TREATMENT OF CRUDE OIL CONTAMINATED WATER USING

CHEMICALLY ACTIVATED RICE HUSK: PROCESS

OPTIMIZATION USING TAGUCHI

BY

OKON, ANDREW ASUQUO-ITA

(16/ENG01/015)

DEPARTMENT OF CHEMICAL AND PETROLEUM

ENGINEERING, COLLEGE OF ENGINEERING,
AFE BABALOLA UNIVERSITY ADO-EKITI, EKITI STATE,
NIGERIA

JUNE, 2021

i
TREATMENT OF CRUDE OIL CONTAMINATED WATER USING
CHEMICALLY ACTIVATED RICE HUSK: PROCESS
OPTIMIZATION USING TAGUCHI

BY

UKUKU, ANDREW ASUQUO-ITA

(16/ENG01/015)

A RESEARCH PROJECT REPORT SUBMITTED TO THE

DEPARTMENT OF CHEMICAL AND PETROLEUM ENGINEERING,
COLLEGE OF ENGINEERING
AFE BABALOLA UNIVERSITY, ADO-EKITI, EKITI STATE,
NIGERIA

IN PARTIAL FULFILMENT OF THE REQUIREMENT FOR THE

AWARD OF BACHELOR OF ENGINEERING (B.ENG.)
DEGREE IN CHEMICAL ENGINEERING

JUNE, 2021

ii
 DECLARATION
I OKON Andrew Asuquo-ita (16/ENG01/015) hereby declare that this project, “Treatment of
Crude Oil Contaminated Water Using Chemically Activated Rice Husk: Process
optimization using Taguchi”, carried out under the supervision of Engr. Dr. Lekan Taofeek
Popoola and submitted to the Department of Chemical and Petroleum Engineering, Afe Babalola
University Ado-Ekiti in partial fulfilment for the award of Bachelor of Engineering (B.Eng.)
degree in Chemical Engineering.

…………………………… …..………………

OKON, Andrew Asuquo-ita (16/ENG)01/015) Date

……………………………

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 CERTIFICATION
This is to certify that this project titled “Treatment of Crude Oil Contaminated Water Using
Chemically Activated from Rice Husk: Process optimization using Taguchi” was carried out
by OKON Andrew Asuquo-Ita (16/ENG01/015) and submitted in partial fulfilment of the
requirements for the award of Bachelor of Engineering (B.Eng.) Degree in Chemical Engineering.

……………………………………….. …….……………..
Eng. Dr. L. T. Popoola Date
(Project Supervisor)

……………………………………….. …….……………..
Engr. Dr. A. S. Yusuff Date
(Project Coordinator)

……………………………………….. …….……………..
Engr. Dr. O. A. Adesina Date
(Head of Department)

……………………………………….. …….……………..
Engr. Prof. J. A. Sonibare Date
(External Examiner)

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 DEDICATION
I dedicate this project to the Almighty God whose grace and wisdom has kept me going in the
accomplishment of this project. I would also like to dedicate this project to my parents Chief Mr.
& Mrs. Okon, my siblings and friends for their moral support throughout this project. Lastly, I
would like to dedicate this project to my lecturers in the department of chemical and petroleum
engineering of Afe Babalola University and my project supervisor Engr. Dr. Lekan Taofeek
Popoola for all the help and great knowledge they have impacted to me which has been extremely
useful during this project.

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 ACKNOWLEDGEMENT
Firstly, I would like to give thanks to Almighty God the one that has guided and kept throughout
the accomplishment of this project successfully, giving me the strength and health to undertake
this research project. He has been very merciful and has continuously showered blessings upon
me. I would also like to thank my family for supporting me and giving me the moral
encouragement in order to finish this project. My gratitude also goes to my supervisor Engr. Dr.
Lekan Taofeek Popoola for his guidance through the duration of this research project. I also want
to thank my lecturers and nonteaching staffs Mr Donatus and Mrs Favour for their cooperation and
assistance during the course of my project.

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 ABSTRACT

This research project is on the treatment of crude oil contaminated water using chemically
activated rice husk while optimizing using the taguchi experimental design. This study is based on
the production of laboratory scale chemically activated rice husk and investigating its efficiency
as a good adsorbent for reducing hydrocarbon content in crude oil contaminated water using
adsorption process. Rice husk activated with sodium hydroxide was applied for remediation of
crude oil-contaminated water. Taguchi experimental design was employed for process parameters
optimization, which include reaction temperature (40-60oC), rice husk dosage (2,4 and 6 grams),
crude oil concentration (10-30 mL/100mL of water) and reaction time (1-3 hrs). Crude oil
concentration after the remediation was determined using gas chromatograph-mass spectroscopy
(GC-MS). The rice husk was characterized before and after activation with sodium hydroxide
using scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy.
Results revealed optimum crude oil removal of 88.75 % for 10 mL/L of crude oil in water, rice
husk dosage of 6 grams at 60OC reaction temperature and 2 hrs reaction time. Conclusively,
characterization revealed removal of hydrocarbons in crude oil-contaminated water from the rice
husk. I recommend that the developed adsorbent can be utilized for grand scale remediation of
crude oil contaminated water. The effect of other adsorption parameters such as, pH and speed can
be investigated

Keywords: Crude oil, Rice husk, Contamination, Adsorption, Chemical activation, Sodium
hydroxide.

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TABLE OF CONTENTS
DECLARATION ........................................................................................................................................... i
CERTIFICATION ........................................................................................................................................ ii
DEDICATION ............................................................................................................................................. iii
ACKNOWLEDGEMENT ........................................................................................................................... iv
ABSTRACT .................................................................................................................................................. v
TABLE OF CONTENTS ............................................................................................................................. vi
LIST OF FIGURES ................................................................................................................................... viii
LIST OF TABLES ....................................................................................................................................... ix
1 INTRODUCTION ................................................................................................................................ 1
1.1 Background of Study .................................................................................................................... 1
1.2 Problem Statement ........................................................................................................................ 2
1.3 Aim ............................................................................................................................................... 3
1.4 Objectives ..................................................................................................................................... 3
1.5 Research scope and limitations ..................................................................................................... 3
1.6 Significance of Study .................................................................................................................... 3
2 LITERATURE REVIEW ..................................................................................................................... 4
2.1 Pollution ........................................................................................................................................ 4
2.1.1 Causes ................................................................................................................................... 6
2.1.2 Effects ................................................................................................................................... 7
2.2 Crude oil........................................................................................................................................ 9
2.2.1 Types of crude oil ............................................................................................................... 11
2.2.2 Chemical Properties of crude oil ......................................................................................... 12
2.2.3 Physical Properties of crude oil........................................................................................... 14
2.3 Adsorption................................................................................................................................... 15
2.3.1 Types of Adsorption............................................................................................................ 15
2.3.2 Applications of Adsorption ................................................................................................. 17
2.3.3 Adsorption Isotherms .......................................................................................................... 17
2.4 Rice husk..................................................................................................................................... 21
2.4.1 Characteristics of the rice husk ........................................................................................... 22
2.4.2 Utilization of the rice husk .................................................................................................. 24
2.5 Taguchi Experimental Design ..................................................................................................... 24
3 METHODOLOGY ............................................................................................................................. 26

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 3.1 Materials used ............................................................................................................................. 26
3.2 Equipment used ........................................................................................................................... 26
3.3 Activation of rice husk using NaOH ........................................................................................... 27
3.3.1 Procedures ........................................................................................................................... 27
3.4 Batch Adsorption Experiment ..................................................................................................... 27
3.4.1 Procedures ........................................................................................................................... 28
4 DISCUSSION OF RESULTS ............................................................................................................. 29
4.1 Analysis of variance .................................................................................................................... 30
4.2 Diagnostic case statistics............................................................................................................. 31
4.3 Paremeter Intearaction ................................................................................................................ 32
4.4 Rice husk characterization .......................................................................................................... 38
4.4.1 Scanning electron microscopy (SEM) analysis................................................................... 38
4.4.2 Fourier transform infrared (FTIR) analysis......................................................................... 40
5 CONCLUSION AND RECOMMENDATIONS ................................................................................ 42
5.1 Conclusions ................................................................................................................................. 42
5.2 Recommendations ....................................................................................................................... 42
REFERENCES ........................................................................................................................................... 44

