CHARACTERIZATION OF WAXY AND ASPHALTENIC CRUDE OIL

USING SARA ANALYSIS

By

Mohamad Hazwan Bin Yusoff @ Mohd Yusoff

Dissertation submitted in partial fulfilment of

the requirements for the

Bachelor of Engineering (Hons)

(Petroleum Engineering)

MAY 2013

Universiti Teknologi PETRONAS

Bandar Seri Iskandar
31750 Tronoh

Perak Darul Ridzuan

 CERTIFICATION OF APPROVAL

Characterization of Waxy and Asphaltenic Crude Oil Using SARA Analysis

By

Mohamad Hazwan Bin Yusoff @ Mohd Yusoff

(12656)

A project dissertation submitted to the

Petroleum Engineering Programme

Universiti Teknologi PETRONAS

in partial fulfilment of the requirement for the

BACHELOR OF ENGINEERING (Hons)

(PETROLEUM ENGINEERING)

Approved by,

……………………...........…..
(Dr Aliyu Adebayor Sulaimon)

UNIVERSITI TEKNOLOGI PETRONAS

BANDAR SERI ISKANDAR
31750 TRONOH, PERAK
May 2013

i
 CERTIFICATION OF ORIGINALITY

This is to certify that I am responsible for the work submitted in this project, that the
original work is my own except as specified in the references and
acknowledgements, and that the original work contained herein have not been
undertaken or done by unspecified sources or persons.

___________________________________________
(MOHAMAD HAZWAN BIN YUSOFF @ MOHD YUSOFF)

ii
 ABSTRACT

Flow assurance is the term used to describe the issues that distort the flow of oil,
water and gas in production and transportation system. The problems are mainly due
to waxes and asphaltenes deposition as temperature and pressure inside wellbore and
pipeline changes. Wax will start to precipitate when temperature falls below cloud
point or known as wax appearance temperature (WAT) as it travels from reservoir to
surface. Experimental data are very limited to confirm the existing prediction models
for different type of crude oils.

The focus of this research were to study the characteristic of crude oil in term of
SARA (saturates, aromatics, resins and asphaltenes) fractions and carbon distribution
by using high performance liquid chromatography (HPLC) and gas chromatography
mass spectrometry (GC-MS) respectively. Differential scanning calorimetry (DSC)
and density meter were used to measure the WAT of crude oils. Comparisons of
WAT obtained from DSC and density meter were provided and the result shows a
good agreement between DSC and density meter technique. Colloidal instability
index (CII) was used to correlate the composition of the crude oil with the potential
of solid precipitation. A study on the effect of continuous carbon dioxide (CO 2)
injection on wax appearance temperature of crude oil was provided.

For this research, five crude oil samples from different location (Dulang, Tapis, Miri,
Dubai and Arab) were analysed. Each sample has different characteristic hence
resulted in different depositional problem. The CII value for Dulang, Arab, Tapis,
Miri, and Dubai is 4.09, 1.21, 5.05, 0.64 and 0.90 accordingly. The SARA fractions,
WAT, and carbon number distribution of the samples were obtained. The results
shows that crude oil samples with higher paraffinic composition have higher wax
appearance temperature and wax content than crude oil samples with lower paraffinic
composition.

As a conclusion, Dulang, Tapis, Arab and Dubai crude oils have high tendency for
asphaltenes deposition while Miri crude oil has low tendency for asphaltenes
deposition. The study shows that the CO2 injection will decrease the WAT as tested
on Dulang crude oil.

iii
 ACKNOWLEDGEMENT

In the Name of Allah, The Most Merciful and Compassionate, praise to Allah, He is
the Almighty. Eternal blessings and peace upon the Glory of the Universe, our
beloved Prophet Muhammad (S.A.W), his family and companions. First and
foremost, thanks to the Almighty for the strength given to carry out the Final Year
Project in the year 2013. A deep gratitude goes to my families, who throughout the
way provide me with motivation in completing the project.

Special regards with deepest appreciation dedicated to Dr Aliyu Adebayor Sulaimon,

my beloved supervisor for his continuous support and help throughout the project
consultation. The supervision and support that he gave truly help the progression and
smoothness in completing the project.

This acknowledgement is extended to all staffs of Chemical Engineering Department

and Petroleum Engineering Department intentionally and unintentionally for any
guidance and information regarding this course. My gratitude also goes to the course
mates in exchanging ideas and provides guidance in application of design and
simulation software. Last but not the least, I would also like to show my heartfelt
gratitude to all those who has directly or indirectly involved in this project, for their
tremendous support and motivation during undertaking this project.

iv
 TABLE OF CONTENTS

CERTIFICATION OF APPROVAL ..................................................................... i

CERTIFICATION OF ORIGINALITY ............................................................... ii

ABSTRACT .......................................................................................................... iii

ACKNOWLEDGEMENT .................................................................................... iv

TABLE OF CONTENTS ....................................................................................... v

LIST OF FIGURES ............................................................................................. vii

LIST OF TABLES ................................................................................................ ix

ABBREVIATIONS AND NOMENCLATURE .................................................... x

CHAPTER ONE: INTRODUCTION ................................................................... 1

1.1 Background of Study ................................................................................ 1

1.2 Problem Statement .................................................................................... 2

1.3 Objective .................................................................................................... 2

1.4 Scope of Studies ........................................................................................ 2

1.5 Relevancy and Feasibility of Study ......................................................... 3

CHAPTER TWO: LITERATURE REVIEW ...................................................... 4

2.1 Crude oil characterization ......................................................................... 4

2.2 Characteristics of wax and asphaltene ..................................................... 5

2.3 Problems and issues related to wax and asphaltene precipitation .......... 6

2.4 SARA analysis .......................................................................................... 8

2.5 Wax Content .............................................................................................12

2.6 Effect of temperature, pressure, water and carbon dioxide on the

behaviour of waxy and asphaltenic crude oil .........................................12

