a constant potential at any given
temperature, and serves to complete the pH measuring circuit within the solution. It
provides a known reference potential for the pH electrode. The difference in the
potentials of the pH and reference electrodes provides a mill volt (mV) signal
proportional to pH. It is calibrated against buffer solutions of known hydrogen ion
activity. A pH value of 7 indicates a neutral solution. Pure water should have a pH
value of 7. Now pH values less than 7 indicate an acidic solution while a pH value
greater than 7 will indicate an alkaline solution. A solution with pH value of 1 is
highly acidic and a solution of pH value of 14 is highly alkaline.

28
3.3.3.1.2 Types of pH meter
1) Handheld pH meter
2) Bench top pH meter
3) Continuous in line pH meter
3.3.3.1.3 Apparatus
1. PH meter
2. Beaker
3.3.3.1.4 Procedure
Turn on the pH meter and allow adequate time for the meter to warm up.
Clean the electrode. Take the electrode and rinse it with distilled water under an
empty waste beaker. Once rinsed, blot dry with clean tissue paper. Be sure to rinse
your electrode in a waste beaker that is different from the beaker you will be
calibrating in. Avoid rubbing the electrode as it has a sensitive membrane around it.
Once the electrode are cleaned place it in the beaker containing the standard
solution, in this case neutral solution of pH 7 was used for calibration. It is advisable
to wait for the reading to get stabilized.
Rinse the electrode with distilled water after the calibration and wipe it dry with a
tissue. Now place the cleaned electrode in the beaker containing the water sample,
wait for 1-2 mins for the reading to get stabilized, note down the reading and repeat
the procedure for the reaming water samples.

29
Figure 3- 5: PH meter
3.3.3.2 Salinity
Salinity is the measure of all the salts dissolved in water. Salinity is usually
measured in parts per thousand (ppt). The average ocean salinity is 35ppt and the
average river water salinity is 0.5ppt or less. This means that in every kilogram
(1000 grams) of seawater, 35 grams are salt.
3.3.3.2.1 Salinity measurement
There are two main methods of determining the salt content of water: Total
Dissolved Salts (or Solids) and Electrical Conductivity.
Total Dissolved Salts (TDS) is measured by evaporating a known volume of water
to dryness, then weighing the solid residue remaining. Electrical conductivity (EC)
is measured by passing an electric current between two metal plates (electrodes) in
the water sample and measuring how readily current flows (i.e. conducted) between

30
the plates. The more dissolved salt in the water, the stronger the current flow and the
higher the EC. Measurements of EC can be used to give an estimate of TDS.
Measurement of TDS is tedious and cannot be carried out in the field. EC
measurement is much quicker and simpler and is very useful for field measurement.
There are however a few simple precautions to note in doing so and these are
outlined here.
3.3.3.2.2 Salinity Measurements Procedure
• Ensure your EC meter has been calibrated (see notes below).
• Remove the protective cap, switch the meter on and insert the probe into the water
sample up to the immersion level.
• Move the probe up and down to remove bubbles from around the electrodes.
• This will ensure good contact is achieved between water and electrodes (do not
swirl it around as this may actually drive water out of the probe).
• Allow the probe to reach the temperature of the water before taking a reading.
• Temperature has a significant impact on the salinity reading. EC units are
standardized to a temperature of 25 o
C. Some meters automatically correct the
reading taken at water temperature to a reading at 25 o
C.
• If the meter has automatic temperature compensation, wait about 30 seconds
before taking your reading if the water and probe are about the same temperature. If
the water is much colder than the probe, allow a longer period, say two minutes
before taking a reading.
• If the meter has no temperature compensation take the temperature of the sample
and use a correction table to get the right value.

