Pre-Conc Treatment of Tar Sand Project Proper

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PRE-CONCENTRATION TREATMENT OF ONDO TAR SAND

RESIDUE FOR RUTILE RECOVERY

By

OJO Adedayo Adeyinka

(MME/2003/036)

A THESIS SUBMITTED TO THE DEPARTMENT OF

MATERIALS SCIENCE AND ENGINEERING,

FACULTY OF TECHNOLOGY, OBAFEMI AWOLOWO UNIVERSITY,

ILE-IFE, OSUN STATE, NIGERIA.

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE AWARD

OF BACHELOR OF SCIENCE (B.Sc HONS) DEGREE IN MATERIALS

ENGINEERING

FEBRUARY 2010


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CERTIFICATION

I certify that this research was carried out by OJO Adedayo Adeyinka of the

department of Materials Science and Engineering, Obafemi Awolowo University,

Ile-Ife, Osun state, Nigeria under my supervision.

______________ ____

Dr. L.E. Umoru Engineer A.A. Adeleke

Head of Department Project Supervisor

______________ ___

Date Date


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DEDICATION

I dedicate this work to the glory of God Almighty, who made it possible despite all

odds and challenges, for me to bring this work to completion. Also to my parents

Mr. and Mrs. OJO, for the grand opportunity given to me to run this degree

programme and all the support they offered me both financially and morally. To my

beautiful sisters, family friends and well wishers; thank you all and God Bless.


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ACKNOWLEDGEMENT

My profound gratitude goes to my supervisor, Engr. A.A. Adeleke whose ideas,

advice, literature and moral support were pivotal in bringing this research to

successful completion. I will also use this opportunity to thank the members of staff

of the departments Metallurgical Testing Laboratory, most especially Mr. Olaoye.

My appreciation also goes to my very good friend and project partner, Oladokun

Babajide for his dedication and selfless efforts during the course of this work, God

bless you. Also to my colleagues, Yahaya, Sanusi, Adeniran, thank you for your

support.

My special thanks and recognition goes to my parents for their immense financial

contribution to the execution of this research, and also to my favorite uncle, Dotun

Somoye for his contributions. God shall surely reward you all greatly. To almighty

God, who made all things possible, I shall always remain grateful to you.

God Bless.

OJO, A.A

February, 2010


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ABSTRACT

Ondo tar sand has been shown in literatures to contain appreciable content of rutile for which

Nigeria has no known large deposits. This research was therefore designed to recover substantial

proportion of rutile from Ondo tar sand.

The sand residue of the Ondo tar sand was subjected to particle size analysis, composition

analysis, and gravity pre-concentration using shaking table, dense medium separation and

leaching treatment.

This research was used to determine the liberation size of rutile in the tar sand residue and

provide process parameters to effectively pre-concentrate the sand residue for rutile recovery.

Rutile is an important raw material used in paints, plastics, rubber, ceramics, high quality

paper as well as other vast applications. The successful recovery of high grade rutile from Ondo

tar sand will provide a reliable source of good grade TiO2 for various industrial applications,

especially the local paint industry; thus, reducing dependence on imports and boosting our foreign

exchange earnings.


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TABLE OF CONTENTS

PRE-CONCENTRATION TREATMENT OF ONDO TAR SAND ............................................. 1

CERTIFICATION ............................................................................................................. 2

DEDICATION ................................................................................................................. 3

ACKNOWLEDGEMENT ................................................................................................... 4

ABSTRACT .................................................................................................................... 5

TABLE OF CONTENTS ................................................................................................... 6

LIST OF TABLES ............................................................................................................ 7

LIST OF FIGURES .......................................................................................................... 8

CHAPTER ONE .............................................................................................................. 9

1.1 Background ............................................................................................................ 9

CHAPTER TWO ............................................................................................................ 13

Definition of Tar Sand ................................................................................................. 14

2.2 Origin of Tar Sand ............................................................................................... 15

2.3 Composition of Tar Sand ..................................................................................... 17

2.4 Microstructure of Tar Sands ................................................................................ 19

2.5 Nigerian Tar Sands ............................................................................................... 21

2.6 Mineral and Metal Content of Tar Sand ............................................................... 25

2.7 Identification and Analysis of tar and sand valuable mineral and metal content . 27

2.8 Rutile .................................................................................................................... 29

2.9 Dense Media Separation (DMS) ............................................................................ 33

2.9.1 Derivation of equation to obtain the required Density from the mixture of two

liquids. ................................................................................................................... 34

2.10 Shaking Tabling ................................................................................................. 36

2.11 Leaching Treatment ........................................................................................... 36

CHAPTER THREE ......................................................................................................... 38

3.1 Materials .............................................................................................................. 38

3.2.3 Determination of most potent reagent ........................................................... 42


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3.2.4 Determination of optimal leaching time ........................................................ 42

3.2.5 Determination of optimal reagent concentration ........................................... 43

3.2.6 Sieve Analysis Ondo Tar sand Residue ........................................................... 43

CHAPTER FOUR .......................................................................................................... 47

4.1 Results ................................................................................................................. 47

4.2 Discussion of Results ............................................................................................ 52

4.2.1 Recovery of Heavy Bitumen and Sand Residue from Tar Sand ......................52

4.2.2 Effect of Sodium Hydroxide in Recovery of Bitumen and Sand Residue ... .....53

CHAPTER FIVE ............................................................................................................ 54

5.1 Conclusion ............................................................................................................ 54

5.2 Recommendations ............................................................................................... 55

REFERENCES .............................................................................................................. 56

LIST OF TABLES

Table 2.1: Comparative Analysis of Tar Sand Samples Collected in Ondo State, Nigeria

Table 2.2: Specific gravity of some Oxides

Table 2.3: Specific gravity of some heavy liquids

Table 4.1: Determination of Suitable Leaching Reagent

Table 4.2: Determination of Contact Time for Highest Recovery

Table 4.3: Determination of Leaching Efficiency Using Sodium Hydroxide

Table 4.4: Analysis of Bitumen and Sand Residue Recovery from Tar Sand


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Table 4.5 Sieve Analysis of Tar Sand Residue

Table 4.6: Mineralogical Composition of Ondo Tar Rich Sand residue

LIST OF FIGURES

Figure 2.1: Microstructure of Tar Sand

Figure 2.2: Raw rutile sample

Figure 3.1: Sieve Shaker

Figure 3.2: Simplified Diagram of Hot Water Recovery Process

Figure 4.1: A graph of recovery of bitumen and sand tailings against contact time

Figure 4.2: A graph showing the weight of sodium hydroxide against sand tailings

Figure 4.3: A graph showing the weight of Bitumen and Sand residue recovery


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CHAPTER ONE

INTRODUCTION

1.1 Background

Over the years, convectional crude petroleum has enjoyed a monopoly of the energy scene. As the

demand for energy begins to be on the rise the world over and as production and distribution problems

of all fuels became pronounced, recovery of synthetic crude and other minerals from tar sands takes

on a new significance.