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LIST OF FIGURES
Figure 2-1:Oil spillage from tanker ................................................................................................ 5
Figure 2-2:oil spill in the ocean ...................................................................................................... 5
Figure 2-3:crude oil sample .......................................................................................................... 11
Figure 2-4: Rice husks (Wikipedia, 2020) .................................................................................... 21
Figure 4-1:Plot of Rice husk dosage and temperature against crude oil removal ........................ 32
Figure 4-2: Plot of crude oil concentration and temperature against crude oil removal............... 33
Figure 4-3: Plot of time and rice husk dosage against crude oil removal ..................................... 34
Figure 4-4: Plot of time and temperature against crude oil removal ............................................ 35
Figure 4-5: Plot of crude oil concentration and rice husk dosage against crude oil removal ....... 36
Figure 4-6:Plot of crude oil concentration and time against crude oil removal............................ 37
Figure 4-7: Scanning electron microscopy (SEM) of chemically activated rice husk before crude
oil adsorption ................................................................................................................................ 38
Figure 4-8: Scanning electron microscopy (SEM) of chemically activated rice husk after crude oil
adsorption ...................................................................................................................................... 39
Figure 4-9:FTIR analysis of rice husk before adsorption of crude oil .......................................... 40
Figure 4-10: FTIR analysis of rice husk after adsorption of crude oil.......................................... 40

viii
LIST OF TABLES
Error! Reference source not found.…………Error! Bookmark not defined.

Table 3-1: Design of Experiment…………………………………………………...28

Table 4-1: Table of Results…………………………………………………………29

Table 4-2: Table for Analysis of variance…………………………………………..30

Diagnostic case statistics

Table 4-3:Table for Diagnostic Case Statistics…………………………………….31

ix
 CHAPTER ONE

1 INTRODUCTION
1.1 Background of Study

Crude oil or just oil, is a naturally occurring, yellowish-black liquid found in geological formations
beneath the Earth's surface. It is commonly refined into various types of fuels. Components of
petroleum are separated using a technique called fractional distillation, i.e. separation of a liquid
mixture into fractions differing in boiling point by means of distillation, typically using a
fractionating column. It consists of naturally occurring hydrocarbons of various molecular weights
and may contain miscellaneous organic compounds. The name petroleum covers both naturally
occurring unprocessed crude oil and petroleum products that are made up of refined crude oil. A
fossil fuel, petroleum is formed when large quantities of dead organisms, mostly zooplankton and
algae, are buried underneath sedimentary rock and subjected to both intense heat and pressure.

Oil Pollution is the resultant contamination of environment due to the introduction/presence of oil
in excessive quantity. Oil pollution is most common in large water bodies like seas and oceans.
Oil spill occurs due to the release of a liquid petroleum hydrocarbon into the aquatic environment.
Marine water is especially affected by this form of pollution. Oil pollution is primarily a man-
made pollution and is a result of human irresponsible activities. Oil pollution is mainly because of
crude oil. Ships and tankers carrying crude oil across the oceans may cause deadly oil spills in
marine water due to various causes, leakage being the most common one. The quantity of oil spills
matter when it comes to the significance of oil and water pollution. During marine accidents, the
oil spills quantity is enormous. Spillages in such large quantities occur on a regular basis. Also,
shallow water oil spills can be more dangerous than deep water ones sometimes. Oil combines
with mud and other dirty substances and sinks to the bottom of the water bodies. As a result of
this, the oil tends to stay at the bottom for ages causing harmful effects on the marine life living
on the bed of the sea. When very large amount of oil pollution occurs, it is extremely tedious to
clean up the water afterwards. Measures taken to reverse the pollution affects may prove futile, if
action is not taken at the right time. So, it is wise to take preventive measures rather than treatment
ones. Prevention is an important action step but awareness precedes this step.

1
Adsorption is a separation process where molecules tend to concentrate on the surface of the
adsorbent as a result of Van der Waals force which exists between the molecules. The
adsorbability of a compound increases with: increasing molecular weight, a higher number of
functional groups such as double bonds or halogen compounds, increasing polarizability of the
molecules. This phenomenon is applied for wastewater reuse. The adsorption force is the sum of
all the interactions between all the atoms. The short range and additive nature of these forces
results in activated carbon having the strongest physical adsorption forces of any known materials.
(Ujile, 2014) Adsorption can be either physical or chemical in nature. Physical adsorption
resembles the condensation of gases to liquids and depends on the physical, or van der Waals,
force of attraction between the solid adsorbent and the adsorbate molecules. There is no chemical
specificity in physical adsorption, any gas tending to be adsorbed on any solid if the temperature
is sufficiently low or the pressure of the gas sufficiently high. In chemical adsorption, gases are
held to a solid surface by chemical forces that are specific for each surface and each gas. Chemical
adsorption occurs usually at higher temperatures than those at which physical adsorption occurs;
furthermore, chemical adsorption is ordinarily a slower process than physical adsorption and, like
most chemical reactions, frequently involves an energy of activation. (Britannica, 2020)

1.2 Problem Statement

If oil contaminated water is not treated it may lead to negative impact on the environment
and can also lead to health risks. These impacts can include harm to fish and wildlife
populations, oxygen depletion, they can also lead to loss of livelihood(i.e. fishing) due to
the absence of wild life due to the inability for animals to survive in such an environment,
which in turn can lead to shortage in food supply especially in riverine areas which majorly
depend on fish for food. It can also lead to water shortages especially in areas which do not
have water treatment facilities. It will also lead to health risks for individuals living in such
areas.

2
1.3 Aim
To treat crude oil contaminated water using chemically activated rice husk by means of adsorption

1.4 Objectives
The objectives of this study are;

• To prepare chemically activated rice husk using sodium hydroxide

• To treat crude oil contaminated water using the chemically activated rice husk
• Characterize the prepared adsorbent in (ii.) above using various techniques such as
scanning electron microscopy (SEM), Fourier Transform Infrared (FTIR)

1.5 Research scope and limitations

This study is based on the production of laboratory scale chemically activated rice husk
using sodium hydroxide and investigating its efficiency as a good adsorbent for the treating of
crude oil contaminated water. Adsorbent dosage, and concentration and temperature were
investigated in this research work which had been known to affect the adsorptive efficiency of
activated carbon and the optimum value for each was obtained.

1.6 Significance of Study

This study is to provide information on the application of adsorption process in the treatment of
crude oil contaminated water and how factors such as temperature, mass dosage and concentration
affect the treatment process.