31
• Read the display, and record the result as mentioned below.
• Rinse the probe with tank water and drain off any excess water, between each
sample and at the end of sampling for the day. This will prevent false readings due
to salt residues on the meter from the last sample.
Figure 3- 6: Salinity meter
3.3.3.3 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.
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

32
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 device use proper calibration with a series of standard
solutions of the ion to be tested click and drag each of the standard solution below
the capillary tube and click on the “Aspirate” button to calibrate the machine.
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 distilled water sample below the Capillary tube and click on
the Start Test" button to measure the concentration.
3.3.3.3.1 Standard solution
Li: Standard solution of Li with 1, 5, 10ppm
Na: Standard solution of Na with 10, 50,100ppm
Ca: Standard solution of Ca with 1, 10, 100,300ppm
K: Standard solution of K with 1, 5, 50,100ppm
3.3.3.3.2 General procedure for preparation of stock standard solution for
flame photometer
1) Sodium (Na):
a) 1000ppm Dissolve 2.5416 g Nacl in one liter of glass distilled water
2) Potassium (K):
a) 1000ppm Dissolve 1.9070 g KCL or 2.5869 g KNO, in one liter of glass distilled
water
b) 100ppm (as K2O) Dissolve 1.5830 g KCL in one liter of glass distilled water
3) Calcium (Ca):

33
a) 1000ppm Dissolve 2.497 g CaCO3, in approx. 300ml glass distilled water and add
10ml conc.
4) Lithium (Li):
a) 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 liter
Figure 3- 7: Flame Photometer
3.3.3.4 Conductivity
3.3.3.4.1 Apparatus
1. Conductivity meter
2. Beaker
3.6.3.4.2 Procedure
Turn on the conductivity meter and allow adequate time for the meter to warm up.
Clean the electrode. Take the electrode and rinse it with distilled water under an
empty waste beaker. Once rinsed, blot dry with clean tissue paper. Be sure to rinse
your electrode in a waste beaker that is different from the beaker you will be
calibrating in. Avoid rubbing the electrode as it has a sensitive membrane around it.

34
Once the electrode are cleaned place it in the beaker containing the standard
solution, in this case solution of 0.1M KCl was used for calibration. It is advisable to
wait for the reading to get stabilized.
Rinse the electrode with distilled water after the calibration and wipe it dry with a
tissue. Now place the cleaned electrode in the beaker containing the water sample,
wait for 1-2 mins for the reading to get stabilized, note down the reading and repeat
the procedure for the reaming water samples.
Figure 3- 8: Conductivity meter used for the experiment

35
CHAPTER 4: RESULTS AND ANALYSIS
4.1 PRODUCED WATER PARAMETERS
Following are the parameter of the produced water which I measured using flame
photometer and pH meter, Salinity mete, Conductivity meter. All parameters as per
bureau of Indian standards and American public health association standard method.
Parameter Value Standard Method
PH 6.95-8.5 (at 28o
c) IS-3025(part 11) 1983- clause-RA 2012
Electrical
Conductivity
4.59(µS/cm) APHA-22nd
ed. 2510B
Salinity 22.2 (ppt) APHA 22nd
ed. 2520- B Electrical
conductivity method
Table 4- 1: Physical parameter of produced water
Metal Value Standard Method
Na 34.66 APHA 22nd
ed. 3500 Na-B Flame photometer
Ca 111.62 APHA 22nd
ed. 3500 Ca-B Flame photometer
Li 1.308 APHA 22nd
ed. 3500 Li-B Flame photometer
K 60.96 APHA 22nd
ed. 3500 K-B Flame photometer
Table 4- 2: Ions measured in produced water

36
4.2 EFFECT OF VARIOUS FACTORS DEPENDS ON
ADSORPTION PROCESS:
4.2.1 EFFECT OF TOTAL SURFACE AREA ON ADSORPTION:
Here to conclude the effect of particle size on adsorption, we have taken three
different samples of rock:
1) Gray Shale
2) White clay
3) Late rite
We have taken the sample in 2000, 1000, 500, 250, 125 micron for each rock and
then, have compared the adsorbed content of Li, Na, K, Ca metals for each grain
sizes. We have also measured adsorbed content of Activated Charcoal and Zeolite
for reference. Detailed results and analysis are given below.
4.2.1.1 Gray Shale:
Shale is a fine-grained, clastic, sedimentary rock composed of mud that is a mix of
flakes of clay mineral and tiny fragments (slit- -sized particles) of other minerals,
especially quartz and calcite. Shale is characterized by breaks along thin laminate or
parallel layering or bedding less than one centimeter in thickness, called fissility. It
is the most common sedimentary rock.
Shale typically exhibits varying degrees of fissility, breaking into thin layers, often
splintery and usually parallel to the otherwise indistinguishable bedding plane
because of the parallel orientation of clay mineral flakes. Non-fissile rocks of similar
composition but made of particles smaller than 0.06 mm are described as
mudstones (1/3 to 2/3 silt particles) or claystones (less than 1/3 silt).Rocks with
similar particle sizes but with less clay (greater than 2/3 silt) and therefore grittier
are siltstones.