2.7 Wax appearance temperature (WAT) .....................................................14

2.7.1 Differential Scanning Calorimetry ................................................14

2.7.2 Cross Polar Microscopy.................................................................15

2.7.3 Viscometry .....................................................................................16

v
CHAPTER THREE: METHODOLOGY ............................................................17

3.1 Research Methodology ............................................................................17

3.1.1 Sample Preparation ........................................................................17

3.1.2 Gas Chromatography Mass Spectrometry (GCMS) ....................18

3.1.3 Differential Scanning Calorimetry (DSC) ....................................19

3.1.4 Wax content ....................................................................................19

3.1.5 Density Measurement ....................................................................20

3.1.6 Density Meter .................................................................................21

3.1.7 SARA Analysis ..............................................................................22

3.2 Project Activities ......................................................................................25

3.3 Key Milestone ..........................................................................................26

3.4 Gantt-Chart ...............................................................................................27

CHAPTER FOUR: RESULT AND DISCUSSION .............................................28

4.1 Density ......................................................................................................28

4.2 SARA Fraction .........................................................................................29

4.3 Gas Chromatography Mass Spectrometry ..............................................30

4.4 Wax Analysis ...........................................................................................34

4.5 Effect of CO2 Injection on Wax Appearance Temperature ...................40

CHAPTER FIVE: CONCLUSION AND RECOMMENDATIONS ..................41

REFERENCES .....................................................................................................43

APPENDICES .......................................................................................................48

vi
 LIST OF FIGURES

Figure 1: Carbon number distribution of n-paraffin fraction separated 5

from gas oil (Khidr et al., 2007)
Figure 2: Asphaltenes deposit formed on the inside of a pipeline in a 7
refinery (McKenna, 2009)
Figure 3: Flowchart of SARA fractionation method- University of 9
Calgary procedure (Tharanivasan, 2012)
Figure 4: Flowchart of SARA fractionation method- DBR procedure 10
(Tharanivasan, 2012)
Figure 5: HPLC- System (Aske, 2012) 11
Figure 6: Colloidal instability index (Choiri, 2010) 12
Figure 7: Trend of amount of asphaltene deposited as temperature and 13
pressure changes (Mansoori, 1999)
Figure 8: DSC thermogram of Kuwait crude oil during cooling 15
(Elsharkawy et al., 1999)
Figure 9: Stock tank oil at 70oF (WAT at 103.6oF) (Jamaluddin et al. 16
2001)
Figure 10: Crude oil samples 17
Figure 11: Agilent 5975C/7890A Gas Chromatography Mass Spectrometry 18
Figure 12: Micro DSC7 Evo system 19
Figure 13: Portable density meter (DMA35N) 20
Figure 14: Anton Paar DMA5000M density meter 21
Figure 15: Solution is stirred under reflex condenser 22
Figure 16: Experiment setup to filter the asphaltene 23
Figure 17: High pressure liquid chromatography (Agilent 1260 Infinity) 24
Figure 18: Resin separation using rotavapor 24
Figure 19: Project activities 25
Figure 20: Key milestone 26
Figure 21: Gantt-chart 27
Figure 22: Chromatogram for Dulang crude oil sample 30
Figure 23: Chromatogram for Tapis crude oil sample 31
Figure 24: Chromatogram for Dubai crude oil sample 32

vii
Figure 25: Chromatogram for Arab crude oil sample 33
Figure 26: Graph of heat flow against furnace temperature for Dulang 35
crude oil sample
Figure 27: Graph of heat flow against furnace temperature for Tapis crude 35
oil sample
Figure 28: Graph of heat flow against furnace temperature for Miri crude 36
oil sample
Figure 29: Graph of heat flow against furnace temperature for Dubai crude 36
oil sample
Figure 30: Graph of density against temperature for Dulang crude oil 37
sample
Figure 31: Graph of density against temperature for Tapis crude oil sample 37
Figure 32: Graph of density against temperature for Miri crude oil sample 38
Figure 33: Graph of density against temperature for Dubai crude oil sample 38
Figure 34: WAT of Dulang crude oil after CO2 injection 40
Figure 35: Refractive index signal for Dulang crude oil 54
Figure 36: Refractive index signal for Arab crude oil 55
Figure 37: Refractive index signal for Tapis crude oil 56
Figure 38: Refractive index signal for Miri crude oil 57
Figure 39: Refractive index signal for Dubai crude oil 58

viii
 LIST OF TABLES

Table 1: Classification of crude oil (Tharanivasan, 2012) 5

Table 2: Elemental composition of asphaltenes from world sources 6
(Speight, 1999)
Table 3: Additional cost due to occurrence of asphaltene deposit 7
problems (Fargas et al., 2010)
Table 4: Density measurement at 26.5oC 28
Table 5: SARA fractions of crude oil 29
Table 6: Total area percent (C20 - C40) 34
Table 7: Wax appearance temperature 34
Table 8: Wax Content 39
Table 9: Gas chromatography data for Dulang crude oil 48
Table 10: Gas chromatography data for Tapis crude oil 49
Table 11: Gas chromatography data for Dubai crude oil 50
Table 12: Gas chromatography data for Arab crude oil 51
Table 13: Normal heptane insoluble measuring procedure 52
Table 14: Measurement of saturates and aromatics percentage for crude 53
oils
Table 15: Concentration of calibration components 53

ix
 ABBREVIATIONS AND NOMENCLATURE

AOP = Asphaltene Onset Pressure

API = American Petroleum Institute
ART = Acoustic Resonance Technique
CF = Cold Finger
CII = Colloidal Instability Index
CPM = Cross Polar Microscopy
DSC = Differential Scanning Calorimetry
EOR = Enhance Oil Recovery
FD = Filter Plugging
FT-IR = Fourier Transform Infrared Spectroscopy
GCMS = Gas Chromatography Mass Spectrometry
HPLC = High Pressure Liquid Chromatography
LST = Light Scattering Technique
LT = Light Transmittance
NMR = Nuclear Magnetic Resonance
PVT = Pressure, Volume, Temperature
RI = Refractive Index
SARA = Saturates, Aromatics, Resins, Asphaltenes
SDS = Solid Detection System
STO = Stock Tank Oil
TLC-FID = Thin Layer Chromatography Flame Ionization Detection
UOP = Universal Oil Product
UV = Ultraviolet
VOC = Volatile Organic Compound
WAT = Wax Appearance Temperature
WDT = Wax Disappearance Temperature

x
 CHAPTER ONE

INTRODUCTION

1.1 Background of Study

Since the first oil well that had been drilled in 1859, billion barrels of crude oil had
been produced from different region and field. The characterization of each crude oil
is distinctive from each other. It can be light crude oil or heavy crude oil depending
on its density and other properties. Besides, heavy crude oil may contain a large
amount of wax, asphaltene and other substance that can cause serious problem during
production operation.

Wax deposition occurs as crude oil generally has n-paraffin as constituents; when the
wellbore temperature falls below the wax appearance temperature (WAT), wax
crystallization forms and contributes to increase in pressure drop, reduction in
productivity and subsequently choking the production lines, causing emergency
shutdown. In subsea completion (where flow lines on the ocean floor ranges about
1.5oC to 5oC), each wax component becomes less soluble until the higher molecular
weight components solidify. The onset of crystallization is known as the wax
appearance temperature (WAT) and as the temperature drop below WAT, the crude’s
flow properties change from a simple Newtonian fluid to a two-phase dispersion
non-Newtonian fluid. This results in gelation of crudes and loss in flow-ability (Li &
Zhang, 2003).

In this study, Saturate, Aromatic, Resin and Asphaltene (SARA) analysis is used to
identify the characterization of the crude oil. This area of study was first introduced
by Jewell et al. (1972) where they developed the basis for SARA fractionation. It is
the method that categorizes crude oil components based on their polarity and
polarizability. The saturate is a nonpolar material such as paraffin while aromatics
are slightly more polarizable. Both resins and asphaltenes have polar substituents.
1
Issues on asphaltene and solid precipitation have always been highlighted as one of
the major fouling precursors. A small change in aromatics, resin and saturates or
temperature can initiate asphaltene dropouts.

1.2 Problem Statement

As the demand increases and the global supply of light crude oil are exhausted,
production and refinery are extremely moving towards heavy conventional and
unconventional crude oil. Therefore, engineers are struggled to overcome the
challenge of handling waxy and asphaltenic crude oil which is proved to cause major
problem in production, transportation and processing process. Flow assurance is the
term used to describe the issues that distort the flow of oil, gas and water in the
production or transportation systems.

Thus, this study is conducted to analyse and compare the characteristic of the waxy
and asphaltenic crude oil so that we will have more knowledge on its behaviour for
the betterment of the oil and gas industry. The research is very significant as the
result gave the composition of the crude oil. The data is very important for the design
of production and stimulation program.