Tar sand deposits, often referred to as bituminous sand or oil sands occur in various parts of the world

including Canada, Madagascar, Venezuela, Russia, United states and Nigeria to mention but a few.

Although exceedingly rich in oil, valuable minerals and metals in varying proportions, development of


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such deposits has been slow. There are few instances in earlier years where saturated sand was mined for

use as paving material and limited amounts of heavy oil were extracted and turned into more or less

conventional-type petroleum products.

Slow development has been attributed to technical problems associated with production and

processing, in other cases, inaccessibility of the deposits. In the particular case of Canada, however, this

general picture has taken significance turn over the last 15 years. The technology of mining tar sand in a

most unfavourable climatic condition has been mastered and plants are in full operation for converting

extracted bitumen to synthetic crude and a subsequent refining to conventional refining products (Allen

and Stanford, 1973).

It is estimated that the Nigeria tar sand is the fourth largest in the world after Canada, Russia and

Venezuela (Adegoke et al, 1980). The estimate is about 35-45 billion barrels of heavy oil trapped in tar

sand deposits in Ondo State alone, with more reserves in Ogun and Delta States (Wood, 1984). Tar sand

reserves in Ondo state alone is estimated to be about 31billion metric tonnes.

The bituminous materials, apart from the production of crude oil, can add to the much desired

flexibility of Nigerias present and future petrochemical industry. The sulphur content of Nigeria tar

sand constitutes a potential source of elemental sulphur for sulphuric and superphosphate fertilizer

production plants (Adegoke et al, 1980). Other industrial applications include production of

anticorrosive coatings, protection for electric cable, bonder adhesives and brake lining to mention a few.

Tar sand deposit can be mined by the use of open-pit method (for thicker over-burden) or by the use

of in-situ method (hot water process). Tar sands can be mined and processed to extract the oil-rich

bitumen, which is then refined into oil. The bitumen in tar sands cannot be pumped from the ground in

its natural state; instead tar sand deposits are mined, usually using strip mining or open pit techniques, or

the oil is extracted by underground heating with additional upgrading. Tar sands are water wetted or


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hydrocarbon wetted. As a result of this, extraction techniques for the tar sand are different (Carrigy,

1960).

After mining, the tar sands are transported to an extraction plant, where a hot or cold water process

separates the bitumen from sand, water, and minerals. The tar sand with 5-10 wt% of bitumen is

designated to be good or medium grade. Basically, tar sand is composed of sand, water, bitumen and

some mineral accessories. Consequently, the oil sands in this deposit have great diversity in their

composition and properties (Shaw et al, 1996). Tar sands are frequently characterized by their

mineralogy, such as the liquid medium which is in contact with the mineral particles of the tar sand.

Tar sand deposits are diverse and contain varying amounts and sizes of mineral components in ores

from various zones. Generally, the predominant mineral is quartz, present as grains, with small amounts

of feldspar, mica flakes and clays (Shaw et al, 1996). The clays consist of kaolinite, illite and chlorite in

different ratios. The tar sands also have varying porosity, ranging from 25 to 35 percent. With several

means of analysis, different component and distribution of minerals and metals existing in Nigeria tar

sand is revealed.

Heavy minerals such as titanium-bearing minerals, Vanadium, Titanium, Nickel and Zircon of

economic importance have also been revealed in tar sands. It has long been established that tar sand

tailings greatly concentrate these minerals. Minerals in several tar sand tailings (clay fraction) are very

similar with little variation in composition (Ignasiak et al, 1983). This study is aimed at the pre-

concentration treatment of Ondo tar sand residue for Rutile recovery.

Rutile is a major mineral source of the element titanium. Rutile is typically about 60% titanium and

40% oxygen. It can have some iron present, sometimes up to 10%. Rutile is one of the most common

titanium minerals, occurring in gneiss, mica, schist, granite, limestone and dolomite. It is also associated

with quartz, hematite and feldspar. As a secondary mineral, it is common in beach sand deposits, along

with the other titanium mineral, ilmenite. Rutile is brownish red and other shades, but not black. It has a


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hardness of 6.6 (on the mohs hardness scale), specific gravity of 4.18 to 5.2, a metallic luster and a pale

brown streak. Its crystals are prismatic, vertically striated or furrowed. It fractures unevenly, to

subconchoidal. Melting point is 1825C (www.mine-engineer.com).

1.2 Aim and Objectives

The aim of the research is to obtain rutile from Ondo tar sand residue. The objectives include the

following;

i. Pre-concentration of Ondo tar sand residue for rutile recovery.

ii. Chemical and instrumental analysis of raw and treated samples.

iii. Pre-concentration of tar sand residue using Shaking tabling, DMS and leaching

treatment.

iv. To produce rutile of improved grade for titanium oxide production.

1.3 Scope

The research involves the development of a process flow sheet for the efficient recovery of rutile from

Ondo tar sand residue. The scope of this work includes;

i. Chemical and instrumental analysis of raw and treated samples of the tar sand residue using the

XRFS, to determine the oxide composition.

ii. Extraction of bitumen content from the tar sand and subsequent collection of the sand

residue.

iii. Conduct dense media separation, shaking tabling and leaching treatment of the sand residue to

concentrate TiO2 and determining the most suitable method.


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iv. Sieve analysis of tar sand residue.

1.4 Justification for the Research

Research on the pre-concentration of Ondo tar sand residue for the recovery of rutile has not

been reported in literatures. Since the raw tar sand is readily available in commercial quantities, the

successful recovery of high grade rutile from it will provide an essential input for the local paint

industry, thus reducing dependence on imports and conserving our foreign exchange earnings. The

success of this research poses to be an economic breakthrough, considering the vast uses and economic

importance of rutile.

CHAPTER TWO

LITERATURE REVIEW


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Definition of Tar Sand

Tar sand is a naturally occurring hydrocarbon described as black mass of solid aggregate,

composed mainly of mineral matter, connate water and heavy oil bitumen. Tar sands is a common

term for what are more accurately called bituminous sands, but also commonly referred to as oil

sands or extra heavy oil. Tar sand, sand or sandstone saturated with bitumen, a dark, and asphalt

like oil. Tar sand, sand or sandstone saturated with bitumen a dark, and asphalt like oil. Bitumen

consists of a mixture of hydrocarbons chemical compounds containing hydrogen and carbon and

small amounts of other compounds. Because of its glue like consistency, bitumen is too viscous

(thick) to extract from the ground by conventional production techniques. Once extracted and

refined, bitumen can be used as fuel and as a raw material in the chemical industry (Adegoke et al,

1980).