3
 CHAPTER TWO

2 LITERATURE REVIEW
2.1 Pollution

Pollution, also called environmental pollution, the addition of any substance (solid, liquid, or gas)
or any form of energy (such as heat, sound, or radioactivity) to the environment at a rate faster
than it can be dispersed, diluted, decomposed, recycled, or stored in some harmless form. The
major kinds of pollution, usually classified by environment, are air pollution, water pollution, and
land pollution. Modern society is also concerned about specific types of pollutants, such as noise
pollution, light pollution, and plastic pollution. Pollution of all kinds can have negative effects on
the environment and wildlife and often impacts human health and well-being. (Nathanson, 2010)

Oil Pollution is the resultant contamination of environment due to the introduction/presence of oil
in excessive quantity. Oil pollution is most common in large water bodies like seas and oceans.
Oil spill occurs due to the release of a liquid petroleum hydrocarbon into the aquatic environment.
Marine water is especially affected by this form of pollution. Oil pollution is primarily a man-
made pollution and is a result of human irresponsible activities. Oil pollution is mainly because of
crude oil. Ships and tankers carrying crude oil across the oceans may cause deadly oil spills in
marine water due to various causes, leakage being the most common one. The quantity of oil spills
matter when it comes to the significance of oil and water pollution. During marine accidents, the
oil spills quantity is enormous. Spillages in such large quantities occur on a regular basis. Also,
shallow water oil spills can be more dangerous than deep water ones sometimes. Oil combines
with mud and other dirty substances and sinks to the bottom of the water bodies. As a result of
this, the oil tends to stay at the bottom for ages causing harmful effects on the marine life living
on the bed of the sea. When very large amount of oil pollution occurs, it is extremely tedious to
clean up the water afterwards. Measures taken to reverse the pollution affects may prove futile, if
action is not taken at the right time. So, it is wise to take preventive measures rather than treatment
ones. Prevention is an important action step but awareness precedes this step.

4
Figure 2-1:Oil spillage from tanker

Figure 2-2:oil spill in the ocean

5
2.1.1 Causes

1. Breakage of oil tankers (oil ships): Mechanical breakage of oil tankers can lead to oil
spillage in extremely large quantities. If a tanker breaks down in shallow land, abrasion
leading to a hole in the tanker might take place during mechanical and aggressive attempts
to get the tanker out of the shoreline. Also, when bunker oil or lubricating oil (required for
engines) is being loaded in to any ship, the loading hose can also undergo mechanical
breakage leading to oil spillage incidents.
2. Oil pipe leakage: Oil pipe leakages are common and cause a lot of oil pollution. Huge
pipelines are laid all across the world and their slightest leakage can prove to of grave danger
to water bodies. Offshore drilling waste should be handled with care and their proper and
lawful disposal should be ensured.
3. Drilling activities: Drilling activities lead to severe oil pollution. Industries after oil
extractions dump the drilling wastes into water bodies. This is extremely detrimental for
natural water sources. Companies act irresponsible towards the environment and carry out
improper disposal of drilling waste.
4. Human transport or recreational activities: Oil spills may be a result of water sports as
well as motor transport on water. Fuel leaks from jet skis, speed boats, etc. can also lead to
oil spills. Some water bodies have regular motor traffic on them. These water bodies tend to
have concentrated oil pollution in their water due to constant oil pollution.
5. Unskilled Manpower: Unprofessional, careless and unskilled man-power can also be a risk
factor for oil pollution. They might do a clumsy job of loading or unloading the crude oil
cargo which may prove to be dangerous. Also, applying shortcuts and not following the
lawful protocol for cleaning, loading, supervising and unloading, when handling crude oil
tankers is often seen among the crew members.
6. Failing to check failures: It is important to check for any failing equipment or parts of a
marine vessel before giving it a green signal for making a sea voyage. Any potential failure
incidents should be immediately addressed and not look past. Even minute failures can
create havoc late. Failing engines in the middle of the sea can lead to substantial oil pollution.
7. Natural causes beyond human control: Natural calamities like storms and tsunamis have
also led to many oil spillage and ship accidents. This is beyond human control and cause

6
 maximum damage to marine water. Climatic conditions are something that cannot be
bypassed when talking about marine life.
8. Operational oil spills: In any ship, bilge is a space found under the ship engines, at the very
base. It is for gathering oil, greasy dirt and water. When the bilge is pumped out by the ship
crew, the oil and water separates. The oily waste is supposed to be stocked into a designated
holding tank, which is to be thrown out at the next available port. The water that is left over
(having oil traces in negligible quantities) is pumped into the ocean after passing it through
an oil water separator. This extensive procedure is done to ensure that only traces amount of
oil is being pumped out overboard. Hence, if an oil slick is found around a ship, it shows
that the ship has not followed the right lawful procedure and has illegally pumped out more
oil into the ocean than it is permitted to.
9. Cleaning of tanks: When oil tanks of ships are cleaned, there is high risk of oil spillage in
the ocean water. Before loading the new cargo of crude oil into their ship, the ship crew
usually cleans the cargo tanks. After thorough cleaning of the cargo oil tank with chemicals
and water, the remnant oil residue float on the water at the very base of the cargo tank. This
water is normally channelled to an oil water separator to separate only the cargo oily residue
at the cargo tank bottom. The fresh crude oil cargo can ideally be loaded over the left-over
old cargo oil. However, some crew members tend to pump out the remnant old cargo oil
residue overboard into the ocean water. This is strictly illegal and should not be encouraged
at any cost. This leads to discharging of tons of dirty oil residue into the marine water to
cause oil pollution.
10. Run offs from land pollution: Polluting human activities on land may also contribute to
water oil pollution. The vehicular oil leaks on land may also get washed off into seas, oceans
and other natural water bodies leading to oil pollution. (importantindia.com, 2016)

2.1.2 Effects
The effect of oil pollution is disastrous, especially on the aquatic flora and fauna. Given below are
various possible adverse effects of oil pollution.

7
1. Damage to ecosystem: Oil pollution is a major threat to our ecosystem, especially the
aquatic ecosystem. Ecological impact of oil spills on the aquatic animals depends on the
location of the oil spills and also on the sensitivity of the local organisms to oil pollution.
Oil spills greatly decrease animal breeding population and also harm their nesting habitats.
This leads to the consequent shrinkage of the local prey population thus unbalancing the
aquatic food chain and ecosystem. Plants in the water also cannot survive in poisonous oily
environment and die a pre mature death, ahead of their life cycles.
2. Damaging effect marine biodiversity: Marine biodiversity will get great affected by oil
pollution. Oil spills can cause potential harm to the marine birds. Their feathers get coated
with the oily water which hampers with the water repelling property of their plumage. This
might increase their chances of drowning in water as their buoyancy might considerably
decrease. Also, aquatic animals and birds and mammals may tend to ingest the oily
contaminated water which could mean harm to their health by poisoning them. Oil spills are
also dangerous for fish and shellfish. Oil ruins the insulating capability of furry mammals
like sea otters. This may adversely affect their body temperature maintenance. Oil spill
happens all over the sea and the location decides the injury or death rate of the birds and
animals. It is a pity how human activities are constantly upsetting the marine biodiversity.
3. Economic loss: Oil spillage if happens in high concentrations is very difficult to clean, no
matter how much effort is invested into it. Also, the cleanliness regime is anything but cheap.
Huge amount of money needs to be spent to tidy up the oil spillage mess and then also the
result may not be 100% satisfactory. Oil pollution is proportional to considerable economic
loss. Also, spillage of crude oil is of great loss as crude oil is precious and very expensive.
4. Altering the water temperature: The oil layer present at the surface of water will tend to
absorb more heat from sun rays and may significantly increase the surface water
temperature. Also, it might block the sunlight from reaching into the depths of water with
uneven heat distribution across the depths of the water body. This can alter the natural
hydrodynamics of the water bodies which may lead to lesser oxygen supply at certain depths
of water.
5. Effect on coastal areas: The shore lines and sandy beaches in coastal areas may also be an
indirect victim of oil water pollution. The oil contaminated water is usually swept across the

8
 shoreline by the waves in high tides. This makes the beaches dirty and unsafe for the human
population as well. Thus, coastal areas are continuously contaminated due to oil pollution.
6. Degrades water quality: Oil pollution seriously degrades the water quality on a long-term
basis. Being insoluble in water, oily water always exists as bi-layer. Also, at the shore lines,
the current of waves might even turn the oily water into a turbid oil water emulsion (wherein
the oil and water exist as a single turbid phase due to constant mechanical mixing forces).
This degrades the quality of water further.
7. Tourism industry affected: Tourism industry is greatly affected by oil spills and oil
pollution. Due to increasing oil pollution on beaches and shorelines, recreational activities
of tourists like boating, swimming, diving, adventure sports are taking a back seat. Unclean
and unhealthy water will repel tourists from undertaking these activities completely.
8. Industry problems: Many industries use clean water from natural water bodies for cooling
purposes. Industries like power plants, nuclear plants and desalination plants need constant
water supply from surface waters. These industries may also pose a risk of getting oily and
contaminated water due to oil pollution. This may lead to contamination in their pipes and
might not yield effective cleaning too.