1.3 Objective

The objective of the study is mainly to know the details of each component of
samples of crude oil such as saturates, aromatics, resins and any others substance that
may appear in the crude oil. Different reservoir or field will produce different crude
oil with different composition. Therefore, this research will aims to:

1) Record and analyse the composition of crude oil samples by using SARA
analysis.
2) Determine the wax appearance temperature (WAT).

1.4 Scope of Studies

The project is based on experimental measurement and analysis. The first part is to
determine the characteristic of paraffinic composition in the crude oil. The
experiment focuses on the following properties: carbon number distribution (C 20 –
C40), WAT as well as wax content. The study of carbon number distribution, WAT
and wax content is conducted using Gas Chromatography Mass Spectrometry

2
(GCMS), Differential Scanning Calorimetry (DSC) and UOP-46 method
respectively. Results from GCMS are used to analyse the paraffin wax ranging from
C20 to C40. For many type of crude oil, analyses of the wax reveal a good correlation
with various parameters such as viscosity and WAT.

1.5 Relevancy and Feasibility of Study

This project is relevant to the author as a Petroleum Engineering student who had
already completed many courses related to production and deliverability of the fluid.
Problems related with wax deposition are very costly because of cleaning operation
as well as production downtime. Therefore, accurate prediction of WAT and wax
content formed at certain environment are very crucial for optimum production
operation. This project aims to provide characteristic of crude oil in order to assist
future development and production plan especially for Malaysian’s oil field.

The development and completion of the project is feasible judging from the
objectives and scope of studies included in the research. The overall period to
complete the research is approximately 8 months. Moreover, this research is
considered as feasible as all the equipment including materials and apparatus are
available in laboratory of Universiti Teknologi PETRONAS. Time constraint also
has been considered and this project has completed within the time specified in the
project Gantt chart.

3
 CHAPTER TWO

LITERATURE REVIEW

This section presents a review of the literature on crude oil characterization,

characteristics of wax and asphaltene, problems and issues related to wax and
asphaltene precipitation as well as SARA analysis method that are being used in
industry. Besides, a review on the factors that affect the behaviour of waxy and
asphaltenic crude oil is also presented.

2.1 Crude oil characterization

Crude oil is a mixture of naturally occurring hydrocarbons, organic compound of

nitrogen, sulphur and oxygen, and small amount of metallic constituents like iron.
The origin of crude oil can have a significant effect on its composition hence have
wide variety in volatility, density, colour and viscosity. Crude oil can be classified as
light oil, heavy oil or bitumen and uses oAPI as a measure of viscosity as shown in
Table 1.

Crude oil can be characterized into pseudo-components based on density, chemical

composition, boiling cut, carbon distribution, H/C atomic ratio and solubility class
(Pedersen & Christensen, 2007). The techniques depend on the oil type and the
required information of its property for pseudo-component. The process of obtaining
the composition of crude oil is complex, time consuming and very expensive. They
need a lot of solvents and each procedure can last for days. However, the procedure
can be simplified by assuming that the petroleum consists of a number of light
discrete components and a heavy end. The heavy end is considered to be part of four
major fractions of similar species (Mansoori et al., 2006).

4
 Table 1: Classification of crude oil (Tharanivasan, 2012)

Crude Oil Type Viscosity (mPa’s) Density (kg/m3) o

API

Light oil <100 <934 >20

Heavy oil 100-100,000 934-1000 10-20
Bitumen >100,000 >1000 <10

2.2 Characteristics of wax and asphaltene

Heavy oil is known to have heavy compounds like waxes and asphaltenes. Wax is a
group of normal paraffin that contain 16 or more carbon atoms that will change to
crystalline solid substances at 20oC. The wax in crude oil is a mixture of normal
hydrocarbons with different carbon number distributions which can be identified by
using Gas Chromatography (GC) as in figure 1. Macrocrystalline wax (C18 - C36) and
microcrystalline wax (C30 - C60) are two different type of wax that can be found in
crude oil. Both of them are made up of aligned paraffinic and naphthenic molecules
(Kok & Saracoglu, 2000).

Macrocrystalline waxes are mainly composed of straight-chain paraffins (n-alkanes)

with different chain length while microcrystalline waxes contains high amount of
isoparaffins and naphthenes (Elsharkawy et al., 1999). The straight-chain structure of
macrocrystalline waxes causes it to be more sensitive to temperature changes. The
existence of solid particles will cause the flow behavior to change from Newtonian to
non-Newtonian.

Figure 1: Carbon number distribution of n-paraffin fraction separated from

gas oil (Khidr et al., 2007)

5
Asphaltenes are defined as a solubility class of petroleum, which precipitate from
crude oil by the addition of an excess amount of n-alkane solvent like n-pentane and
are soluble in aromatic solvents like benzene. “Pentane (C5)-asphaltenes” and
“heptane (C7)-asphaltenes” is the name of the precipitate produced when adding the
n-pentane and n-heptane to the oil respectively. The oil is called “asphaltenes-free” if
there is no precipitate. Speight (1999) tabulated the elemental composition of
asphaltenes from different crude oil of different region which are Canada, Iran,
Kuwait and Venezuela as in Table 2.

Table 2: Elemental composition of asphaltenes from world sources

(Speight, 1999)

Canada Iran Kuwait Venezuela

Carbon (wt %) 79.0-88.7 83.7 81.6-82.4 81.1-84.7

Hydrogen (wt %) 6.9-11.1 7.8 7.8-8.1 7.8-8.3
Nitrogen (wt %) 0.7-2.8 1.7 0.6-1.7 0.2-2.0
Sulphur (wt %) 0.3-8.1 5.8 7.4-8.0 2.7-6.9
Oxygen (wt %) 0.4-3.9 1.0 0.6-1.8 1.0-4.2
H/C Ratio 0.98-1.56 1.19 1.14-1.19 1.13-1.19
N/C Ratio 0.007-0.029 0.017 0.008-0.017 0.002-0.02
S/C Ratio 0.001-0.038 0.026 0.034-0.039 0.012-0.032
O/C Ratio 0.004-0.037 0.009 0.005-0.017 0.013-0.039

2.3 Problems and issues related to wax and asphaltene precipitation

Asphaltene is the heaviest component compared to saturates, aromatic, and resin in

crude oil and it is readily dissolved in crude oil. When it is separated from the crude
oil because of composition change or pressure loss, asphaltene may deposit on the
rock surface and plug some pore throats that will cause more flow resistance for oil
in porous medium. After some period of time, the deposits at certain concentration
can cause major formation damage (Choiri, 2010).

Asphaltenes from crude oils can also be deposited inside of refinery’s pipeline as
shown in figure 2. It will reduce the flow of crude oil and the process is described to
be like coronary artery disease and cause significant problems further downstream.

6
Figure 2: Asphaltenes deposit formed on the inside of a pipeline in a refinery
(McKenna, 2009)

The main factors that contribute to the precipitation of asphaltenes are temperature,
pressure and composition variation due to gas injection and phase separation (Goual,
2012). Apart from that, the process of refining heavy oil is very challenging as
asphaltene can cause fouling and coking while wettability alteration and formation
damage can happen if the asphaltenes is absorbed by the mineral rocks.

Solids depositions which are asphaltenes and wax in reservoir, subsurface and
surface equipment, wellhead equipment, tanks and separator can lead to problems in
operation which will reduce the production rate significantly (Mansoori & Leontartis,
1988). Krishna (1989) stated that gelling process may happen at 2% of precipitated
wax. Clean up and downtime due to plugging in pipelines is very costly especially in
offshore oil production as shown in in Table 3.