The material is a naturally occurring mixture of sand or clay, water, and extra heavy crude

oil or bitumen which is found in significant amounts. The organic constituent of tar sand is

bitumen, a heavy oil that cannot be recovered by ordinary petroleum production methods. Tar

sands (also called oil sands) are mixtures of organic matter, quartz sand, bitumen, and water that

can either be mined or extracted in-situ using thermal recovery techniques. Typically, oil sands

contain about 75% inorganic matter, 10% bitumen, 10% silt and clay, and 5% water. The bitumen

has high density, high viscosity, and high metal concentration. There is also a high carbon-to-

hydrogen molecule count (i.e. oil sands are low in hydrogen). This thick, black, tar-like substance

must be upgraded with an injection of hydrogen or by the removal of some of the carbon before it

can be processed. Tar sand products are sold in two forms: as a raw bitumen that must be blended

with a diluents (becoming a bit-blend) for transport and as a synthetic crude oil (SCO) after being

upgraded to constitute light crude. The diluents used for blending is less viscous and often a by-

product of natural gas, e.g. a natural gas condensate. Bitumen may be of variable hardness and

volatility, ranging from crude oil to asphalt, and is largely soluble in carbon disulphide. Tar sand


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is generally granular. Upon separation from the mineral components of the tar sand, bitumen has

many useful applications and also can be refined into valuable commodities, such as oil. However,

bitumen is high viscous material with viscosity between 5,000 to 40,000 poises at 60 0F. due to its

viscosity, on extraction, it requires chemical alteration (called upgrading) to make it fluid enough

for transportation by pipeline and it makes it suitable as refinery feedstock, thus its final product is

termed synthetic crude oil (Adegoke et al, 1980). However, it is pertinent to mention that oil

bearing stones have to be mined and specifically processed to recover contained minerals (Fine

Tailings Fundamentals Consortium, 1995).

2.2 Origin of Tar Sand

Most tar sand are form oil bearing sand by evaporation of more volatile components which

results in great loss of fluidity. On the formation of tar sand, geologies have not yet agreed on how

the oil got into the sand. These sands were at the shore of a sea, blown by wind, washed by water

forming dunes of all shapes and description (Shaw, 1996).

The tar sands deposits are the remains of marine life inhabiting an ancient ocean, which

covered what today is Alberta. With time the remains of marine organisms formed organic

material in the depressions in the pre-historic seabed. The presence of organic material, bacteria,

heat and pressure combined with a reservoir for the oil to accumulate, millions of years ago,

provided the right circumstances for the creation of oil (Alberta Community Development, 2005).

The age of the source rocks for the oil found in the Alberta oils sands deposits is still a matter of

uncertainty. The uncertainty centres on whether the source rocks are Mississippian (320-355

million years ago) or of Jurassic age (145-205million years ago), or perhaps a combination of the

two (National Energy Board, 2000).

The first stages in the creation of the oil sands were in principle similar to the origination

of conventional oil. During the creation of the oil, bacterial removed most of the oxygen and


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nitrogen leaving primarily hydrogen and carbon molecules. Heat and pressure caused by layer

upon layer of rock and silt accumulating over time, somewhat pressure-cooked the organic

material. Decomposition by microscopic organism led to a reorganization of their carbon and

hydrogen bonds to form hydrocarbons or oil (Wood, 1984).

It is the later stages of development that differ the creation of the tar sands form that of the

creation of conventional oil deposits. The generated oil was probably sourced in the deeper

portions of in pre-Cretaceous formations due to pressure from the formation of the Rocky

Mountains, and then migrated long distances north into the existing sand deposits, left behind by

ancient river beds, thus forming the present tar sands. The equivalent sands became primary

collector of the generated oil and provided the main channel for migration. For the creation of the

tar sands, the oil was mixed with fine particles of clay and other minerals such as various metals

and sulphur. The lighter oils that remained in the sands deposits were then subjected to

biodegradation by microbes, transforming them into bitumen (National Energy Board, 2000). The

microbial action preferentially decomposed the lighter hydrocarbon molecules, leaving the more

complex heavy molecules, heavy minerals and sulphur behind. As a result, the specific gravity

and sulphur content of the crude oil increased. For similar reasons the concentration of heavy

minerals such as vanadium, nickel, magnetite, gold and silver also increased. It has been estimated

that prior to biodegradation, the original volume of oil in the tar sands was two to three times as

large as it is today. The characteristics of the bitumen and reservoir properties of the oil sands are

in large part a function of the degree of biodegradation that took place. Tar sands represent a

potentially vast supply of energy. World reserves of tar sands contain an estimated 3.58 trillion

barrels of bitumen. The worlds largest tar sand deposits are located in the province of Alberta,

Canada, and contain a total of about 2.5 trillion barrels of bitumen. One of these deposits, located

near Fort McMurray along the lower Athabasca River, contains an estimated 919 billion barrels of

bitumen the largest known deposit of crude oil in the world. 1995 the output of the worlds only


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75 to 80 percent inorganic material, with this inorganic portion composed 90 percent of quartz

sand.

3 to 5 percent water.

10 to 12 percent bitumen, with bitumen saturation varying between zero and 18 percent by

weight.

A key aspect of the tar sand reservoirs is the presence of bound formation water, which

surrounds the individual sand grains as layer. The bitumen is trapped within the pore space of the

rock itself. This is similar to most conventional oil reservoirs, and the rock is said to be water-

wet, that is, each sand grain is surrounded by an envelope or film of water about 10 nanometres

thick. The presence of the water layer around the grains enables the bitumen to be recovered more

easily since the bonding forces between the bitumen and water are much weaker than those

between the water and the sand grains (Takamura, 1982).

In comparison to conventional crude oils, bitumen contained in the tar sands is

characterized by high densities, very high viscosities, high metal concentration, high amounts of

sulphur and a high ratio of carbon to hydrogen molecules. With a density range of 1970 to 1015

kilograms per cubic meter (8-140API), and a viscosity at room temperature typically greater than

50,000 centipose, bitumen is a thick, black, tar-like substance that pours extremely slowly. The

average composition of Albertas bitumen is 83.2 percent carbon, 10.4 percent hydrogen, 0.94

percent oxygen, 0.36 percent nitrogen and 4.8 percent sulphur, along with trace amounts of heavy

metals such as vanadium, nickel and iron.