2.2 Crude oil

Crude oil is a colloidal mixture of huge number of hydrocarbon and non-hydrocarbon (Cadwallaer,
1993). The source material for nearly all petroleum products is crude oil. Spill, leaks and other
releases of gasoline, diesel, fuels, heating oils and other petroleum products often result in the
contamination of soil and water. Hydrocarbon form over 90 percent petroleum oil are grouped
according to their chemical structures such as straight, branched and cyclic alkanes and aromatics.
The non-hydrocarbon components of petroleum include (O2, N, S ---) and some metals related
porphyrin oxygen containing compounds e.g. naphthenic acid, carboxylic acid, esters, ketones,
phenols etc (Odu, 1981). Oil pollution occurs when oil is introduced into the environment directly
or indirectly by men’s impacts resulting in unfavourable change in such a way that safety and
welfare of any living organisms is endangered. Crude oil if spilled into the water spreads over a
wide area forming a slick and oil in water immediately begins to undergo a variety of physical,
chemical and biological changes including evaporation of high volatile fractions, dissolution of
water-soluble fractions, photochemical oxidation, drill, emulsification, microbial degradation and

9
sedimentation (Muller, 1987). Crude oil is a complex mixture of hydrocarbon and organic
compounds of sulphur, nitrogen, oxygen and a certain quantity of water which varies in
composition from place to place (Anoliefo, 1991). Crude oil is produced from decay of plants and
animals over millions of years. It is also referred to as mineral oil. Crude oil, which is a mixture
of hydrocarbons and inorganic compounds is drilled through rocks. Crude oil discharged on the
sea surface undergoes physical, chemical and biological alteration. Rapid physical and chemical
processes include spreading and movement by wind and currents, injection into the air, evaporation
of volatile components, dispersion of small droplets into water, dissolution and chemical oxidation
(Nelson Smith, 1972). Concurrent with these are relevant biological processes. They include
degradation by micro-organisms and uptake by larger organisms followed by metabolism and
storage or discharge (Edema, 2012)

Crude oil occurs underground, at various pressures depending on depth. It can contain considerable
natural gas, kept in solution by the pressure. In addition, water often flows into an oil well along
with liquid crude and gas. All these fluids are collected by surface equipment for separation. Clean
crude oil is sent to storage at near atmospheric pressure, usually aboveground in cylindrical steel
tanks that may be as large as 30 metres (100 feet) in diameter and 10 metres (33 feet) tall. Often
crude oil must be transported from widely distributed production sites to treatment plants and
refineries. Overland movement is largely through pipelines. Crude from more isolated wells is
collected in tank trucks and taken to pipeline terminals; there is also some transport in specially
constructed railroad cars. Overseas transport is conducted in specially designed tanker ships.
Tanker capacities vary from less than 100,000 barrels to more than 3,000,000 barrels.

The primary destination of crude oil is a refinery. There any combination of three basic functions
is carried out: (1) separating the many types of hydrocarbon present in crude oils into fractions of
more closely related properties, (2) chemically converting the separated hydrocarbons into more
desirable reaction products, and (3) purifying the products of unwanted elements and compounds.
The main process for separating the hydrocarbon components of crude oil is fractional distillation.
Crude oil fractions separated by distillation are passed on for subsequent processing into numerous
products, ranging from gasoline and diesel fuel to heating oil to asphalt. The proportions of
products that may be obtained by distillation of five typical crude oils, ranging from heavy
Venezuelan Boscan to the light Bass Strait oil produced in Australia, are shown in the figure. Given

10
the pattern of modern demand (which tends to be highest for transportation fuels such as gasoline),
the market value of a crude oil generally rises with increasing yields of light products (Britannica,
2020)

Figure 2-3:crude oil sample

As we have now established, ‘Crude Oil’ is a term used to describe many different types of raw
oil extracted from the ground. Within the industry, we categorize these different types into four
main categories based on three factors: their viscosity, volatility, and toxicity.

• Viscosity refers to the oils ability to flow. Higher viscosity oils do not flow as easily and
therefore take more energy and effort to pump from the ground.
• Volatility describes how quickly and easily the oil evaporates into the air. Higher volatility
oils need additional processes to control their environments during extraction to ensure that
as little oil as possible is lost.
• Toxicity refers to how poisonous and harmful the oil is to the environment, wildlife, and
humans during the extraction and refinement process. When oil spills do occasionally
occur, each oil poses different challenges and priorities during the clean-up.

2.2.1 Types of crude oil

With that said, the four main types of Crude Oil are:

11
 • Very light oils – these include: Jet Fuel, Gasoline, Kerosene, Petroleum Ether, Petroleum
Spirit, and Petroleum Naphtha. They tend to be very volatile, evaporating within a few
days which in turn evaporates their toxicity levels.
• Light oils – These include Grade 1 and Grade 2 Fuel Oils, Diesel Fuel Oils as well as Most
Domestic Fuel Oils. They are both moderately volatile and toxic.
• Medium oils – These are the most common types of Crude Oil. They generally have low
volatility and a higher viscosity than the light oils which leads to higher toxicity and a
greater environmental impact during clean-ups.
• Heavy fuel oils – These include the heaviest Grade 3,4,5 and 6 Fuel Oils along with Heavy
Marine Fuels. These are the most viscous and least volatile Crude Oils as well as the most
toxic. (Plainsman Mfg. In, 2017)

2.2.2 Chemical Properties of crude oil

The chemical properties of crude oil deal with the chemical nature and the changes in composition
in relation to temperature and pressure variations occurring at all times within the oil pool. Some
of the chemical properties are related to the origin, migration, and accumulation of the crude oil.
(Madu Anthony, 2015)

• Chemical Nature: Crude oils are composed of liquid hydrocarbon compounds of: paraffin
series ranging from pentane to pentadecane (C5- C15), varying amounts of naphthenes,
alkyl benzenes, aromatics, trace amount of semi-solid to solid phase hydrocarbons such as
asphaltic matters and waxes. Other secondary constituents are sulphur, nitrogen, oxygen,
carbon dioxide, trace metals which include silicon, iron, aluminium, calcium, magnesium,
copper, lead, tin, zinc, nickel, molybdenum and vanadium. Various hydrocarbon
compounds in crudes have been isolated and analysed at different temperatures ranging
from 40 – 1800C. These hydrocarbons consist essentially of hydrogen and carbon. Some
of the compounds are saturated with hydrogen while others are not. A crude oil is
categorized on the basis of the most abundant group of hydrocarbons it contains. A crude
oil can be described as paraffin base, naphthene base or mixed base (i.e naphthenic-paraffin
base) depending on the percentage composition of its hydrocarbon fractions The paraffin
base crude oils have low density (high A.P.I gravities), and in chemical refineries yield

12
 high amount of gasoline and kerosene. The naphthene base crudes produce high amount of
lubricating oils, less gasoline and kerosene as the refinery products. Hydrogenation of
crude oils: During the early stages of crude oil formation, there is a remarkable thermal
cracking of the organic materials into decomposed complexes, and the coupling activity of
anaerobic bacteria processes, and the catalytic influence of such available trace metals as
vanadium and nickel, lead, to the transformation of the complex organic matter into alkene
rich paraffinic oil. And according to Zobel (1947), reservoir catalytic chemical reactions
lead to the dissociation of avail sulphides into free sulphur and hydrogen. The elemental
hydrogen would convert the alkene rich paraffinic crude oil into an accumulation of
gaseous paraffinic oils (of high A.P.I gravity), in relatively close association with the
kerogen (or organic source rock).