Table 3: Additional cost due to occurrence of asphaltene deposit

problems (Fargas et al., 2010)

Operation Cost

Removal of deposit $300k-$3,500K/well

Side track $50,000K/well
Downtime $700k/day (for production of 7,000BPD)

7
2.4 SARA analysis

The SARA analysis defines the content of saturate aromatics, resins and asphaltenes
in crude oil, heavy cuts and residues. The data is beneficial in refinery design and
operations. The analysis is preparative which means that the test provides enough
samples of saturate, aromatics, resins and asphaltenes for further testing and analysis
(Speight, 1991). The compound is separated in different stages. The first stage is to
precipitate the asphaltenes by n-heptane. Deasphalted oil or known as Maltenes is
subjected to liquid chromatography which has similar principles as gas
chromatography. In this case, the compound is eluted from a packed column by a
liquid. The saturated hydrocarbon are eluted by n–heptane, the aromatics by a 2:1
volume mixture of n-heptane and toluene and the resins by an equal volume mixture
of methanol, toluene and dichloromethane by using ASTM D4124 (Fahim et al.,
2010).

Measurements the result from SARA analysis of different method will be always
different therefore it is not comparable (Fan, 2002). The TLC-FID technique is not
suitable for oil with medium gravity if there is no additional analysis to include
components that boil at temperature up to 250oC. It is recommended to use high
pressure liquid chromatography (HPLC) method as it will yield similar result as
time-consuming ASTM method.

According to Tharanivasan (2012), there are two procedures for SARA fractionation
which are University of Calgary procedure and DBR procedure which based on
traditional ASTM method as shown in figure 3 and figure 4 respectively.

8
Figure 3: Flowchart of SARA fractionation method- University of Calgary
procedure (Tharanivasan, 2012)

9
Figure 4: Flowchart of SARA fractionation method- DBR procedure
(Tharanivasan, 2012)

10
Aske (2012) had developed HPLC system for SARA analysis which consist of
HPLC-pump, two 7.8 x 300 mm µBondapak NH2 columns in series, and an
ultraviolet (UV) and a refractive index (RI) detector. The system is shown in figure
5. The first step of the process is to take out the asphaltene by n-hexane precipitation.
The remaining of the oil is then diluted in n-hexane and injected onto the system
through the injection valve ahead of the separation columns. Hexane is used as
mobile phase. Saturates which have no retention on the column material, elutes first
and are detected on the RI-detector. Both fractions are collected in separate vials
after the detectors. The resins should be eluted with a more polar mobile phase. This
can be done by reversing the flow through the columns by a backflush valve, and by
using trichloromethane as mobile phase. Finally, the solvent is evaporated by all
three collected fractions, and SARA distribution may be calculated by including the
asphaltene yield.

Figure 5: HPLC- System (Aske, 2012)

Colloidal instability index (CII) is one of the methods to analyse crude oil system
with asphaltene deposit problems (Yen et al., 2001; Choiri, 2010). It is the ratio of
the total asphaltenes and saturates to the total of aromatics and resins as illustrated in
figure 6. CII below 0.7 is considered as stable while CII higher than 0.9 is considered
as unstable.

11
 Figure 6: Colloidal instabilit y index (Choiri, 2010)

2.5 Wax Content

Wax is an organic solid that appears as the temperature of the system drop. To
quantify the amount of wax in crude oil, the sample has to be chilled to a very low
temperature (e.g. -30 oC) before being filtered (Carnahan, 2007). UOP-46 method
can be used to determine the wax content of crude oil (Vara & Gonzalez, 2011). This
method involved dissolving a sample of deasphalted crude oil in petroleum ether as
well as the addition of Fuller’s earth to the solution. The mixture was then filtered
and evaporated. Lastly, a mixture of one part of petroleum ether and three part of
acetone was added to the solution which was chilled to -18oC and filtered by a cold
filter funnel, after which the sample was washed with hot petroleum ether which was
evaporated to recover the wax. The results and findings are useful in designing a
pipeline system.

2.6 Effect of temperature, pressure, water and carbon dioxide on the

behaviour of waxy and asphaltenic crude oil

EOR method which is miscible-C02 flooding can cause asphaltenes to precipitate

because the CO2 may contact with oil and change the behaviour and equilibrium of
the fluid (Choiri, 2010). Based on the research conducted by Mansoori (1999), it is
stated that the higher the pressure, the greater the asphaltene deposits in live oil as in
figure 7.

12
 Figure 7: Trend of amount of asphaltene deposited as temperature and
pressure changes (Mansoori, 1999)

Li (2010) reported that by using Daqing waxy crude oil sample with different water
cut, an increase of pressure from 0.1Mpa to 12Mpa will increase the wax appearance
temperature (WAT) and wax disappearance temperature (WDT) linearly. At constant
pressure, WAT is always lower than WDT.

There are several experimental methods to analyst the problems of asphaltene deposit
such as Gravimetric Method, Acoustic Resonance Technique Method (ART) and
Light Scattering Method (LST) (Choiri, 2010). Gavimetric method relies on the
selected pressure steps using PVT cell. The asphaltene will start to precipitate and
fall to the bottom of PVT cell at the onset point. Therefore, choosing a small pressure
steps is important for accurate result. The result will be illustrated on the plot of
asphaltene concentration versus pressure.

ART method measures the changes in the acoustic fluid properties while asphaltene
drops out from the solution. Acoustic receiver is used in the ART method to detect
acoustic resonance which is emitted by an acoustic transducer. During
depressurization, a sharp drop in acoustic responses is detected representing the
upper Asphaltene onset pressure (AOP).Light scattering method or solids-detection
system (SDS) uses near-infrared light to probe fluid as asphaltene precipitates either
at isothermal depressurization or at isobaric with decreasing temperature. When the

13
asphaltene is precipitated, the light is scattered and the transmittance power of the
light is reduced. The light’s transmittance power is measured by fiber-optic sensors
located at the other side of the cell. The result shows that when the pressure
decreases, the light transmittance power increases due to denser fluid which gives
more light transmission.

2.7 Wax appearance temperature (WAT)

Laboratory measurements of the cloud points are made on stock tank oil (STO)
samples. It can be predicted from several empirical models and thermodynamic as
well as from laboratory experiments such as Differential Scanning Calorimetry
(DSC), Viscometry, Density, Filter Plugging, Cross-Polar Microscopy (CPM),
Fourier Transform Infrared Spectrometry (FT-IR) and Nuclear Magnetic Resonance
(NMR) techniques. DSC, CPM and Viscometry have been mostly used by researches
(Ronningsen et al., 1991; Hamouda et al., 1993; Calange et al., 1997; Pan et al.,
1997; Cazaux et al., 1998; Elsharkawy et al., 1999; Thomason, 2000;; Chen et al.,
2004; Alboudwarej et al., 2006; Bordalo et al., 2007; Ekweribe et al., 2008; Vara &
Gonzalez, 2011).

The ASTM D2500-88 method relies on visual observation of the wax crystals.
Therefore, it requires the sample to be transparent in layers about 30 mm in thickness
and the method is not suitable for dark crude oil (e.g. black oil). WAT are usually
determined by using DSC, CPM, Light Transmittance (LT) or viscometry for black
oil. DSC, LT and viscometry techniques require that sufficient paraffin crystallize
before the properties of the crude oil change enough for the liquid/solid (L/S) phase
transition to be detected. The limit of detection of DSC and LT techniques is larger
and WAT values from these techniques will lay further inside the solid-liquid phase
envelop. For low wax content crude oil, WAT may go completely undetected by
viscometry, DSC and LT. The CPM is generally deemed to be the most sensitive and
the only direct visual technique applicable for all non-biodefraded oil including
opaque fluids (Hammami et al., 1999).