Average crude oils contain about 84 percent (by weight) carbon, 14 percent hydrogen, 1 to

3 percent sulphur and minor amounts of nitrogen, oxygen, metals and salts. In order to transport

bitumen to refineries equipped to process it, bitumen must first be blended with a diluent,

commonly referred to as condensate, to met pipeline specification for density and viscosity.


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Tar sands generally are categorized into three grades:

i. The outcrop

ii. The rich tar sand

iii. The lean tar sand

The outcrop contains the highest oil content (about 35%). It sticky and easily flows out of

the soil. The rich tar sand, also known as the high grade, is rich in hydrocarbon and darker with oil

content of about 12-17 wt% while the lean tar sands or low grades contain between 3-6 wt% of

oil, it is not all that rich in hydrocarbon.

This corresponds to a tar sand mixture of roughly 83wt% sand, with the bitumen and water

making the balance. In fact, it was found with considerable regularity that the bitumen and water

total about 12-17wt% of the rich tar sand. Mineral matter content is also found to be 78%. Tar

sands are sand deposit impregnated with dense viscous petroleum. Tar sand deposits are widely

distributed throughout the world often in the same geographical area as conventional petroleum

(Codd, 1972). The target deposit is in the Athabasca area in the Province of Alberta Canada. This

reserve contains about 7000 billion tones of bitumen. Reserves of tar sand, each containing over

15billion barrels of bitumen, had been located in the United State, Venezuela, Albania, Romania,

and former Soviet Union. Nigerian reserves are at about 40billion barrels which occur in parts of

Ondo, Ogun and Edo States (Adegoke et al, 1980)

2.4 Microstructure of Tar Sands

Takamura has summarized the evolution of the microstructure model of oil sands

(Takamura, 1982). Before the commencement of commercial bitumen separation operations in

1967, Cottrell proposed a model for the microstructure of tar sands of interactions between water,

bitumen and mineral particles. He concluded that a water film of uniform thickness surrounds the


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Figure 2.1: Microstructure of Tar Sand

2.5 Nigerian Tar Sands

Nigerian tar sand deposit is known to occur in part of Ondo, Ogun and Edo States.

According to Adegoke et al (1980), the first attempt at commercial exploitation was by the

defunct Nigeria Bitumen Corporation, between 1908 and 1914. The Ondo State tar sands occur in

the eastern margin of the Dahomey basin, coastal sedimentary basin. This extends from the

Ghana-Ivory Coast boundary, through Togo and Benin Republic to Western Nigeria. The basin

was formed during the early cretaceous by extensive block fauthing of basement complex during

the geological events which led to the opening of the Atlantic Ocean.

In Nigeria, the crude has migrated up-deep into near surface losing, in the process, its

volatile component thus forming the highly viscous bitumen. The Nigerian tar sands can be


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categorized, according to Wood (1984), into three grades; the outcrop, the high grade called the

rich tar sand, and low grade called the lean tar sand. The over burdened thickness of the deposit is

general considered shallow, ranging from about 0.5m to 13m with an average of 6m. The tar sand

reserves have been conservatively estimated to be more than 40billion barrels (Clark, 1923).

Based on an average bitumen content of 15% by weight, the Nigerian rich tar sands deposits

constitute a potential reserve of over 78million barrels of bitumen. However, it is pertinent to

mention that the water wet structure, similar to that of Athabasca, has been postulated for the

Nigerian deposit only because it is similarly amenable to the hot water process. Bitumen reserve

in the south-western area of Nigeria is tentatively estimated at about 15billion barrels. The total

area of possible bitumen coverage is estimated at about 189 sq.km (73 sq.miles), the average

thickness of pay is estimate at about 20m (65.6ft) with a mean hydrocarbon content of about 112.

The similarities in the Athabasca and Nigeria tar (oil) sands imply that process technology applied

in the former can be adopted for the later, with limited modifications. Compared to the Athabasca

tar sands, the Nigeria variety exhibits the following characteristics.

i. Higher Sand Porosity

ii. Low Content Clay and Fines

iii. Less Lean Tar Sand

iv. Higher Bitumen

v. No External Stress

vi. Absence of Basal Aquifer

vii. Less Basal-Gas

viii. Less Sulphur and Heavy Metal

As a result of these characteristics and advantages, the Niger tar sands have some potential for

easy development namely:

i. Amenability to gravity drainage


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ii. Potential for steam assistance (SAG-D)

iii. Amenable to open-pit mining

It could be concluded that the Okitipupa tar sand, when encountered in the sub-surface

would be amenable to gravity drainage, as well as steam injection because of the good reservoir

properties while the surface and near-surface occurrences would be won by open cast mining. The

differences between the Nigeria tar sand and the Athabasca tar sand includes:

i. The over-burdened Nigeria tar sand is smaller compared to that of Athabasca i.e. more

of Nigeria tar sand can be recovered by surface mining, whereas only about 3% of the

Athabasca tar sand can be obtained by surface mining with the rest recoverable by in-

situ process, which is a more expensive process.

ii. The Nigeria tar sand deposit had very low clay content ranging from 2%-7% with an

average of 5%. This low clay content is a great advantage since it means that there

could be less environmental problem to cope with during oil extraction than has been

the case with Alberta.

iii. The Ondo State bitumen deposit, tested by a German construction company Longed

Rhugas (L/R) process in 1972, was found to be better in road surfacing than its

Athabasca equivalent (Wood, 1984).


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2.6 Mineral and Metal Content of Tar Sand

Tar sands are frequently characterized by their mineralogy, such as by the liquid medium

which is contact with the mineral particles of the tar sand. The water wet tar sands such as the tar

sand deposits generally found in the Ondo State deposit of Nigeria comprise mineral particles

surrounded by an envelope of water, sometimes referred to as connate water. Generally, the

bitumen of such water wet tar sands is not in direct physical contact with the mineral particles but

rather forms a relatively thin film which surrounds the water envelope around the mineral

particles. In addition, tar sands are frequently characterized by their richness or the amount of

bitumen they contain and the quality thereof. They heavy metals concentration in the tar sands

samples is consistent with concentration. The Nigeria tar sand samples contains the varying

amounts of Ti02 (0.4wt %) and Zr02 (0.08wt %). The bitumen-free mineral sand deposit also

contains only 0.06 wt% Ti02 and 0.008 wt% zircon. On average, about 70wt% of the Ti02 and

63wt% of the Zr02 are concentrated in the sand fraction. The Nigeria Tar sands has been known

to have striking similarities with the Canadian tar sand which has been confirmed to have the

following valuable heavy minerals such as titanium-bearing minerals, vanadium, titanium, nickel

and zircon. It has long been known that the tar sand tailings greatly concentrate these minerals.

Minerals in several Tar sands tailing (clay fraction) are very similar with little variation in

composition (Ignasiak et al., 1983).