37
4.2.1.1.1 Lithium (Li)
Mesh Size(µm) 2000 1000 500 250 125
Li (ppm) 1.69 1.64 1.66 1.68 1.65
Untreated(Li) 2
Activated Charcoal(Li) 1.44
Zeolite (Li) 1.43
Table 4- 3: Lithium concentration analysis for treated produced water for different
grain size of grey shale
Figure 4- 1: Effect of grain size of gray shale on adsorption of Lithium from
produced water
Here as shown in table when we change mesh sizes of gray shale from 2000 µm to
125 µm, Lithium concentration in treated sample reduces from 1.69 ppm to 1.65
ppm. While concentration in untreated is 2 ppm. Lithium concentration in treated
sample by Activated charcoal and zeolite is 1.44 ppm and 1.43 respectively. And
here a graph of lithium concentration varying in different mesh sizes is shown so we
can understand better. Here, we can conclude that Lithium concentration does not
vary too much when we change mesh sizes from 2000 µm to 125 µm. Adsorption in
Gray shale Compared to activated charcoal and zeolite is low.
2
1.69 1.64 1.66 1.68 1.65
1.441.43
2000 1000 500 250 125
Concentration(ppm)
Mesh Size (µm)
Gray Shale-Li
Untreated Treated Activated Charcole Zeolite

38
4.2.1.1.2 Sodium (Na)
Mesh Size(µm) 2000 1000 500 250 125
Na (ppm) 41.1 40.16 40.04 39.7 39.2
Untreated(Na) 49.1
Activated Charcoal(Na) 39.03
Zeolite (Na) 41.3
Table 4- 4: Sodium concentration analysis for treated produced water for different
Figure 4- 2: Effect of grain size of gray shale on adsorption of Sodium from
produced water
125 µm, Sodium concentration in treated sample reduces from 41.1 ppm to 39.2
ppm. While concentration in untreated is 49.1 ppm. Sodium concentration in treated
here a graph of Sodium concentration varying in different mesh sizes is shown so we
can understand better. Here, we can conclude that Sodium concentration does not
Gray shale Compared to activated charcoal and zeolite is low.
49.1
41.1 40.16 40.04 39.7 39.239.0341.3
2000 1000 500 250 125
Concentration(ppm)
Mesh size (µm)
Gray Shale - Na

39
4.2.1.1.3 Calcium (Ca)
Mesh Size(µm) 2000 1000 500 250 125
Ca (ppm) 127.9 126.8 127.8 124.4 125.6
Untreated(Ca) 131.5
Activated Charcoal(Ca) 124.56
Zeolite (Ca) 122.54
Table 4- 5: Calcium concentration analysis for treated produced water for different
Figure 4- 3: Effect of grain size of gray shale on adsorption of Calcium from
produced water
125 µm, Calcium concentration in treated sample reduces from 127.9 ppm to 125.6
ppm. While concentration in untreated is 131.5 ppm. Calcium concentration in
treated sample by Activated charcoal and zeolite is 124.56 ppm and 122.54
respectively. And here a graph of Calcium concentration varying in different mesh
sizes is shown so we can understand better. Here, we can conclude that Calcium
concentration does not vary too much when we change mesh sizes from 2000 µm to
125 µm. Adsorption in Gray shale Compared to activated charcoal and zeolite is
low.
131.5
127.9
126.8
127.8
124.4
125.6
124.56
122.54
2000 1000 500 250 125
Concentration(ppm)
Mesh size (µm)
Gray Shale - Ca