2.7.1 Differential Scanning Calorimetry

The Differential Scanning Calorimetry (DSC) measures the difference in the heat
released (or absorbed) between test sample and a reference heated to 80 oC and

14
cooled at a specific cooling rate. The reference should be thermally inert and stable
over the temperature range and with known properties. During cooling period, the
test sample at WAT starts to cool slower than the reference due to the release of heat
of crystallization which will be captured by an analyzer. This point is seen as a
deviation from the straight line trend above the WAT measure on the thermogram as
in figure 8. The weight fraction of crystallized wax can be measured if the enthalpy
of fusion of a sample is determined. This solid weight fraction as a function of
temperature defines the solubility curve for crude oil.

Figure 8: DSC thermogram of Kuwait crude oil during cooling (Elsharkawy

et al, 1999)

2.7.2 Cross Polar Microscopy

The Cross Polar Microscope (CPM) is based on the property of wax crystals to rotate
the polarization plane of linearly polarized light. There are two type of polarizers
used in the CPM: the first forces light to undulate in only one direction while the
second placed at 90oC from the first, totally blocks the light wave. When the sample
is cooled on a cooling stage of the microscope, wax crystals form which can rotate
the polarization plan of light i.e. light will be transmitted as paraffin crystals form.
The first white dot will appear as the temperature reaches the wax appearance
temperature of the sample as in figure 9.

15
 Figure 9: Stock tank oil at 70 o F (WAT at 103.6 o F) (Jamaluddin et al. 2001)

2.7.3 Viscometry

Rheological properties of crude oil will change as wax precipitates hence making
viscometry method possible for WAT measurement (Ronningsen et al., 1991). Pan et
al. (1997) studied wax precipitation using four oil samples. During the experiment,
the sample was cooled at specified rate and measurements were taken at testing
temperature down to equilibrium temperature. The process was repeated for lower
temperatures until WAT was established. Several researchers studied this approach
and successfully measured the WAT of crude oil by plotting the logarithm of
viscosity (μ) against the inverse of temperature (1/T) (Ronningson et al., 1991;
Giordani, 1993; Bordalo et al., 2007).

16
 CHAPTER THREE

METHODOLOGY

3.1 Research Methodology

The methodology for this research project is based on experiment and analysis. The
results obtained from this research are used to compare with other literature results
for different methods and samples.

3.1.1 Sample Preparation

The samples were obtained from Petronas Penapisan (Melaka) Sdn Bhd which comes
from different field, namely: Tapis, Dubai, Arab, Miri and Dulang. The crude oil
received is in large volume which around two to three litre so they are heated to 80 oC
for 8 hours in water bath to prevent separation of light crudes and heavy crudes as
well as to eliminate the thermal history which can affect the results. During the
heating process, the crude oils are stirred from time to time for complete
homogeneity and dissolution. After that, the samples are immediately transferred to
smaller container as shown in figure 10. This procedure reduces the time taken for
pre-heating before each experiment to one to two hour as smaller volume is involved.

Figure 10: Crude oil samples

17
3.1.2 Gas Chromatography Mass Spectrometry (GCMS)

For the project, Agilent 5975C/7890A Gas Chromatography Mass Spectrometry is

used to determine the sample’s carbon distribution as in figure 11. Inner diameter of
0.32 millimetres, phase thickness of 0.25 millimetres and DB-5 capillary column of
30 meters is used for the experiment. Helium is used as carrier gas.

Figure 11: Agilent 5975C/7890A Gas Chromatography Mass Spectrometry

Below are the lists of procedures for the experiment:

1) The temperature of oven is set at 120oC and hold for 3 minutes. Then, the
temperature is increased to 270oC and hold for 40 minutes. Temperature increase
rate set at 10oC/min.
2) Splitless injection is carried when the temperature reaches 300oC.
3) Constant flow rate mode is set at 2cm3/min.
4) Mass Spectrometry (MS) transfer line is set at 300oC.
5) Ion source is set at 230oC and kept constant.
6) Procedures 1 to 5 are repeated by using different crude oil samples.

18
3.1.3 Differential Scanning Calorimetry (DSC)

Setaram Micro DSC7 Evo is used to determine the wax appearance temperature for
this project. It allows the experiment to be run from sub-ambient temperature of -
45oC up to 120oC and under high pressure up to 400 bars. Figure 12 shows the setup
for DSC which consist of gas bottle, high pressure gas panel and Micro DSC7 Evo
equipped with high pressure cell.

Figure 12: Micro DSC7 Evo system

Below are the lists of procedures for the experiment:

1) Around 50 mg of each sample is prepared and put into DSC for analysis
2) The samples are heated for from 20 oC to 70oC and hold for 3 minute to achieve
stable state
3) The samples are cooled to -20oC.
4) The samples are heated back to 70oC.
5) The heating and cooling rate is 2oC/min.

3.1.4 Wax content

UOP (Universal Oil Product) 46-85 method is used to determine the wax content of
crude oil samples. The procedures of the experiment are listed as below:

1) Crude oil are dissolved in hexane and stirred continuously on a hot plate.

19
2) Sulphuric acid (H2SO4) is added to the solution to produce an acidic tar with the
asphaltene.
3) The oil-paraffin solution is poured into a separator funnel and the asphaltene
product is washed for a few times in hexane.
4) Water is added to dilute the concentrated acid. Aqueous layer is then removed
upon separation.
5) Ammonium hydroxide and water washes are used and repeated for several times
to neutralize the sulphuric acid. Neutrality which indicated by colour change is
checked by an aqueous phenolphthalein solution.
6) Hexane-wax solution is moved to a flask and reduced by evaporation before
being re-dissolved in warm methylene chloride (MeCl2).
7) Dry ice is used to cool MeCl2 to -30oC to make sure that complete precipitation
of wax is achieved in the solution.
8) The solution is then filtered under vacuum and the flask is rinsed with a series of
chilled MeCl2.
9) The filter which contains wax is dissolved with warm hexane and collected in
tarred flask before being evaporated.
10) Wax is weighted and the wax content is calculated.

3.1.5 Density Measurement

Portable density meter (DMA32N) is used for this project to find the density of the
sample at temperature of 26.5 oC as in the figure 13.

Figure 13: Portable density meter (DMA35 N )

20
The procedures are as follows (ASTM D7777):

1) The samples are poured into the beaker.

2) The lever of the pump is pushed down and the filling tube is submerged in the
sample.
3) The pump lever is slowly released and the reading is recorded.
4) The procedures are repeated for each sample of crude oil.

3.1.6 Density Meter

Anton Paar DMA 5000M density meter is used to determine the density of the
sample as in figure 14. The equipment is setup for a temperature scan by cooling the
samples from 50oC to 0oC at atmospheric pressure. Temperature step of 2oC was
selected. The measurements by Anton Paar density meter are carried out according to
ASTM Standard D5002-99. The density meter gives fast, reliable and accurate
measurement as well as requires only small amount of sample.