However other minerals are also contained in tar sands. It is clear that Tar sands deposits

are diverse and contain varying amounts and sizes of mineral components in ores from the various

zones. Generally, the predominant mineral is quartz, present as grains, with small amounts of

feldspar, mica flakes and clays (Shaw et al, 1996). The clays consist of kaolinite illite and chlorite

in different ratios. The tar sands also have varying porosity, ranging from 25 to 35 percent. Iron-

bearing minerals are known to occur in the tar sand Ells (1926) made comments on this

occurrence. Siderite is considered indicative of littoral shallow-water strata containing abundant


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2.7 Identification and Analysis of tar and sand valuable mineral and metal content

The classical wet analysis was developed and widely used in the 19 th century. Classical

analysis, also termed wet chemical analysis, consists of those analytical techniques that use no

mechanical or electronic instruments other than a balance. The method usually relies on chemical

reactions between the material being used. Classical wet analysis may be used to empire a

traditional instrumental approach for accuracy. In addition to more conventional titration analysis,

classical wet analysis plays an important role in many other analytical applications including

identification and analysis of valuable minerals and metals in tar sand.

The tar sand residue is used directly; no wet separation process is employed (Wood, 1984).

You may observe the following phenomena:

a. Change in the condition or appearance of the assay

b. The formation of gases which collect in the tube

c. The formation of sublimates or condensed liquids on the cold walls of the tube.

Only materials with a low melting point fuse in the closed tube. Such boiling melt points

to minerals of the zeolite group, or to crystal hydrates. They can be distinguished by their

hardness; zeolites are not scratched by steel. Minerals containing liquid inclusions may snap and

explode owing to the evolution of steam during heating. Sometimes they break up into very fine

powder or dust, e.g. milky quartz. This phenomenon is called Decrepitation.

Some minerals emit a bright, often coloured light when heated below redness, (T >>

300oC). The effect can be observed only in darkness. It is caused by the healing of lattice defects

on heating. The lattice defects are always due to radioactive radiation which had hit the crystal

since its formation. This effect is called thermo luminescence, it is often found on fluorite, quartz,

calcite, apatite, zircon, and diamond in specimens from different outcrops.


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Sometimes the colour of mineral changes due to the healing of lattice defects on moderate

heating, mostly from dark colours to lighter ones. Such bleaching is a common procedure used in

treating raw gemstones, especially zircons. But minerals may also change colour after heating,

owing to decomposition. Sometimes minerals containing fluorine as well as OH-groups cause

hydrofluoric acid HF to form; it will etch the glass, gives an acid reaction to pH-paper and has a

pungent odour. This reaction occurs only at higher temperatures (e.g. topaz)

The present technique used in the industry is X-ray fluorescence analysis or XRF, XRF

is for the most part capable of yielding satisfactory results when carried out by highly trained

personnel. X-ray Fluorescence (DRT) spectroscopy is a non destructive qualitative and

quantitative analytical used to determine the chemical composition of samples.

According to the present invention there is provided a method for determining the mineral

and metal composition of a sample from x-ray data obtained by subjecting a pellet of the tar sand

sample to x-ray energy in an X-ray fluorescence spectrometer. The collected data gives precision

and data of known minerals to determine the mineral and metal composition of the sample.

Energy dispersive x-ray emitted to determine the chemical composition for many type of material.

The atoms in the samples are excited by x-ray emitted from XRF-tube or radioisotope. In a source

excited DRF analysis, primary X-rays emitted from a sealed radioisotope source are utilized to

irradiate samples. During interaction with samples, source X-rays may either undergo scattering

(dominating process) or absorption by sample atoms in a process known as the photoelectric

effect (absorption coefficient). This phenomenon originates when incident radiation knocks out an

electron from the innermost shell of an atom creating a vacancy. The atom is excited and releases

its surplus energy almost instantly by filling the vacancy with an electron from one of the higher

energy shells. This rearrangement of electrons is associated with the emission of X-rays

characteristic (in terms of energy) or the given atom. This process is referred to as emission of

fluorescent X-rays (fluorescent yield). The overall efficiency of the fluorescence process is


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referred to as excitation efficiency and is proportional to the product of the absorption coefficient

and the fluorescent yield.

The features and uses include:

Most accurate, most economic and simple analytical methods for determination of the

chemical composition of many type of material.

It can be sued for a wide range of elements; from sodium to uranium.

Detection limits at the sub-ppm level and can measure concentration up to 100% easily and

simultaneously.

2.8 Rutile

Rutile is a major mineral source of the element titanium. Rutile is typically about 60%

titanium and 40% oxygen. It can have some iron present, sometimes up to 10%. Rutile is one of

the most common titanium minerals, occurring in gneiss, mica, schist, granite, limestone and

dolomite. It is also associated with quartz, hematite and feldspar. As a secondary mineral, it is

common in beach sand deposits, along with the other titanium mineral, ilmenite.

Rutile is brownish red and other shades, but not black. It has a hardness of 6.6 (on the mohs

hardness scale), specific gravity of 4.18 to 5.2, a metallic luster and a pale brown streak. Its

crystals are prismatic, vertically striated or furrowed. It fractures unevenly, to subconchoidal.

Melting point is 1825C (www.mine-engineer.com).

Rutile is found in igneous and metamorphic rocks, chiefly in Switzerland, Norway, Brazil,

and parts of the United States. Rutile occurs as an accessory in many rock types, ranging from

plutonic to metamorphic rocks, and even as a detrital material in sediments and placers because of

its resistance to weathering. Large crystals have been found in some granite pegmatites; in Brazil

it often occurs as inclusions in clear quartz crystals (rutilated quartz). Rutile is commonly


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associated with apatite in high-temperature veins. In sufficient quantities, it is marketed as an ore

of titanium. (www.mineral.galleries.com)

Figure 2.2: Raw rutile sample (Source: www.mine-engineer.com)

Rutile is mined in Norway and is widespread in the Alps, the southern U.S., Mexico, and

elsewhere. In groups of acicular crystals it is frequently seen penetrating quartz as in the "flches

d'amour" from Grisons, Switzerland. In 2005 the Republic of Sierra Leone in West Africa had a

production capacity of 23% of the world's annual rutile supply, increasing to approx. 30% in

2008. The reserves, lasting for about 19 years, are estimated at 259 million tons.

(www.answers.com;en.wikipedia.org).

Rutile can also be extracted from tar sand deposits. According to Oladapo (2008) tar sand

deposits, often referred to as bituminous sand or oil sand occurs in various parts of the world

including Canada, Madagascar, Venezuela, Russia, United states and Nigeria to mention but a

few. Although exceedingly rich in oil, valuable minerals and metals in varying proportions,

development of such deposits has been slow. Slow development has been attributed to technical

problems associated with production and processing and in other cases, inaccessibility of the

deposit.