40
4.2.1.1.4 Potassium (K)
Mesh Size(µm) 2000 1000 500 250 125
Ca (ppm) 80.31 77.75 74.58 72.27 70.21
Untreated(Ca) 81.4
Activated Charcoal(Ca) 66.54
Zeolite (Ca) 61.45
Table 4- 6: Potassium concentration analysis for treated produced water for different
Figure 4- 4: Effect of grain size of gray shale on adsorption of Potassium from
produced water
125 µm, Potassium concentration in treated sample reduces from 80.31 ppm to
70.21 ppm. While concentration in untreated is 81.4 ppm. Potassium concentration
in treated sample by Activated charcoal and zeolite is 66.54 ppm and 61.45
respectively. And here a graph of Potassium concentration varying in different mesh
sizes is shown so we can understand better. Here, we can conclude that Potassium
125 µm. Adsorption in Gray shale Compared to activated charcoal and zeolite is
low.
81.480.31 77.75 74.58 72.27 70.2166.54
61.45
2000 1000 500 250 125
Concentration(ppm)
Mesh Size (µm)
Gray Shale - K

41
4.2.1.2 White Clay:
Kaolinite is a clay mineral, part of the group of industrial minerals, with the
chemical compositional Al2Si2O5 (OH) 4. It is a layered silicate mineral, with one
tetrahedral sheet of silica (SiO4) linked through oxygen atom to one octahedral sheet
of alumina (AlO6) octahedral. Rocks that are rich in kaolinite are known as kaolin or
china clay.
Mesh size(ppm) 2000 1000 500 250 125 63
Li(ppm) 1.54 1.51 1.53 1.52 1.5 1.48
Untreated (Li) 2
Activated charcoal (Li) 1.44
Zeolite (Li) 1.43
grain size of White clay
Figure 4- 5: Effect of grain size of White clay on adsorption of Lithium from
produced water
Here as shown in table when we change mesh sizes of White Clay from 2000 µm to
125 µm, Lithium concentration in treated sample reduces from 1.54 ppm to 1.48
here a graph of Lithium concentration varying in different mesh sizes is shown so
we can understand better. Here, we can conclude that Lithium concentration does
not vary too much when we change mesh sizes from 2000 µm to 125 µm.
Adsorption in White Clay Compared to activated charcoal and zeolite is almost
same.
2
1.54 1.51 1.53 1.52 1.5 1.481.441.43
2000 1000 500 250 125 63
Concentration(ppm)
Mesh Size (µm)
White Clay - Li

42
4.2.1.2.2 Sodium (Na)
Mesh size(ppm) 2000 1000 500 250 125 63
Na(ppm) 42.17 39.46 37.61 36.74 36.6 36.2
Untreated (Na) 49.1
Activated charcoal (Na) 39.03
Zeolite (Na) 41.3
Figure 4- 6: Effect of grain size of White clay on adsorption of Sodium from
produced water
Here as shown in table when we change mesh sizes of White clay from 2000 µm to
125 µm, Sodium concentration in treated sample reduces from 42.17 ppm to 36.2
White Clay Compared to activated charcoal and zeolite is high in low mesh sizes
such as 125 µm.
49.1
42.17 39.46 37.61 36.74 36.6 36.239.0341.3
2000 1000 500 250 125 63
Concentration)ppm)
Mesh Size(µm)
White Clay - Na

43
Mesh size(ppm) 2000 1000 500 250 125 63
Ca(ppm) 124.5 125.6 129.8 123.7 126.7 124.3
Untreated (Ca) 131.5
Activated charcoal (Ca) 124.56
Zeolite (Ca) 122.54
Figure 4- 7: Effect of grain size of White clay on adsorption of Calcium from
produced water
125 µm, Calcium concentration in treated sample reduces from 124.5 ppm to 124.3
ppm. While concentration in untreated is 131.5 ppm. Calcium concentration in
125 µm. Adsorption in White Clay Compared to activated charcoal and zeolite is
low.
131.5
124.5
125.6
129.8
123.7
126.7
124.3124.56
122.54
2000 1000 500 250 125 63
Concentration(ppm)
Mesh Size (µm)
White Clay - Ca