Figure 14: Anton Paar DMA5000M density meter

21
3.1.7 SARA Analysis

Sara analysis is divided into two stages. The first stage is to collect and remove
asphaltene from the sample using ASTM D3279. The procedures for asphaltene
separation is as listed below:

1) 1 gram of crude oil and 100 ml of n-heptane is inserted into 250 ml 2-neck round
bottom flask.
2) The solution is gently stir for 20 minutes using magnetic stirrer and secured
under the reflux condenser as in figure 15.
3) The Gooch crucible plus one thickness of the glass-fiber filter pad is placed in an
oven at 107oC for 15 minutes and it is then placed in desiccator for cooling for
15 minutes.
4) The Gooch crucible plus one thickness of the glass-fiber filter pad is then
weighted to the nearest 0.1mg. It is then set up in the suction flask.
5) The content of the flask (50oC) is poured through the filter using a gentle
vacuum. The setup is as in figure 16.
6) The precipitate is washed with three portions of n-heptane of 10ml each.
7) Finally, the crucible plus filter pad along with asphaltene is placed in the oven at
107oC for 15 minutes before being cooled down and weighted.

Figure 15: Solution is stirred under reflex condenser

22
 Figure 16: Experiment setup to filter the asphaltene

Then the de-asphalted crude oil (maltenes) is isolated to saturates, aromatics and
resins using Agilent 1260 Infinity HPLC as in figure 17. The HPLC unit is setup
using Volatile Organic Compounds (VOC) standards provided by Agilent for various
conditions. The mixture comprises of 100μg mL -1 each of n-pentadecane, n-decane,
n-octadecane, n-tridecane, toluene, 1-methylnaphthalene, 1,3 diisopropylbenzene and
phenanthrene dissolved in n-pentane. Two 9.4x250mm Zorbax NH2 columns with 5
µm packing is used in series with a UV detector operating at a wavelength of 254
mm as suggested by Mansoori et al. (2007).

Dichloromethane (DCM), n-hexane, and iso-propanol (IPA) is used as a solvents.

The de-asphalted crude oil is filtered using a 0.2 μm PTFE syringe filter into 1.5
glass vial. Saturates and aromatics are firstly eluted and dichloromethane is used to
extract the resins which are retained in the column during HPLC separation. The
Rotavapor is used to extract the resins as in figure 18. The system is flushed and
cleaned for the next analysis by flushing with iso-propanol and n-hexane for 15 min.

23
Figure 17: High pressure liquid chromatography (Agilent 1260 Infinity)

Figure 18: Resin separation using rotavapor

24
3.2 Project Activities

Start

Preliminary Research
(Literature Review)

Preparation of samples Density, Viscosity & Pre-

(Crude oil) heating

Carbon Distribution
(GCMS)
Characterization of
Paraffinic Composition Wax Content
in Crude oil (UOP-46)

Wax Appearance
Temperature
(DSC & Density meter)
Characterization of
SARA Fraction

Analysis of Data and

Results

End

Figure 19: Project activities

25
3.3 Key Milestone

Several key milestones for this research project must be achieved in order to meet the
objective of this project. Figure 20 shows the key milestones that need to be achieved
by the author throughout the period of the research which is about 8 month.

Problem Statement and Objective of the project

Identifying the purpose of this project

Literature Review
Gathering as much information as possible from various sources such as
journals and technical paper

Experiment Design
Identifying the subjects that need to be investigated and the experimental
procedures, as well as the chemicals needed and the collection of results

Data Analysis and Interpretation

The findings obtained are analyzed and interpreted critically. Comparison
with other literature readings will also be done

Documentation and Reporting

The whole research project will be documented and reported in detail.
Recommendations or aspects that can be further improved in the future
will also be discussed.

Figure 20: Key milestone

26
3.4 Gantt-Chart
Final Year Project 1 Final Year Project 2
Task 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Topic selection
Prelim Research
Collecting reference
Preparation for extended proposal
Submission of extended proposal
Prepare methodology
Proposal defence
Prepare the equipment to be used
Preliminary results
Preparation for Interim Report
Submission of Interim Draft Report
Submission of Interim Report
Start the experiment
Analyse the result
Verify the result with other journal
Preparation for progress report
Submission of progress report
Pre-EDX
Preparation for Final Report
Preparation for Technical Paper
Submission of Draft Report
Submission of Soft Bound
Submission of Technical Paper
Preparation for Oral Presentation
Oral Presentation
Submission of Hard Bound

Figure 21: Gantt-chart

Process
Key Milestone

27
 CHAPTER FOUR

RESULT AND DISCUSSION

The results obtained from various experiments are presented and analysed in this
chapter.

4.1 Density

Density of all samples has been tested at normal laboratory temperature which is
26.5oC and converted into oAPI density using Equation 1. The result is tabulated in
Table 4.

Table 4: Density measurement at 26.5 o C

o
Sample Density API

Dulang 0.837 g/cm3 37.60

Tapis 0.828g/cm3 39.39
Miri 0.869g/cm3 31.33
3
Dubai 0.871g/cm 30.95
Arab 0.862g/cm3 32.65

According to the table, we can observe that the density of Dubai crude oil is the
highest while the density of Tapis Crude oil is the lowest. The calculated oAPI
density shows that all of the samples are categorized as light oil.

28
4.2 SARA Fraction

The SARA fractions measured for Dulang, Arab, Tapis, Miri and Dubai is
summarized in Table 5. Colloidal Instability Index (CII) is calculated by using
Equation 2.

Table 5: SARA fractions of crude oil

Samples Saturates Aromatics Resins Asphaltenes Colloidal

(wt%) (wt%) (wt%) (wt%) Instability
Index
Dulang 82.15 17.85 2.26 0.18 4.09
Arab 51.36 38.16 7.15 3.33 1.21
Tapis 84.92 15.09 1.75 0.13 5.05
Miri 52.34 47.66 34.42 0.12 0.64
Dubai 57.22 42.78 20.83 0.34 0.90

From the table, we can see that Tapis has the highest CII value followed by Dulang,
Arab, Dubai and Miri. Basically, the weight percentage of resins and asphaltenes is
obtained through their weight after being filtered out while the weight percentage of
saturates and aromatics is obtained through the refractive index which is compared to
the standard. Refer to figure 35, figure 36, figure 37, figure 38 and figure 39 in
appendix for the refractive index signal which indicates the ratio of saturates and
aromatics in the samples.

It is observed that the weight percentage of asphaltene in Arab crude oil is high, but
the average value of CII is 1.21 while Tapis crude oil with low asphaltene content
has higher CII value which is 5.05. All samples have CII value higher than 0.9
except Miri and this indicates higher tendencies towards asphaltene deposition (Yen
et al., 2001 and Choiri, 2010). It means that crude oil possessing low asphaltenes
content can also have higher tendency for precipitation as compared to those with
higher asphaltene content and vice versa.

29
4.3 Gas Chromatography Mass Spectrometry

The purpose for GCMS is to analyse the hydrocarbon number distribution of the
paraffinic composition in the crudes samples. From the GCMS, the experimental
measurement is shown in the form of chromatogram where the peaks represent the
types of component present in the compound. The Y-axis of the chromatogram
represents the abundance while the X-axis represents the retention time. The lighter
components are more towards the left of the chromatogram while the heavier
components are more towards the right of the chromatogram. The chromatograms
are shown in figure 22, figure 23, figure 24 and figure 25 for Dulang, Tapis, Dubai
and Arab respectively.