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Tar sand deposits are widely distributed throughout the world often in the same

geographical area as conventional petroleum (Codd, 1972). The target deposit is in the Athabasca

area in the province of Alberta, Canada. This reserve contains about 700 billion tones of bitumen.

Reserves of tar sand, each containing over 15billion barrels of bitumen, had been located in the

United States, Venezuela, Romania, and the former Soviet Union. Nigeria reserves are at about 40

billion barrels which occur in parts of Ondo, Ogun and Edo states (Adegoke et al, 1980).

The Nigeria tar sand samples contains varying amount of TiO2 (0.4 wt %) and ZrO2

(0.08wt %). The bitumen-free mineral sand deposit also contains only 0.06 wt % TiO 2 and 0.008

wt % Zircon. On the average, about 70 wt% of the TiO2 and 16 wt% of the ZrO2 are concentrated

in the sand fraction. The Nigeria tar sand has been known to have striking similarities with the

Canadian tar sand which has been confirmed to have the allowing valuable heavy minerals such as

titanium-bearing minerals, vanadium, titanium, nickel and zircon. It has been long known that the

tar sand tailings greatly concentrate these minerals. Minerals in several tar sand tailings are very

similar with little variation in composition (Ignasiak et al, 1983).

Major uses of this lightweight, high strength, non-corrosive metal are aerospace, automobiles,

sports, and medicine. Still, its main use is in paint as a paint pigment. It replaced lead as the most

common paint pigment used in the manufacture of paint. Other uses include a coating for tiles,

and it is used to treat the air, both to preserve fruits and vegetables and to remove pollution.

Today, rutile is used for four main purposes. These include the production of titanium dioxide

pigment, the production of titanium metal, flux coatings and finally as mineral specimens and

gemstones on the precious stone market. The most important of these by far is for the production

of titanium dioxide white pigment.

The titanium dioxide pigment is extracted directly from rutile, which contains 92 96 %

TiO2. This is done by calcining a mixture of rutile, coke and chlorine to form gaseous titanium

tetrachloride (TiCl4).


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density are used, so that those minerals lighter than the liquid float, while those denser than it

sink.

In this method, liquids covering a range of densities in incremental steps are prepared and

the representative sample of crushed tar sand is introduced into the liquid of highest density. The

float products from the liquid of highest density are removed and washed, then placed in the next

liquid of lower density, whose float product is then transferred to the next liquid of lower density,

until all the densities are exhausted. Usually the results of the heavy liquid tests are used in

producing theoretical washability, evaluating the performance of an existing plant (Yaro et al,

2003).

2.9.1 Derivation of equation to obtain the required Density from the mixture of two liquids.

Given; Vm = V0 + V1 .. (1)

Also, DmVm = D0V0 + D1V1 .. (2)

Substituting for Vm in (2)

Dm (V0 + V1) = D0V0 + D1V1

The formula takes the form,

Dm = D0V0 + D1V1

V0 + V1

Where Dm density of the mixture

D0 density of liquid 1

D1 density of liquid 2

V0 volume of liquid 1

V1 volume of liquid 2

(C.R. Tottle, 1994)


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Table 2.2: Specific gravity of some Oxides

Oxide Specific Gravity

SiO2 (Silica)

Al2O3 (Alumina)

Fe2O3 (Haematite)

TiO2 (Rutile)

MgO (Calcined Magnesite)

Fe3O4 (Magnetite)

Na2O (Di-Sodium oxide)

K2O (Potassium oxide)

CaO (Lime)

MnO (Manganese II oxide)

2.65

3.9 4.1

5.0 6.0

4.2

3.65

5.5 6.5

2.51

2.30

3.34

4.4 4.7

Table 2.3: Specific gravity of some heavy liquids

Liquid Specific Gravity

Bromoform

Choloroform

Tetrabromoethane

Carbontetrachloride

Di-iodomethane

2.89

1.48

2.96

1.58

3.30


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2.10 Shaking Tabling

In this method, a flowing film of water effectively separates coarse light particles from

small dense particles, this mechanism is utilized in the shaking-table concentrator which is

perhaps the most metallurgically efficient form of gravity concentrator being used to treat the

smaller, more difficult flow streams, and to produce finished concentrates from the products of

other forms of gravity system..

The shaking table consists of a slightly inclined deck, on to which feed, at about 25%

solids by weight, is introduced at the feed box and is distributed along; wash water is distributed

along the balance of the balance of the feed side from the launder. The table is then vibrated

longitudinally by the mechanism, using a slow forward stroke and a rapid return, which causes the

mineral particles to crawl along the deck parallel to the direction of motion. The minerals are

thus subjected to two forces, force due to the table motion and that, at right angles to it, due to the

flowing film of water.

The net effect is that the particles move diagonally across the deck from the feed end, and

since the effect of the flowing film depends on the size and density of the particles, they will fan

out on the table, the smaller, denser particles riding highest towards the concentrate launder at the

far end. While the larger lighter particles are washed into the tailings launder, which runs along

the length of the table. An adjustable splitter at the concentrate is often used to separate the

product into two fractions, which are; a high-grade concentrate and a middling fraction.

2.11 Leaching Treatment

This is a method for upgrading a concentrate of tar sands bitumen containing fine mineral

matter and optionally coarse mineral matter in which solvent-diluted bitumen is contacted for a

short time in a riser with hot attrition-resistant substantially catalytically inert acid-resistant

fluidizable particles, causing a selective vaporization of the lighter high hydrogen content

components of the bitumen. The preferred particles are composed of silica-alumina, most


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preferably a mixture of mullite and crystalline silica or mullite, crystalline silica and an acid-

resistant form of alumina. A portion of the heavier asphaltenes and most of the components which

contain metals, sulfur and nitrogen remain on the attrition-resistant fluidizable particles. Fine

mineral matter in the bitumen feed also deposits on the fluidized particles instead of being carried

over with the vaporized hydrocarbon product. The contact material, with deposit, is contacted

with a solution of acid to remove the deposit of mineral matter and deposited metals without

decomposing the particles of contact material. The heated particles of contact material are

reintroduced into the riser for further contact with incoming diluted bitumen charge (Reagan and

Bartholic, 1989)

A variety of acid leach procedures may be used to remove the ashes deposited mineral

matter from the withdrawn contact material samples. Reagan (op.cit) further explained that the

preferred acid leach procedures will remove at least about 40% by weight of the calcium oxide

present of the surface of the materials. Typically, CaO and TiO2 contents of up to about 3% can be

tolerated. Iron oxide is easily removed, so most processes capable of reducing CaO and TiO 2 to

the desired levels will also reduce iron to levels below about 1.5%, which is usually satisfactory.