44
Mesh size(ppm) 2000 1000 500 250 125 63
K(ppm) 67.85 67.94 67.5 67.75 66.9 66.86
Untreated (K) 81.4
Activated charcoal (K) 66.54
Zeolite (K) 61.45
Table 4- 10: Potassium concentration analysis for treated produced water for
different grain size of White clay
Figure 4- 8: Effect of grain size of White clay on adsorption of Potassium from
produced water
125 µm, Potassium concentration in treated sample reduces from 67.25 ppm to
125 µm. Adsorption in White Clay Compared to activated charcoal and zeolite is
almost same.
81.4
67.85 67.94 67.5 67.75 66.9 66.8666.54
61.45
2000 1000 500 250 125 63
Concentration(ppm)
Mesh Size (µm)
White Clay - K

45
4.2.1.3 Laterite Rock
Late rite is a soil and rock type rich in iron and aluminum, and is commonly
considered to have formed in hot and wet tropical areas. Nearly all late rites are of
rusty-red coloration, because of high iron oxide content. They develop by intensive
and long-lasting weathering of the underlying parent rock. Tropical weathering
(laterization) is a prolonged process of chemical weathering which produces a wide
variety in the thickness, grade, chemistry and ore mineralogy of the resulting soils.
Mesh size(ppm) 2000 1000 500 250 125
Li(ppm) 1.45 1.43 1.42 1.41 1.41
Untreated (Li) 2
Activated charcoal (Li) 1.44
Zeolite (Li) 1.43
grain size of laterite
Figure 4- 9: Effect of grain size of laterite on adsorption of Lithium from produced
water
Here as shown in table when we change mesh sizes of Laterite Rock from 2000 µm
to 125 µm, Lithium concentration in treated sample reduces from 1.45 ppm to 1.41
here a graph of Lithium concentration varying in different mesh sizes is shown so
we can understand better. Here, we can conclude that Lithium concentration does
not vary too much when we change mesh sizes from 2000 µm to 125 µm.
Adsorption in Laterite rock Compared to activated charcoal and zeolite is almost
same.
2
1.45 1.43 1.42 1.41 1.411.441.43
2000 1000 500 250 125
Concentration(ppm)
Mesh Size (µm)
Laterite Rock - Li

46
4.2.3.2 Sodium (Na)
Mesh size(ppm) 2000 1000 500 250 125
Na(ppm) 38.35 38.44 37.41 37.65 37.6
Untreated (Na) 49.1
Activated charcoal (Na) 39.03
Zeolite (Na) 41.3
Figure 4- 10: Effect of grain size of laterite on adsorption of Sodium from produced
water
to 125 µm, Sodium concentration in treated sample reduces from 38.35 ppm to 37.6
Laterite Rock Compared to activated charcoal and zeolite is high in low mesh sizes
such as 125 µm.
49.1
38.35 38.44 37.41 37.65 37.639.0341.3
2000 1000 500 250 125
Concentration(ppm)
Mesh Size (µm)
Laterite Rock - Na

47
Mesh size(ppm) 2000 1000 500 250 125
Ca(ppm) 122.3 125.7 124.6 128.9 128.8
Untreated (Ca) 131.5
Activated charcoal (Ca) 124.56
Zeolite (Ca) 122.54
Figure 4- 11: Effect of grain size of laterite on adsorption of Calcium from produced
water
to 125 µm, Calcium concentration in treated sample reduces from 122.3 ppm to
128.8 ppm. While concentration in untreated is 131.5 ppm. Calcium concentration in
125 µm. Adsorption in Laterite Rock Compared to activated charcoal and zeolite is
low.
131.5
122.3
125.7
124.6
128.9 128.8
124.56
122.54
2000 1000 500 250 125
Concentration(ppm)
Mesh size (µm)
Laterite Rock - Ca