• Paraffin wax content Paraffin waxes in crude oils are semi-solid to solid forms of
hydrocarbons, consisting mainly of normal paraffins. These n-paraffins range from about
C5 – C30. Admixtures of branched-chain paraffins are also contained. Hedberg (1968),
described waxes as complex petroleum substances whose complexity is caused by
molecular mixture of branched chain and n-paraffin hydrocarbons, with molecular weights,
high enough to be solids at ordinary temperatures.

• Trace Metals in Crude Oils: Crude oils contain varying amounts of trace elements some of
which include, iron, aluminium calcium, magnesium, copper, lead, tin, astemum,
antimony, zinc, silver, nickel, chromium, molybdoniura and vanadium. But the most
important of these trace elements are vanadium, nickel and iron. The concentration of any
of these trace metals is so small that the value is expressed in parts per million. The
concentration of trace metals in any crude oil is found to be inversely proportional to the
A.P.l gravity of the oil.

Some other chemical properties include;

• Porphyrins in crude oil

13
 • Odd carbon chain lengths

• Carbon isotope ratio, etc.

2.2.3 Physical Properties of crude oil

The physical properties of crude oils are the quantitatively measurable characteristics of crude oils.
They vary according to the composition of the oil, the relative abundance of the groups of
hydrocarbons, and essentially depend on reservoir temperatures and pressures. (Madu Anthony,
2015)

• Viscosity: This is the measure of resistance to flow in crude oils due to internal friction. It
is expressed in 'poise' or ‘centipoise’. crude oil is said to have a viscosity of 1 poise when
a tangential force of 1 dyne causes a plane surface of 1 square centimetre area; spaced 1
cm from a stationary plane surface to move with a constant velocity of 1 cm per second,
the space being filled with the viscous c. The viscosity of a crude oil is influenced by the
amount of dissolved gases at the prevailing temperature. Crudes characterized by high
amount of dissolved gases have high A.P.I gravities and low viscosity or moderately high
fluidity; illustrated in figure 2. At high temperatures molecular agitation (or velocity) of
the crude increases, making for a volumetric expansion and reduction in internal molecular
friction, thus, reducing the oil. The greater the quantity of a high-molecular weight
hydrocarbon group in a crude, the denser and more viscous.
• Colour: This is the light transmitted through crude oils. It is yellowish to red for light oils
and dark or even opaque for heavy (or low A.P.I gravity) oils.
• Odour: This varies greatly in crude oils. High content of light hydrocarbons (paraffins and
naphthenes) in a crude gives rise to a gasoline-like odour. A pleasant odour is produced if
the crude has abundant aromatic hydrocarbons. But with high amount of unsaturated
hydrocarbon compounds, sulphur and nitrogen compounds in the oil, it produces a
repugnant odour.
• Flash Point This is the temperature at which the volatiles rising off the surface of heated
oil will ignite with a flash, on passing a flame over the surface. This provides some clue
about the gaseous content of the crude oil.

14
Some other physical properties of crude oil;

• Refractive index
• Surface tension effect
• Aqueous solubility
• Coefficient of expansion, etc.

2.3 Adsorption

Adsorption is a separation process where molecules tend to concentrate on the surface of the
adsorbent as a result of Van der Waals force which exists between the molecules. The
adsorbability of a compound increases with: increasing molecular weight, a higher number of
functional groups such as double bonds or halogen compounds, increasing polarizability of the
molecules. This phenomenon is applied for wastewater reuse. The adsorption force is the sum of
all the interactions between all the atoms. The short range and additive nature of these forces
results in activated carbon having the strongest physical adsorption forces of any known materials.
(Ujile, 2014) Adsorption can be either physical or chemical in nature. Physical adsorption
resembles the condensation of gases to liquids and depends on the physical, or van der Waals,
force of attraction between the solid adsorbent and the adsorbate molecules. There is no chemical
specificity in physical adsorption, any gas tending to be adsorbed on any solid if the temperature
is sufficiently low or the pressure of the gas sufficiently high. In chemical adsorption, gases are
held to a solid surface by chemical forces that are specific for each surface and each gas. Chemical
adsorption occurs usually at higher temperatures than those at which physical adsorption occurs;
furthermore, chemical adsorption is ordinarily a slower process than physical adsorption and, like
most chemical reactions, frequently involves an energy of activation.

2.3.1 Types of Adsorption

On the basis of interaction forces between adsorbate and adsorbent, adsorption is of two types.

15
Physical adsorption: This type of adsorption is also known as physisorption. It is due to weak
Van der Waals forces between adsorbate and adsorbent. H2 and N2 gases adsorb on coconut
charcoal.

Characteristics of physical adsorption:

• This type of adsorption is caused by physical forces.

• Physisorption is a weak phenomenon.
• This adsorption is a multi-layered process.
• Physical adsorption is not specific and takes place all over the adsorbent.
• Surface area, temperature, pressure, nature of adsorbate effects physisorption.
• Energy for activation is low (20 – 40 kg/mol).

Chemical adsorption: This type of adsorption is also known as chemisorption. It is due to strong
chemical forces of bonding type between adsorbate and adsorbent. We can take the example
involving the formation of iron nitride on the surface when iron is heated in N2 gas at 623 K.

Characteristics of chemical adsorption:

1. This type of adsorption is caused by chemical forces.

2. It is a very strong process.
3. This type of adsorption is almost a single-layered phenomenon.
4. Chemisorption is highly specific and takes place at reaction centres on the adsorbent.
5. Surface area, temperature, nature of adsorbate effects chemisorption.
6. Energy of activation is very high 40 – 400 kJ/mol.

16
2.3.2 Applications of Adsorption

• Air pollution masks: These consists of silica gel or activated charcoal powder, when dust
or smoke are paused through them, those particles get adsorbed on the surface of these
materials.

• Separation of noble gases by Dewar’s flask process: A mixture of noble gases of Ne, Ar,
Kr is passed through Dewar’s flask in presence of heated coconut charcoal. Argon and
Krypton gels adsorbed leaving Neon.

• Purification of water: By the addition of alum stone to the water, impurities get adsorbed
on the alum and water gets purified.

• Removal of moisture and humidity: Moisture in the air is removed by placing silica gel on
which water molecular gets adsorbed.

• Adsorption chromatography: It is used to separate pigments and hormone.

• Ion exchange method: In this method of removing the hardness of water, calcium and
magnesium ions get adsorbed on the surface of ion exchange resin

• In metallurgy: In froth floatation process of concentration of ore, the particle gets adsorbed
on the froth.

2.3.3 Adsorption Isotherms

The adsorption of gases and solutes is usually described through isotherms, that is, the amount of
adsorbate on the adsorbent as a function of its pressure (if gas) or concentration (for liquid phase
solutes) at constant temperature. The quantity adsorbed is nearly always normalized by the mass
of the adsorbent to allow comparison of different materials

In 1909, Freundlich gave an empirical expression representing the isothermal variation of

adsorption of a quantity of gas adsorbed by unit mass of solid adsorbent with pressure. This

17
equation is known as Freundlich Adsorption Isotherm or Freundlich Adsorption equation or simply
Freundlich Isotherm.

Where x is the mass of the gas adsorbed on mass m of the adsorbent at pressure p and k, n are
constants whose values depend upon adsorbent and gas at particular temperature. Though
Freundlich Isotherm correctly established the relationship of adsorption with pressure at lower
values, it failed to predict value of adsorption at higher pressure.