The presently preferred process uses a high temperature mineral acid leach to remove deposited

mineral matter and metals from the substrate material followed by filtration to separate the metals-

containing solution from the contact material. The metals may be separated from the leachate and

purified in separate processing steps and can be sold as by-products. The leachate to be used is

ammonium nitrate at temperatures in excess of about 88 C.


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3.2.2 Hot water extraction (Bitumen and Sand Residue separation)

The basic method commonly used for tar sand analysis is the hot water extraction process

to determine the bitumen, water and sand content. The hot water extraction process for primary

extraction of bitumen from tar sands is used to clean up the bitumen for further processing. A

beaker was filled with distilled water and heated to a temperature of about 75C; the temperature

was measured with the aid of a Thermometer. Pellets of Sodium hydroxide were fed into the

beaker to obtain an aqueous solution. Sodium hydroxide which acts as a wetting agent was added

to maintain a pH of around 8.2. The addition of the Sodium hydroxide aids the optimal recovery

of bitumen and tar sand residue. A lump of the tar sand was weighed and placed in the mixture

which was heated on the magnetic stirring hot plate, which has a combined heating and stirring

effect. The stirrer agitates the mixture, and the combined effect of hot water and agitation releases

bitumen from the tar sand and causes tiny air bubbles to get attached to the bitumen droplets that

float to the top of the plastic container where the bitumen is skimmed off. The remaining mixture

is decanted to fully separate the softened lumps of tar sand (bitumen and sand) from the tar sand

residue. The resulting residue still contained tiny lumps of bitumen which was dissolved using

benzene, after which a finer and cleaner sand residue was obtained. The sand residue was then

poured into a container and allowed to dry at room temperature, after which it was further dried

on the electric cooker at a temperature of about 90-95C. The stream of middlings was carefully

scavenged for recovery of incremental amounts of bitumen.

The hot water extraction yielded an oily product of essentially pure, but diluted bitumen.

Water and mineral with any unrecovered bitumen removed from the froth constitute an additional

tailing stream.


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3.2.3 Determination of most potent reagent

The basic method commonly used for tar sand analysis was the hot water extraction

process to determine the bitumen, water and sand content. The determination of most potent

reagent was carried out for both sodium hydroxide and sodium carbonate. 2g of tar sand was

placed in a 250ml beaker. 25ml of distilled water was added to it with 0.1g of leaching reagents. A

Stuart scientific magnetic stirrer hotplate was used which agitate the reagent and the tar sand

simultaneously. Continuous heating of the mixture of the tar sand, sodium hydroxide and hot

water was done. The combined effect of hot water and agitation releases bitumen from tar sand

and causes tiny air bubbles to get attached to the bitumen droplets, that that float to the top of the

beaker where bitumen was skimmed off. The remaining softened lump of tar sand in the mixture

(consisting of sand and bitumen) was removed into a beaker and weighed. The solution was

allowed to cool, settle and decantation process was used to separate the tailings. Benzene and

toluene were used to dissolve some traces of bitumen in the tailings and it was later filtered, and

tar sand residue was obtained.

3.2.4 Determination of optimal leaching time

The time efficiency was carried out using 0.1g of Na0H, 1g of tar sand and 25ml of

distilled water in the beaker with varying extraction time. Different contact time was used for

leaching starting from 5mins, 10mins, 15mins, 30mins and 45mins. 1g of tar sand was placed in a

250ml beaker. 25ml of distilled water was added to it with 0.1g of leaching reagent. A magnetic

stirrer hotplate was used which agitate the reagent and the tar sand simultaneously. Continuous

heating of the mixture of the tar sand, sodium hydroxide and hot water was done. The combined

effect of hot water and agitation releases bitumen from tar sand and causes tiny air bubbles to get

attached to the bitumen droplets, that that float to the top of the beaker where bitumen was

skimmed off. The remaining softened lump of tar sand in the mixture (consisting of sand and

bitumen) was removed into a beaker and weighed. The solution was allowed to cool, settle and


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decantation process was used to separate the tailings. Benzene and toluene was used to dissolve

some traces of bitumen in the tailings and it was later filtered, and the sand residue was obtained.

3.2.5 Determination of optimal reagent concentrationThe optimal reagent concentration was carried out using hot water extraction method.1g of tar

sand was placed in a 250ml beaker. 25ml of distilled water was added to it with a contact time of

15mins and varied leaching reagent. A Stuart scientific magnetic stirrer hotplate was used which

agitate the reagent and the tar sand simultaneously. Continuous heating of the mixture of the tar

sand, sodium hydroxide and hot water was done. The combined effect of hot water and agitation

releases bitumen from tar sand and causes tiny air bubbles to get attached to the bitumen droplets,

that that float to the top of the beaker where bitumen was skimmed off. The remaining softened

lump of tar sand in the mixture (consisting of sand and bitumen) was removed into a beaker and

weighed. The solution was allowed to cool, settle and decantation process was used to separate the

tailings. Benzene and toluene was used to dissolve some traces of bitumen in the tailings and it

was later filtered, and the residue was sand recovery.

3.2.6 Sieve Analysis Ondo Tar sand Residue

Sieve analysis was carried out on the tar sand residue to obtain finer particles of sizes less

than 150 m. The sizes of sieves used are 150 m, 125 m, 106 m and 63 m. The electrically

operated sieve shaker was used to conduct the analysis for 30 mins. The retained particles in each

of the sieves were then weighed separately.


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Figure 3.1: Sieve Shaker.

3.2.7 Determination of the mineral content of Ondo Tar sand residue


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0.10 50.60 47.80 98.40

0.12 49.80 47.40 97.20

0.14 50.10 47.10 97.20

.....................4.1

Table 4.4 Analysis of Bitumen and Sand Residue Recovery from Tar Sand using the Hot

Water Extraction Process (Bulk Extraction)

Weight of Tar Sand

(g)

Weight of Bitumen

Recovered (g)

Weight of Sand

Residue (g)

Contact time

(mins)

10 4.2 3.3 30


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Zircon (Zirconium silicate)

Ilmentite

Rutile

Mica

Siderite

Magnetite

Kaolinite

Quartz

Silimanite

0.1 - 0.1

0.05 - 0.5

2

0.3 0.9

0.02

0.43

0.01

0.01

4

Fig 4.1: A graph of recovery of bitumen and sand tailings against contact time


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Fig 4.2: A graph showing the weight of sodium hydroxide against sand tailings.