48
Mesh size(ppm) 2000 1000 500 250 125
K(ppm) 67.25 66.98 64.23 65.41 61.57
Untreated (K) 81.4
Activated charcoal (K) 66.54
Zeolite (K) 61.45
Table 4- 14: Potassium concentration analysis for treated produced water for
different grain size of laterite
Figure 4- 12: Effect of grain size of laterite on adsorption of Lithium from produced
water
to 125 µm, Potassium concentration in treated sample reduces from 67.25 ppm to
125 µm. Adsorption in Laterite Rock Compared to activated charcoal and zeolite is
almost same.
81.4
67.25 66.98 64.23 65.41 61.57
66.54
61.45
2000 1000 500 250 125
Concentration(ppm)
Mesh Size (µm)
Laterite Rock - K

49
4.2.2 EFFECT OF CONTACT TIME ON ADSORPTION
As can be seen from below tables and graphs the amount of ion concentration
adsorbed on the mixture of rock sample 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 is point, the amount of ion concentration desorbing from soil and
activate maximum adsorption carbon is in state of dynamic equilibrium time reflects
the maximum adsorption capacity of the adsorbent under those operating condition.
4.2.2.1 Gray shale
4.2.2.1.1 Lithium
Time(min) Untreated(ppm) Treated(ppm) Adsorption(ppm) Adsorption
30 2 1.63 0.37 18.50%
60 2 1.512 0.488 22.40%
120 2 1.448 0.552 27.60%
180 2 1.314 0.686 34.30%
240 2 1.308 0.692 34.60%
Table 4- 15: Effect of contact time on adsorption of Lithium from produced water
for gray shale
Figure 4- 13: Concentration Lithium v/s contact time for gray shale
Here as shown in table when adsorption time is increased in Gray Shale from 30
minutes to 240 minutes adsorption of Lithium on Gray Shale is increased from 0.37
ppm to 0.692 ppm. If adsorption is expressed in percentage of total concentration,
adsorption increases from 18.50% to 34.60% as adsorption time increases from 30
minutes to 240 minutes. Also Lithium concentration in treated sample decreases
from 1.63 ppm to 1.308 ppm as adsorption time increases from 30 minutes to 240
minutes. A graph of Concentration v/s Time is plotted that indicates adsorption on
Gray Shale increases at lower adsorption time. At higher adsorption time Lithium
concentration in treated sample and Gray shale remains almost constant which is
obtained at time above 180 minutes. Hence it is concluded that equilibrium
concentration of Lithium in Gray Shale is 1.314 ppm at 180 minutes.
0
0.5
1
1.5
2
0 50 100 150 200 250 300
Concentration(ppm)
Time (min)
Gray Shale - Li
Treated
Adsorption

50
4.2.2.1.2 Sodium
Time(min) Untreated(ppm) Treated(ppm) Adsorption(ppm) Adsorption
30 49.1 42 7.8 15.60%
60 49.1 39.69 9.31 18.90%
120 49.1 37.61 11.48 23.10%
180 49.1 34.79 14.21 28.90%
240 49.1 34.66 14.34 29.20%
Table 4- 16: effect of contact time on adsorption of Sodium from produced water for
gray shale
Figure 4- 14: Concentration Sodium v/s contact time for gray shale
Here as shown in table when adsorption time is increased in Gray Shale from 30
minutes to 240 minutes adsorption of Sodium on Gray Shale is increased from 7.8
ppm to 14.34 ppm. If adsorption is expressed in percentage of total concentration,
adsorption increases from 15.60% to 29.20% as adsorption time increases from 30
minutes to 240 minutes. Also Sodium concentration in treated sample decreases
from 42 ppm to 34.66 ppm as adsorption time increases from 30 minutes to 240
minutes. A graph of Concentration v/s Time is plotted that indicates adsorption on
Gray Shale increases at lower adsorption time. At higher adsorption time Sodium
concentration in treated sample and Gray shale remains almost constant which is
obtained at time above 180 minutes. Hence it is concluded that equilibrium
concentration of Sodium in Gray Shale is 34.79 ppm at 180 minutes.
0
5
10
15
20
25
30
35
40
45
0 50 100 150 200 250 300
Concentration(ppm)
Time (min)
Gray Shale - Na
Treated
Adsorption

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