Langmuir Adsorption Isotherm

In 1916 Langmuir proposed another Adsorption Isotherm known as Langmuir Adsorption

isotherm. This isotherm was based on different assumptions one of which is that dynamic
equilibrium exists between adsorbed gaseous molecules and the free gaseous molecules.

Where A(g) is unadsorbed gaseous molecule, B(s) is unoccupied metal surface and AB is
Adsorbed gaseous molecule.

Based on his theory, he derived Langmuir Equation which depicted a relationship between the
number of active sites of the surface undergoing adsorption and pressure.

Where θ the number of sites of the surface which are covered with gaseous molecule, P represents
pressure and K is the equilibrium constant for distribution of adsorbate between the surface and
the gas phase. The basic limitation of Langmuir adsorption equation is that it is valid at low
pressure only.

At lower pressure, KP is so small, that factor (1+KP) in denominator can almost be ignored. So,
Langmuir equation reduces to

18
θ = KP

At high pressure KP is so large, that factor (1+KP) in denominator is nearly equal to KP. So,
Langmuir equation reduces to

BET adsorption Isotherm

BET Theory put forward by Brunauer, Emmett and Teller explained that multilayer formation is
the true picture of physical Adsorption.

One of the basic assumptions of Langmuir Adsorption Isotherm was that adsorption is monolayer
in nature. Langmuir adsorption equation is applicable under the conditions of low pressure. Under
these conditions, gaseous molecules would possess high thermal energy and high escape velocity.
As a result of this smaller number of gaseous molecules would be available near the surface of
adsorbent.

Under the condition of high pressure and low temperature, thermal energy of gaseous molecules
decreases and more and more gaseous molecules would be available per unit surface area. Due to
this multilayer adsorption would occur. The multilayer formation was explained by BET Theory.
The BET equation is given as

The another form of BET equation is

Where V mono be the adsorbed volume of gas at high pressure conditions so as to cover the surface
with a unilayer of gaseous molecules,

19
the ratio is designated C. K1 is the equilibrium constant when single molecule adsorbed per vacant
site and KL is the equilibrium constant to the saturated vapor liquid equilibrium.

Factors which affect the extent of adsorption

1 Nature of the adsorbate (gas) and adsorbent (solid)

• In general, easily liquefiable gases e.g., CO2, NH3, Cl2 and SO2 etc. are adsorbed to a
greater extent than the elemental gases e.g. H2, O2, N2, He etc. (while chemisorption is
specific in nature.)
• Porous and finely powdered solid e.g. charcoal, fullers earth, adsorb more as compared to
the hard non-porous materials. Due to this property powdered charcoal is used in gas
masks.

2 Surface area of the solid adsorbent

• The extent of adsorption depends directly upon the surface area of the adsorbent, i.e. larger
the surface area of the adsorbent, greater is the extent of adsorption.
• Surface area of a powdered solid adsorbent depends upon its particle size. Smaller the
particle size, greater is its surface area.

3 Effect of pressure on the adsorbate gas

• An increase in the pressure of the adsorbate gas increases the extent of adsorption.
• At low temperature, the extent of adsorption increases rapidly with pressure.
• Small range of pressure, the extent of adsorption is found to be directly proportional to the
pressure.
• At high pressure (closer to the saturation vapour pressure of the gas), the adsorption tends
to achieve a limiting value.

4 Effect of temperature

20
 • As adsorption is accompanied by evolution of heat, so according to the Le-Chatelier’s
principle, the magnitude of adsorption should decrease with rise in temperature.
• The relationship between the extent of adsorption and temperature at any constant pressure
is called adsorption isobar.
• The isobar of chemisorption shows an increase in the beginning and then decrease as the
temperature rises.

2.4 Rice husk

Rice husk, also called rice hull, is the coating on a seed or grain of rice. It is formed from hard
materials, including silica and lignin, to protect the seed during the growing season. Each kg of
milled white rice results in roughly 0.28 kg of rice husk as a by-product of rice production during
milling.

Figure 2-4: Rice husks

Rice husk is a promising adsorbent material for removing different contaminants because it is a
low-cost and renewable resource. The typical chemical composition of rice husks is about 32%
cellulose, 20% hemicellulose, 21% of lignin, and 20% of other organic matter, such as protein and
fat Presently, much rice husk is discarded directly into the soil or burnt, which results in
environmental pollution. However, thermochemical conversion of rice husk, such as by pyrolysis,

21
gasification, and combustion, can be used to generate value-added by-products [8], and thus
substantially reduce the pressure on the environment. Rice husk has been extensively utilized to
adsorb phenolic compounds copper, lead, hexavalent chromium [Cr(VI)], malachite green, 2, 4-
dichlorophenol, cadmium, zinc and manganese, selenium, humic acids, oil and oil products, dye,
and fluoride (Samah Babiker Daffalla, 2020).

Common products from rice husk are: solid fuel (i.e., loose form, briquettes, and pellets),
carbonized rice husk produced after burning, and the remaining rice husk ash after combustion.
Rice husk in its loose form is mostly used for energy production, such as combustion and
gasification. Combustion is the process of burning carbon in the rice husk, which emits CO 2 and
generates heat energy for further use. One of the most efficient uses of this by-product is its direct
combustion without the need for a heat exchanger with a proper furnace to generate heat for
drying paddy. Gasification is the process of converting rice husk to synthesis gas (syngas) in a
gasifier reactor with a controlled amount of air. Syngas can be used as fuel for drying and cooking
or in a cogeneration system to produce electricity.
Rice husk briquettes and pellets are produced using densification to increase the density of
materials and their combustion performance. These densified rice husks are mainly used in
industrial boilers as a substitute for fossil fuel.
Rice husk ash is the remaining by-product after combustion is done. The amount of carbon
remaining in ash depends on the combustion performance (i.e., complete or incomplete
combustion). Rice husk ash can be used as a soil amendment and as additive in cement and steel,
among others. However, only small amounts compared to the total rice husk production are used
for such purposes.

Carbonized rice husk is produced by thermal decomposition of the rice husk under a limited supply
of oxygen (O2) and at relatively low temperatures (less than 700°C). Biochar produced from
carbonization can be used as soil amendment, for processing fertilizer, and as activated carbon,
etc.

2.4.1 Characteristics of the rice husk

Produced during rice milling, the rice husk is already dried and accumulated at the factory. The
specific weight of uncompressed rice husk is about 100 kg/m3. Average properties of rice husk in

22
 proximate analysis a and ultimate analysis b are shown in Tables 1 and 2, respectively, according
to various research on the rice husk by Beagle (1978), Jeng et al. (2012), and Jenkins (1998).

Table 1. Rice husk composition in % of weight (dry basis) based on proximate analysis.a

Fixed carbon (%) Volatile matter (%) Ash (%)

15 67 18

a. Proximate analysis is a partitioning of compounds in a feed into six categories based on the
chemical properties of the compounds. The six categories are: moisture, ash, crude protein, crude
lipid, crude fibre, and nitrogen-free extracts (digestible carbohydrates) (Aquaulture, accessed
2016).

Table 2. Compositions of rice husk in % of weight (dry basis) based on ultimate analysis.b

C H O N S Ash HHV
(%) (%) (%) (%) (%) (%) (MJ/kg)

40 5 34.8 0.8 0.1 19.5 14.8

b. The determination of the percentage of elements contained in a chemical substance

(Encyclopedia, accessed 2016)
Silicon oxide forms the main component of the ash with trace amounts of Al2O3, Fe2O3, CaO,
MgO, K2O, and Na2O. The physical and chemical properties of rice husk ash are dependent on the
components of the combustion process, such as combustion type, feeding type, temperature,
residence time, and availability of oxygen (aerobic or anaerobic).
The characteristics of rice husk compared with other solid fuels can be summarized as follows:

• Its high silica content causes excessive wear to parts of processing machines, such as conveyors
or grinders, and hampers digestibility in livestock. The content of volatile matter in the rice husk
is higher than in wood and much higher than in coal; whereas, fixed carbon is much lower than in

23
 coal. Ash content in the rice husk is much higher than in wood and coal, which causes barriers in
energy conversion.
• The high content of ash, alkali, and potassium causes agglomeration, fouling, and melting of the
parts of combustors or boilers.