Figure 22: Chromatogram for Dulang crude oil sample

30
Figure 23: Chromatogram for Tapis crude oil sample

31
Figure 24: Chromatogram for Dubai crude oil sample

32
 Figure 25: Chromatogram for Arab crude oil sample

The total area percent (area %) for carbon number range from C20 to C40 was
tabulated in Table 6. Refer to Table 9 to Table 12 in appendix for the list of Carbon
number with respect to retention time and area percent. It is observed that Dulang
crude oil has the highest total area percent followed by Tapis, Arab and Dubai.

33
 Table 6: Total area percent (C 20 - C 40 )

Samples Dulang Tapis Dubai Arab

Total Area Percent 24.599 % 24.291 % 8.514 % 8.017 %

4.4 Wax Analysis

Wax appearance temperature (WAT) of crude oil samples wax measured by using
DSC and density meter while the wax content was measured using UOP-46 method.
Figure 26, figure 27, figure 28 and figure 29 shows the graph of heat flow against
furnace temperature obtained from DSC for Dulang, Tapis, Miri and Dubai
respectively. It represents the cool down portion of the heat flow curve. The wax
appearance temperature is denoted by the section of the curve where the heat flow
begins to decrease as the oil sample gives off heat energy.

Each experiment is repeated with different weight of sample and the result shows
that the value of WAT is almost constant as in Table 7. Therefore, it can be conclude
that the weight of sample does not affect the measurement of WAT.

Table 7: Wax appearance temperature

Sample Weight (mg) WAT (oC)(DSC) WAT (oC)

(Density meter)
Dulang #1 60 37.52 37
Dulang #2 79 36.97 -
Dulang #3 118 36.99 -
Tapis #1 52 26.36 25
Tapis #2 61 26.69 -
Tapis #3 130 26.86 -
Miri #1 65 12.34 12
Miri #2 75 12.30 -
Miri #3 101 12.44 -
Dubai #1 49 15.62 -
Dubai #2 81 15.41 -
Dubai #3 126 15.88 -

34
 WAT= 37.2oC

Figure 26: Graph of heat flow against furnace temperature for Dulang crude
oil sample

WAT= 26.6oC

Figure 27: Graph of heat flow against furnace temperature for Tapis crude oil
sample

35
 WAT= 12.3oC

Figure 28: Graph of heat flow against furnace temperature for Miri crude oil
sample

WAT= 15.6oC

Figure 29: Graph of heat flow against furnace temperature for Dubai crude
oil sample

36
The results for wax appearance temperature measured by using density meter are
shown in figure 30, figure 31, figure 32 and figure 33. The wax appearance
temperature can be determined by drawing a straight line over density data. A slight
change of slope will indicate the wax appearance temperature of the sample. As
observed, the curve for Dulang, Tapis, and Miri crude oil samples shows a clear and
significant change of slope. However, for Dubai crude oil, there is no significant
change of slope for the whole density data. This is due to the low content of wax in
Dubai crude oil. Therefore, method of density meter is suitable only for crude oil
samples with high wax content.

Figure 30: Graph of density against temperature for Dulang crude oil sample

Figure 31: Graph of density against temperature for Tapis crude oil sample

37
 Figure 32: Graph of density against temperature for Miri crude oil sample

Figure 33: Graph of density against temperature for Dubai crude oil sample

Table 8 shows the wax content for each crude oil sample. Dulang crude oil has the
highest total area percent followed by Tapis, Dubai and Miri.

38
 Table 8: Wax Content

Sample Wax Content (wt. %)

Dulang 28.5
Tapis 17.1
Miri 4.7
Dubai 6.2

By comparing the results obtained from Dulang, Tapis and Dubai crude oil samples,
we can see a relationship between paraffinic composition, wax appearance
temperature and wax content. Dulang crude oil with highest content of paraffinic
composition seems to have higher wax appearance temperature and wax content
while Dubai with lowest content of paraffinic composition seems to have lower wax
appearance temperature and wax content. This relationship is important for
development of wax deposition prediction models. Generally, heavier oil should
have more wax than lighter oil strictly based on the definition of wax. Dulang, Tapis,
Miri and Dubai were sorted by API gravity to compare wax content with increasing
specific gravity. It is noted that the API gravity of the samples had no absolute
relationship with the wax content.

As for SARA analysis, the presence and abundance of asphaltenes and high carbon
number paraffins typically, but not always, indicates the potential for asphaltene
and/or paraffin deposition during oil recovery. The relative abundance of aromatics
and resins reduce the tendency of paraffins and asphaltenes to drop out of solution
during petroleum production. Hence, the entire petroleum composition must be taken
into account not only the presence of asphaltenes and paraffins, but also the relative
abundance of aromatics and resins. If there are no asphaltenes and high carbon
number paraffins present in a crude oil, no asphaltene and/or paraffin deposition
should be expected. Their presence, however, does not necessarily imply problematic
organic deposition.

39
4.5 Effect of CO2 Injection on Wax Appearance Temperature

An experiment was conducted to study the effect CO2 injection on wax appearance
temperature. Dulang crude oil was run through continuous CO 2 flooding at 98oC and
3000psia. The sample then was run through differential scanning to measure the wax
appearance temperature. The result shows that the wax appearance temperature for
Dulang crude oil after CO2 injection to be 32.4oC which is lower than the Dulang
crude oil before CO2 injection which is 37.2oC. This is due to the effect of
supercritical carbon dioxide which will dissolve the wax (Stauffer et al., 2000).
Supercritical carbon dioxide occurred when the carbon dioxide was held above its
critical temperature and critical pressure which is 30 oC and 1070psia respectively.
Figure 34 shows the graph of heat flow against furnace temperature for Dulang crude
oil after CO2 injection.

WAT= 32.4oC

Figure 34: WAT of Dulang crude oil after CO 2 injection

40
 CHAPTER FIVE

CONCLUSION AND RECOMMENDATIONS

The project which derived from a problem statement in which to study the problems
related with the solid precipitation in the production system has successfully done.
The key is to study the solid precipitation by using colloidal instability index and
WAT method. All the objectives listed for this project have been achieved by using
the experimental result from the laboratory by using various equipment and methods
such SARA analysis, DSC, density meter, GCMS as well as UOP 46 method.
However, with several available wax appearance temperature measurement
techniques still have not been able to measure the true wax appearance temperature
because each technique require some amount of wax to form for a detectable signal,
the sensitivity and mode of detection varies for all techniques (Kulkarni et al. 2008)

Wax appearance temperature methods used in this work showed to be sensitive to the
amount of wax content. DSC and density meter gave almost similar results of WAT
for samples with high wax content. Result shows that crude oil with higher content of
paraffinic composition will give higher wax appearance temperature as well as wax
content. Dulang crude oil is identified to has the highest risk for both asphaltene and
wax precipitation. A continuous CO2 injection also is proved to affect the WAT as
the result shows a decrease in WAT for Dulang crude oil. Besides, SARA
fractionation was successfully quantified using available laboratory equipments
which based on ASTM D 3279-97 and modified ASTM D 6591-06.

In order to improve the project execution and experimental result, there are several
recommendations that need to be considered which are:

1) Early preparation need to be done to ensure the materials and equipment are set
up properly and ready for the experiment.