Fig 4.3: A graph showing the weight of Bitumen and Sand residue recovery


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4.2 Discussion of Results

4.2.1 Recovery of Heavy Bitumen and Sand Residue from Tar Sand

The process used in separating the bituminous content of the tar sand from the sand

residue was effective in obtaining a good grade of both bitumen and tar sand. The hot water

extraction is a process which objective is to effectively separate bitumen from mineral particles

which are heavily present in the tar sand residue. The process involves mixing, mass and heat

transfer, and chemical reactions leading to the separation of bitumen from the sand tailings. The

process also involves agitation of the reacting particles, the effect of which increases the

probability of collision and adhesion of the particles. The results of the hot water extraction

process can be used to analyse the varying weights of tar sand samples treated, as shown in Table

4.4. From the table, it can be observed that the recovery of bitumen decreased on extracting larger

samples of the tar sand. However, there is an increase in the recovery of sand residue when


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treating larger samples in the solution of sodium hydroxide. The optimal recovery of tar sand

residue is obtained when 70g of tar sand is used.

4.2.2 Effect of Sodium Hydroxide in Recovery of Bitumen and Sand ResidueTar sand samples were leached with sodium hydroxide and sodium carbonate in separate

experiments. The results of the treatment are presented in table 4.1. The leaching of the tar sand

with sodium hydroxide produced bitumen recovery of 48.00% and 40.00% sand residue, while

that of sodium carbonate produced 20.95% bitumen and 39.20% sand residue. The overall

recoveries of sodium hydroxide and sodium carbonate are 88.60% and 60.15% respectively.

These results show that leaching with sodium hydroxide yielded higher bitumen and sand tailings

recoveries. The recovery of bitumen with sodium hydroxide exceeds that of sodium carbonate by

27.05%, while the overall recovery with sodium hydroxide is 28.45% greater than that of sodium

carbonate. From these results, it can be deduced that sodium hydroxide reacts more actively with

tar sand to liberate the bitumen from the sand admixture with more sand residue obtained. The

role of NaOH is to produce natural surfactants from the bitumen, and it is normally used to

optimize bitumen recovery.

The determination of bitumen and sand residue recovery by the leach contact time is

presented in table 4.2. The results shows that the highest recovery of bitumen (52.40%) occurred

with 5mins leach time, while the highest recovery of tailings was at 15mins contact. The overall

recovery of 98.40% for bitumen and sand residue was obtained at 15mins leach contact time.

From these results, it can be seen that the 15mins contact time yielded the second highest bitumen

recovery of 50.60% with the highest sand tailings recovery of 47.80%. The low recovery of

13.60% for sand tailings at 5mins contact time may be due to high tailing loss during

sedimentation and decantation coupled with a poor liberation from the bituminous tar sand. The

15mins contact time may thus be preferable as it not only indicates pure bitumen but also

produces a large amount of sand tailings from which a useful mineral like TiO2 can be recovered.


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significance of TiO2 (rutile) as a raw material in Titanium dioxide pigment, production of titanium

metal and gemstones, as well as its presence in Ondo tar sand has been discussed. Literatures have

also shown that rutile is present in varying composition of tar sand residue and is of very high

economic importance. However, the successful recovery of rutile from tar sand residue was not

achieved because of the unavailability of chemicals to concentrate the rutile content of the sand.

Also, there is very little information in literatures on the recovery of rutile from tar sand residue;

therefore further research is expected to be carried out.

5.2 Recommendations

From the results obtained in this investigation, the following recommendations are made:

i. Follow-up analysis by experts in the field of minerals extraction and processing.

ii. Government and private establishments should explore the opportunities available in the

successful extraction of valuable minerals and metals present in tar sands.

iii. The successful recovery of rutile for paint making will reduce the dependence on imports

and increases the economys Gross Domestic Product (GDP).

iv. Further research work could focus on understanding the association between bitumen

recovery and heavy metals recovery from tar sands. This would be beneficial to plant

operations, and lead to improved recovery of bitumen and other minerals.


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REFERENCES

Adegoke, O.A. (1980). Geotechnical investigation of Ondo State Bituminous Sands, vol.1

Geology and Reserves estimate: Unpublished Proprietary Report, Geological Consultancy Unit,

University of Ife.

Allen and Stanford (1973), Mineralogy of tar sand in the upper part of the Green River Formation in

the eastern Utah Basin, Utah: U.S. Geological Survey Open-File Report 76-381, 27 p.

Alberta Community Development (2005). Oil Sands Discovery Center,

www.oilsandsdiscovery.com [2005-03-31] Alberta Energy and Utilities Board (AEUB)

Andrew, P.L. (2001). Uses of rutile. http://www.google.com.

Carrigy, J.R., Oil sands facies, ultra-fines and tailings; Oil Sands Fundamental Consortium c/o Oil

Sands Research Division of Alberta Energy, Report No: ER-1332-95S, (1960).


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Clark, K.A., Hot-water Separation of Alberta Bituminous Sand, The Canadian Institute of Mining

and Metallurgy, 17, 257-374, (1994).

Cuddy, G.A., Syncrude Canada private communications Ltd., (1998).

C.R. Tottle. Encyclopedia of Metallurgical and Materials Engineering, (1984).

Ells, T.E. (1926). The Science and Practice of Heavy minerals processing, 6th ed., Cambridge

University Press.

Ignasiak, A.K. (1983). Microscopic structure of Athabasca Oil sand. The Canadian Journal of

Chemical Engineering, 60, 538-545.

Oladapo, O.F. (2008). Investigation of the Mineral and Metal Content of the Ondo Bitumen Rich Tar

Sand, B.Sc Thesis: Department of Materials Science and Engineering, OAU, Ile-Ife, Osun State.

Pearson, M. (1979). The Future of Heavy Crude and Tar Sands. UNITAR, AOSTRA, Edmonton. pp

295-300.

Reagan W.J and D.B Bartholic (1989). Process for Upgrading tar and bitumen. Free patents

online.com, USA.

Shaw, M.T. (1996) Geology of Canadian Oil sands, America Chemical Society, vol.13, 639-675.


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W. O. Siyanbola, A. Y. Fasasi, I. I. Funtua, O. M. Afolabi , T. A. Adesiyan, A. R. Adetunji.

Elemental composition of rutile from south-western Nigeria using X-ray techniques. Nuclear

Instruments and methods in Physics Research Section B: Beam Interactions with Materials and Atoms.

Vol. 215, Issues 1-2, January 2004, pp. 240-245.

Wikipedia The free encyclopedia (en.wikipedia.org), 2005.

www.nation master.com; en.wikipedia.org.

Yaro, S.A., and Abubakar, S.M. (2003). Determination of the liberation size of Manganese deposit

using heavy sink-float method. Unpublished report, Minerals Processing Research unit; Federal

University of Technology, Minna.

Documents

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