2.4.2 Utilization of the rice husk

Rice husk was long considered a waste from the rice milling process and was often dumped and/or
burned. But because it can be easily collected and is cheap, some amount of rice husk has always
been used as an energy source for small applications, such as for brick production, for steam
engines and gasifiers used to power rice mills, and for generating heat for rice dryers. The high
silica content of rice husk ash makes it a good additive for the steel and concrete industries. To a
lesser degree, rice husk ash is used as soil conditioner, activated carbon, insulator, and others.
More recently, creation of electrical power on a small to medium scale—up to 5 megawatts—has
been piloted throughout Asia, with some promising approaches but also some demonstrated limits.
Failure was mostly due to feedstock supply problems once the formerly free waste rice husk
becomes a traded commodity and due to logistical problems and the high cost when transport
distances become too large.

2.5 Taguchi Experimental Design

The Taguchi method involves reducing the variation in a process through robust design of
experiments. The overall objective of the method is to produce high quality product at low cost to
the manufacturer. The Taguchi method was developed by Dr. Genichi Taguchi of Japan who
maintained that variation. Taguchi developed a method for designing experiments to investigate
how different parameters affect the mean and variance of a process performance characteristic that
defines how well the process is functioning. The experimental design proposed by Taguchi
involves using orthogonal arrays to organize the parameters affecting the process and the levels at
which they should be varies. Instead of having to test all possible combinations like the factorial
design, the Taguchi method tests pairs of combinations. This allows for the collection of the
necessary data to determine which factors most affect product quality with a minimum amount of
experimentation, thus saving time and resources. The Taguchi method is best used when there is
an intermediate number of variables (3 to 50), few interactions between variables, and when only
a few variables contribute significantly.

24
The Taguchi arrays can be derived or looked up. Small arrays can be drawn out manually; large
arrays can be derived from deterministic algorithms. Generally, arrays can be found online. The
arrays are selected by the number of parameters (variables) and the number of levels (states). This
is further explained later in this article. Analysis of variance on the collected data from the Taguchi
design of experiments can be used to select new parameter values to optimize the performance
characteristic. The data from the arrays can be analysed by plotting the data and performing a
visual analysis, ANOVA, bin yield and Fisher's exact test, or Chi-squared test to test significance.

25
 CHAPTER THREE
3 METHODOLOGY

A batch adsorption experiment from the liquid phase, also known as immersion experiment, is one
of the most common tests used to remove a liquid or gas from solution. It consists of the addition
of a known mass of sample to a fixed volume of liquid at an initial concentration. The liquid is
mixed either using a stirrer or the entire cell is agitated to mix the liquid phase. The liquid is
sampled or is circulated to a detector and the evolution of the liquid concentration in time is
monitored up to equilibrium.

3.1 Materials used

• Rice husk
• NaOH
• Crude oil
• Distilled water

3.2 Equipment used

• Beakers
• Measuring cylinder
• Funnel
• Conical beaker
• Magnetic stirrer/ heating mantle
• Oven
• Sample bottles
• Filter Paper
• Weighing balance
• Sieve
• Sieve Shaker

26
3.3 Activation of rice husk using NaOH
The rice husk is ground into a smaller size and is then sieved to get fine particles. 60 grams of
NaOH is mixed in a beaker with distilled water. The ground rice husk is then added to the solution
and mixed, it is then left for 24 hours before it is dried in an oven before ground again into fine
particles.

3.3.1 Procedures
• The ground rice husk was placed in a sieve shaking machine to get 130 grams if rice husk
with a particle size of 0.04mm
• Two 100ml beakers were filled with distilled water
• 60 grams of NaOH were measured and was mixed in each of the beakers to form a solution
• The rice husk was then added to the NaOH and water mixture
• The rice husk mixture was then left for 24 hours
• The rice husk mixture was then put in oven till it is dry
• The dry rice husk mixture was then put in a grinder to become powder

3.4 Batch Adsorption Experiment

In the process the crude oil and activated rice husk were mixed together at different concentrations
in 100ml of water in different runs. The resultant mixtures of these runs are then filtered using
filter paper the resultant adsorbate is then analysed for the remaining percentage of crude oil. The
rice husk dosage is varied between 2 grams, 4grams and 6 grams. The crude oil concentration is
varied between 5ml, 10ml, 15ml. The time is also varied between one two three hours shown in
the table 3-1 below

27
Table 3-1: Design of Experiment

RH
Run Crude Oil Concentration Dosage Time Temperature % of HC removal
ml/100 mL of distilled
o
water g hr C
1 15 2 3 40
2 15 6 2 30
3 10 6 1 40
4 10 2 2 50
5 5 6 3 50
6 5 4 2 40
7 5 2 1 30
8 15 4 1 50
9 10 4 3 30

3.4.1 Procedures
• The beaker was filled with 100ml of water
• The crude oil was then added to the water at varying concentrations of 5ml, 10ml and 15ml
• The chemically activated rice husk was then added at varying concentrations of 2g, 4g, 6g
• The mixture was then placed on magnetic stirrer mantle where it was stirred at varying
temperature of 30C,40C and 50C
• The magnetic stirring mantle was turned on
• The mixture while stirring was timed at varying times of 1hour, 2hours and 3hours
• After stirring the resultant mixture was then filtered using filter paper.
• The resultant filtrate was then kept in sample bottles after each run

28
 CHAPTER 4

4 DISCUSSION OF RESULTS

The amount of crude oil removed from the crude oil-water mixture was calculated using a
GC-MS. The table 4-1 below shows the results of the crude oil removal of the nine runs done.

Table 4-1: Table of Results

Run Temperature Rice husk Time Crude oil Crude oil

Dosage concentration removed
(oC) (g) hrs ml/100ml of (%)
water
1 40 6 3 30 67.06
2 60 4 1 30 81.25
3 50 4 3 10 79.01
4 50 6 1 20 74.44
5 40 4 2 20 64.61
6 50 2 2 30 70.92
7 40 2 1 10 54.15
8 60 2 3 20 77.31
9 60 6 2 10 88.75

From table 4-1 it can be seen that from all the runs, run 9 had given the greatest percentage of
crude oil removal. Run 9 had the following conditions; temperature of 60oC, rice husk dosage of 6
grams, time of 2 hours and a crude oil concentration of 10ml/100ml of water. These conditions
gave a crude oil removal of 88.75%.

It can also be seen from the table above that run 7 had the least percentage of crude oil removal.
Run 7 was operated on the following conditions: temperature of 40oC, rice husk dosage of 2 grams,

29
time of 1 hour and a crude oil concentration of 10ml/100ml of water. These conditions gave a
crude oil removal of 54.15%.

4.1 Analysis of variance

Table 4-2: Table for Analysis of variance

Source Sum of Degree of Mean square F value P-value

squares freedom Prob>F
Model 833.06 6 138.84 54.07 0.0183

Temperature 643.71 2 321.85 125.34 0.0079

Rice husk 145.72 2 72.86 28.37 0.034

dosage
Time 43.63 2 21.81 8.50 0.1053

Residual 5.14 2 2.57

Corrected 838.19 8
total

Table 4-2 shows the analysis of variance of the experiment. The analysis of variance was gotten
using the Taguchi experimental design model. The Model F-value of 54.07 implies the model is
significant. There is only a 1.83% chance that a "Model F-Value" this large could occur due to
noise.Values of "Prob > F" less than 0.0500 indicate model terms are significant.