41
2) Repetition of measurement should be practice to gain more reliable and accurate
result.
3) More samples should be tested to have more rigid statement and justification.
4) Utilized more approaches to get the data of WAT such as Cross Polar
Microscopy (CPM), Solid Detection System (SDS) as well as Fourier Transform
Infrared Spectroscopy (FTIR).
5) Design the wax and asphaltene inhibitors (e.g. ionic liquid) and test it with flow
loop.
6) Test the risk of solid deposition with different blending options. E.g. Dulang and
Tapis.
7) Measure the wax curve for Malaysian crudes to justify with thermodynamic
model.
8) Collaboration with oil and gas production companies, such as PETRONAS
Research Sdn. Bhd is important to get more accurate result by using high quality
samples as well as utilizing equipment with higher sensitivity.
9) Determine the mole percent of each carbon numbers as well as the molecular
weight experimentally so that we can use it to predict WAT using empirical
models.

42
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 APPENDICES

Table 9: Gas chromatography data for Dulang crude oil

Carbon Retention Time Area

Number Percent
C8 4.156 0.112
C9 6.945 0.230
C10 9.678 0.310
C11 12.562 0.214
C12 15.512 0.940
C13 18.340 2.368
C14 21.025 2.172
C15 23.549 3.089
C16 25.937 2.670
C17 28.226 4.204
C18 30.364 2.961
C19 32.419 2.437
C20 34.379 2.296
C21 36.254 2.079
C22 38.048 1.999
C23 39.770 1.927
C24 41.421 1.899
C25 43.014 1.959
C26 44.542 1.828
C27 46.020 1.732
C28 47.442 1.565
C29 48.818 1.320
C30 50.141 1.343
C31 51.429 1.167
C32 52.668 0.662
C33 53.880 0.574
C34 55.045 0.310
C35 56.185 0.225
C36 57.299 0.130
C37 57.617 0.561
C38 58.504 0.254
C39 59.876 0.215
C40 61.460 0.554

48
Table 10: Gas chromatography data for Tapis crude oil

Carbon Retention Time Area

Number Percent
C8 4.192 1.752
C9 6.405 2.276
C10 9.151 2.534
C11 12.082 2.120
C12 14.979 2.222
C13 17.770 2.844
C14 20.426 3.014
C15 22.919 3.292
C16 25.283 2.927
C17 27.546 4.584
C18 29.658 2.740
C19 31.702 2.398
C20 33.639 2.382
C21 35.486 2.391
C22 37.261 2.241
C23 38.962 2.358
C24 40.596 2.175
C25 42.163 2.136
C26 43.668 1.930
C27 45.128 1.906
C28 16.520 1.639
C29 47.874 1.530
C30 49.165 1.036
C31 50.429 0.906
C32 5.636 0.520
C33 52.826 0.439
C34 53.966 0.200
C35 55.084 0.150
C36 56.168 0.135
C37 57.223 0.111
C38 58.504 0.036
C39 59.666 0.020
C40 61.143 0.050

49
Table 11: Gas chromatography data for Dubai crude oil

Carbon Retention Time Area

Number Percent
C8 4.170 2.215
C9 6.365 2.261
C10 9.089 2.187
C11 12.003 2.265
C12 14.895 2.279
C13 17.675 2.066
C14 20.308 2.400
C15 22.807 2.120
C16 25.166 1.709
C17 27.417 1.992
C18 29.652 0.953
C19 31.573 1.318
C20 33.510 1.153
C21 35.363 1.238
C22 37.132 1.033
C23 38.962 0.094
C24 40.456 0.801
C25 42.084 0.618
C26 43.528 0.669
C27 44.976 0.500
C28 46.380 0.434
C29 47.823 0.345
C30 49.148 0.292
C31 50.305 0.266
C32 51.529 0.219
C33 52.793 0.189
C34 53.871 0.153
C35 55.106 0.120
C36 56.140 0.124
C37 57.392 0.098
C38 58.554 0.090
C39 59.857 0.063
C40 61.351 0.015

50
Table 12: Gas chromatography data for Arab crude oil

Carbon Retention Time Area

Number Percent
C8 4.176 5.16
C9 6.371 2.43
C10 9.100 2.73
C11 12.020 1.88
C12 14.912 1.75
C13 17.686 2.10
C14 20.325 2.12
C15 22.819 1.43
C16 25.183 1.62
C17 27.429 1.62
C18 29.557 1.44
C19 31.663 1.37
C20 33.521 1.30
C21 35.369 1.02
C22 37.138 0.97
C23 38.918 0.81
C24 40.535 0.84
C25 42.096 0.75
C26 43.533 0.56
C27 44.982 0.68
C28 46.392 0.69
C29 47.739 0.60
C30 49.053 0.73
C31 50.311 0.57
C32 51.541 1.54
C33 52.726 0.55
C34 53.961 1.62
C35 55.129 2.91
C36 56.353 2.91
C37 57.403 8.44
C38 58.566 8.44
C39 59.638 0.48
C40 61.295 1.46

51
 Table 13: Normal heptane insoluble measuring procedure

A B
Sample Sample Weight of crucible + Weight of crucible + Insoluble weight NHI % [(B/A) x
weight glass fibre (gram) glass fibre + asphaltenes (gram) 100]
(gram) (gram)
Dulang #1 1.0000 25.8805 25.8805 0.0000 0.000
Dulang #2 1.0076 25.8736 25.8754 0.0018 0.179
Tapis #1 1.0000 25.8695 25.8706 0.0011 0.110
Tapis #2 1.0027 25.8710 25.8726 0.0016 0.160
Miri Light #1 1.0046 25.8779 25.8792 0.0013 0.129
Miri Light #2 1.0000 25.8754 25.8766 0.0012 0.120
Dubai #1 0.9984 25.8397 25.8458 0.0037 0.371
Dubai #2 1.0034 25.8421 25.8452 0.0031 0.310
Arab #1 1.0002 25.8769 25.9072 0.0303 3.025
Arab #2 1.0056 25.8771 25.9137 0.0366 3.641

NHI = Normal Heptane Insoluble (Asphaltene)

52
 Table 14: Measurement of saturates and aromatics percentage for crude oils

Sample Sample Asphaltene Asphaltene Maltene Maltene Sample Maltene Resin (mg) Resin Saturates &
weight (g) (wt%) (g) (mg) injection injected (wt%) aomatics
(g) (ml) (mg) (wt%)
Dulang 1.0076 0.0018 0.18 1.00580 1005.80 6.300 48.74 1.10 2.256752108 97.56
Tapis 1.0014 0.00135 0.13 1.00000 1000.00 10.20 78.46 1.37 1.746078431 98.12
Miri 1.0023 0.00125 0.12 1.00105 1001.05 10.15 78.16 26.9 34.41706405 65.46
Dubai 1.0009 0.0034 0.34 0.99750 997.500 10.20 78.27 16.3 20.82657624 78.83

Table 15: Concentration of calibration components

Calibration Cyclohexane O-Xylene Cyclohexane Area of Area of Saturates Aromatics
Standard (g/100mL) (g/100mL) + O-Xylene cyclohexane O-Xylene (%) (%)
(g/100mL)
A 5 4 9 700231.9 1665691.9 55.56 44.44
B 2 1 3 281287.3 415751.6 66.67 33.33
C 0.5 0.25 0.75 71595.6 105265.3 66.67 33.33
D 0.1 0.05 0.15 17520.9 21086.7 66.67 33.33

53
Figure 35: Refractive index signal for Dulang crude oil

54
Figure 36: Refractive index signal for Arab crude oil

55
Figure 37: Refractive index signal for Tapis crude oil

56
Figure 38: Refractive index signal for Miri crude oil

57
Figure 39: Refractive index signal for Dubai crude oil

58