30
4.2 Diagnostic case statistics
Table 4-3:Table for Diagnostic Case Statistics

Run number Actual value Predicted value Residual

1 70.92 70.91 0.021
2 67.06 67.04 0.021
3 64.61 65.55 -0.94
4 74.44 75.38 -0.94
5 77.31 78.25 -0.94
6 54.15 53.24 0.91
7 81.25 81.23 0.021
8 88.75 87.84 0.91
9 79.01 78.10 0.91

Table 4-3 above shows the diagnostic case statistics which shows the comparison between the
predicted values (The response value predicted by the model for this set of experimental
conditions) and the actual values (The actual measured response value for this observation). The
residual is the difference between the predicted values and the actual values. The value of the
residual shouldn’t be more than 1.

31
4.3 Paremeter Intearaction

Design-Expert® Software

R1

X1 = A: temperature
X2 = B: rh dosage
84
Actual Factors
C: time = 1
D: crude oil concentration = 1
76.5
R1

69

61.5

54
3 3

2 2

B: rh dosage 1 1 A: temperature

Figure 4-1:Plot of Rice husk dosage and temperature against crude oil removal

The figure above shows the 3D-plot of rice husk dosage and temperature against crude oil removal.
From the plot it can be seen that the percentage of crude oil removal increases with increasing
temperature and rice husk dosage. The graph was plotted using design expert

32
 Design-Expert® Software

R1

X1 = A: temperature
X2 = D: crude oil concentration
75
Actual Factors
B: rh dosage = 1
C: time = 1
69.25
R1

63.5

57.75

52
3 3

2 2

D: crude oil concentration 1 1 A: temperature

Figure 4-2: Plot of crude oil concentration and temperature against crude oil removal

From the 3D plot above we can see that crude oil removal increases with increasing temperature
but the same cant be said for crude oil concentration as the first crude oil concentration variable
has the highest crude oil removal rate while the second crude oil concentration variable has the
lowest crude oil removal rate.

33
 Design-Expert® Software

R1

X1 = B: rh dosage
X2 = C: time
69
Actual Factors
A: temperature = 1
D: crude oil concentration = 1
65.25
R1

61.5

57.75

54
3 3

2 2

C: time 1 1 B: rh dosage

Figure 4-3: Plot of time and rice husk dosage against crude oil removal

The plot above shows the plot of time and rice husk dosage against crude oil removal it is seen
that as rice husk dosage increases so does the crude oil removal. But as we look at the time it is
seen that the second variable gives the highest crude oil removal while the first variable gives the
lowest crude oil removal.

34
 Design-Expert® Software

R1

X1 = A: temperature
X2 = C: time
80
Actual Factors
B: rh dosage = 1
D: crude oil concentration = 1
73.5
R1

67

60.5

54
3 3

2 2

C: time 1 1 A: temperature

Figure 4-4: Plot of time and temperature against crude oil removal

The above plot shows the plot of time and temperature against crude oil removal. From the plot it
can be seen that crude oil removal increases with increasing temperature while for time the second
variable gives the highest amount of crude oil removal while the first variable gives the lowest
amount of crude oil removal

35
 Design-Expert® Software

R1

X1 = B: rh dosage
X2 = D: crude oil concentration
64
Actual Factors
A: temperature = 1
C: time = 1
61
R1

58

55

52
3 3

2 2

D: crude oil concentration 1 1 B: rh dosage

Figure 4-5: Plot of crude oil concentration and rice husk dosage against crude oil removal

36
 Design-Expert® Software

R1

X1 = C: time
X2 = D: crude oil concentration

Actual Factors 59
A: temperature = 1
B: rh dosage = 1

57.3
R1

55.6

53.9

52.2
3
2
2 C: time
1 1
D: crude oil concentration

Figure 4-6:Plot of crude oil concentration and time against crude oil removal

The plot above shows the plot of crude oil concentration and time against crude oil removal. As
seen in the diagram above the first variable of the crude oil concentration gives the highest crude
oil removal while the second variable has the lowest crude oil removal. While for time the second
variable gave the highest crude oil removal while the first variable gave the lowest crude oil
removal.

37
4.4 Rice husk characterization
4.4.1 Scanning electron microscopy (SEM) analysis

Figure 4-7: Scanning electron microscopy (SEM) of chemically activated rice husk before crude
oil adsorption

38
Figure 4-8: Scanning electron microscopy (SEM) of chemically activated rice husk after crude
oil adsorption
This analysis was carried out on the prepared activated carbon before and after adsorption of the

crude oil in order to see the structural change of the activated rice husk. Figure 4-7 and 4-8 depicts

the SEM images of prepared activated carbon before and after adsorption of crude oil. As shown

in Figure 4-7, the adsorbent possessed undefined structure with pores of various sizes on its surface

which pave way for the adsorption of the crude oil. However, there was change in adsorption

structure due to the crude oil adsorption adsorption as can be seen in Figure 4-8. More so, those

pores earlier seen before adsorption have been blocked. This result is a trend with those reported

by previous researchers.

39
4.4.2 Fourier transform infrared (FTIR) analysis
140

120

100
T%
80

60

40

20

0
4400 4000 3600 3200 2800 2400 2000 1600 1200 800 400
cm-1

Figure 4-9:FTIR analysis of rice husk before adsorption of crude oil

140

120
T%
100

80

60

40

20

0
4400 4000 3600 3200 2800 2400 2000 1600 1200 800 400
cm-1

Figure 4-10: FTIR analysis of rice husk after adsorption of crude oil

40
In order to identify the functional groups, present on the surface of prepared activated carbon
before and after adsorption, FTIR analysis was conducted. As can be seen in the spectrum, Figures
4-9 and 4-10 some peaks were shifted, disappeared and new peaks were formed. Those changes
observed in Figure 4-10 indicated the possible involvement of detected functional group in the
adsorption of crude oil.

41
 CHAPTER FIVE
5 CONCLUSION AND RECOMMENDATIONS
5.1 Conclusions
This project investigated the factors influencing the removal of crude oil from water by use of
chemically activated rice husk. Four variables at three levels were examined using an L9
orthogonal approach with a set of nine experiments. Subsequently, statistical analysis using
ANOVA and further optimization using Taguchi design matrix were applied. Successively, the
developed model equations were found as effective tools in predicting the percentage of crude oil
removed as actual and predicted values were in good agreement as there was no residual of over
1.0. Optimum crude oil removal of 88.75 % from water was achieved when 10 mL/L of crude oil
in water, with a rice husk dosage of 6g at a temperature of 60oC reaction temperature and 2 hrs
reaction time. While the least crude removal of 54.15% occurred when 10 mL/L of crude oil in
water, with a rice husk dosage of 2g at a temperature of 40oC reaction temperature and a 1 hr
reaction time. It was also discovered that the factors which had the most significant effect on crude
oil removal are rice husk dosage and temperature due to the fact that as these values increased so
did the crude oil removal. This research proved that rice husks are a good low-cost adsorbent for
the adsorption of crude oil from water. The Model F-value of 54.07 gotten from the analysis of
variance implies the model is significant. Also the characterization of the activated rice husk the
scanning electron microscopy (SEM) showed that there was effective adsorpyion of the crude oil.

5.2 Recommendations
Following the successful completion of this project, I will like the following recommendations to

be put into consideration

1. The developed adsorbent can be utilized for industrial scale remediation of crude oil from
water.
2. The effect of other adsorption parameters such as, pH and Speed can be investigated using the
adsorbent.
3. Equilibrium studies which was not obtained in this study should be carried out using the
prepared adsorbent.
4. More study should be done to determine the optimum adsorption condition.

42
5. Experiments should be done to certify the predicted optimal conditions for the
process by u the MATLAB Programme.

43
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treatment wet lands. nature partner journal, 1-10.
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