‫‪Northern Technical‬‬

‫‪University‬‬
‫‪Technical college – Kirkuk‬‬
‫‪Fuel & Energy Tech. Dept.‬‬

‫‪BACHELOR’S PROJECT‬‬
‫– ‪– JUNE 2020‬‬
‫ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

‫‪Desulfurization of petroleum fuels by‬‬

‫‪solvent extraction process‬‬
‫ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬
‫ـ‬

‫‪Student‬‬
‫‪Alaa Jaafar Kadhim‬‬

‫‪Supervised by‬‬
‫‪Dr. Habib A. Hassan‬‬
 CHAPTER ONE: THEORETICAL CONTENT
‫ـــــــــــــــــــــــــــــــــــــــــــ ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

1.1 Introduction
1.2 Gasoline
1.2.1 Definition
1.2.2 SOURCES OF GASOLINE
1.3 SULFUR AND ITS EFFECT
1.4 DESULFURIZATION OF GASOLINE METHOD
1.4.1 HYDRODESULFURIZATION
1.4.2 Oxidative desulfurization
1.4.3 BIODESULFURIZATION
1.4.4 ABSORPTION DESULFURIZATION
1.4.5 SUPERCRITICAL WATER DESULFURIZATION
1.4.5 Extraction desulfurization
1.4.5.1 PROCESS DESCRIPTION

1.4.5.2 ADVANTAGE OF EXTRACTION BY CAUSTIC

TREATMENT

1.4.5.3 DISADVANTAGE OF EXTRACTION BY CAUSTIC

TREATMENT

1.5 THE PROBLEM AND OBJECTIVE

I
 CHAPTER TWO: EXPERIMENTAL SECTION
CONTENT
‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

2.1 ANALYSIS TEST AND APPARATUS

2.2 THE MATERIALS THAT USED
2.3 SAMPLES OF GASOLINE
2.4 PREPARATION OF IONIC LIQUIDS NAOH
2.5 PROCESS DESCRIPTION
2.6 PROCEDURE OF ANALYSIS
2.6.1 DOCTOR TEST
2.6.2 AUTO TITRATION FOR THE DETERMINATION OF SULFUR
COMPOUNDS
2.6.2.1 PERPRATION OF AgNO3
2.6.2.2 PROCEDURE OF THE TEST
2.6.3 TOTAL SULFUR
1.3.6.2 MEASUREMENT OF SULFUR IN GASOLINE
2.6.3.2 CALIBRATION
2.6.3.3. FIND THE CONCENTRATION OF THE STANDARD
SOLUTION

CHAPTER THREE: RESULTS, CALCULATION, AND DISCUSSION

CONTENT
‫ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

3.1 THE RESULTS BEFORE TREATING

3.2 THE RESULTS AFTER TREATING
3.3 DISCUSSION

3.3.1 THE SULFUR COMPOUND BEFORE TREATING

3.3.2 THE SULFUR COMPOUND AFTER TREATING

3.4 CONCLUSION

Bibliography

II
 LIST OF FIGURE
‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

Figures Pages

Fig (1.1):- Schematic representation of a petroleum refinery

Fig (1.2):- NGL Consumption by Sector

Fig (2.1) Dr.Test

Fig (2.2):- Auto titration device

Fig (2.3) gasoline curve
Fig (2.4) total sulfur chart
Fig (2.5) Full range Calibration curve covering typical range of ASTM
D5453
Fig (2.6) Curve I (0.5-10 ng/µL)
Fig (2.7) Curve II (5-100 ng/µL)

Fig (2.8) Curve III (100-1000 ng/µL)

Fig (2.9) total sulfur device

Fig (3.1) sulfur compound before treating
Fig (3.2) sulfur compound before treating
Fig (3.3) sulfur compound after treating
Fig (3.4) sulfur compound after treating

Fig (3.5) sulfur compound after and before treating

III
 LIST OF TABLE
‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

Tables Pages

Table1.1: Health Effects of H2S

Table (2.1) gasoline components

Table (2.1) Response values

Table (3.1) analysis of determine sulfur content before treating

Table (3.2) analysis of determine sulfur content before treating

Table (3.3) analysis of determine sulfur content after treating

Table (3.4) analysis of determine sulfur content after treating

IV
 LIST OF SYMBOLS

‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

symbol Names
H2S Hydrogen Sulfide
SO2 sulfur dioxide
SO4 Sulfate
HDS Hydrodesulphurization
ODS Oxidative desulfurization
SCW Supercritical Water
Aaq Water
Aorg organic liquid
NaOH Sodium hydroxide
AgNO3 Silver nitrate
S Pure sulfur
Na2S H2S
NaSR RSH
N Normality
V Volume
W Weight
Sp.gr specific gravity
M.wt molecular weight
𝛒 Density
Dr.test Doctor test
T.S Total sulfur
NIL Zero
RSH Mercaptans

V
 ACKNOWLEDGMENT
‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

First and foremost, I am grateful to the God for the good health and wellbeing
that were necessary to complete this thesis.

I wish to express my sincere thanks to Mr.Habib A. Hassan, Principal of the Faculty,

for providing me with all the necessary guidance and feedback throughout the
research.

I am also grateful to my friend Ahmed Othman, Whom his support and

encouragement has been invaluable throughout this study.

I take this opportunity to express gratitude to all of the Department faculty members
for their help and support. I also thank my family, and especially my sister Shaymaa
for the unceasing encouragement, support, and attention. I am also grateful to my
partner who supported me throughout this venture.

I also place on record, my sense of gratitude to one and all, who directly or
indirectly, have let their hand in this venture.

VI
 ABSTRACT
‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

In order to obtain the ultra-low sulfur fuels, deep desulfurization of fuels has become a
vital subject of environmental studies. Extraction desulfurization system is one of the most
promising desulfurization processes. The aim of this study is to investigate the possible use
of Ionic liquids as an extractant for the removal of sulfur components.

Desulfurization of a fluid model gasoline by solvent extraction process was

investigated. Many devices was used to determined sulfur compounds in gasoline. A
caustic solvent (NaOH) was selected as the solvent for extractive desulfurization. The
desulfurization effect of gasoline was investigated on a continuous extractive distillation
column. At the optimal conditions. Sulfur content was 198 ppm. Results showed that the
sulfur compounds could be reduced to 25ppm. This method is producing low sulfur
gasoline.

Keywords: Extractive desulfurization, liquid fuel, ionic liquids, gasoline, caustic

VII
 C h a p t e r 1

General Introduction
1.1 INTRODUCTION

Fuel combustion cause pollution to the environment due to the sulfur compounds in fuel
oils, which forms SOX during combustion (Aydına, 2017). In recent years, considerable
attention has been paid to deep desulfurization of fuels. In the petroleum industry,
hydrodesulfurization as a traditional method is used to remove various sulfur compounds
from fuels. The hydrodesulfurization efficiency is limited to remove sulfur compounds
such as thiols, sulfides, and disulfides in fuels. This method cannot be used for hard-to-
remove aromatic sulfur compounds such as dibenzothiophene, benzothiophene (BT),
thiophene (T) (Olawumi O. Sadare F. O., 2017), and their derivatives in fuels. Therefore,
it is necessary to develop other desulfurization processes based on adsorption, oxidation.
Among these methods, extractive desulfurization (EDS) using inorganic solvents were
used for the removal of sulfur compounds from the fuels. Ionic liquids are mixtures of salts
and water. Recently, these compounds were found to be effective in the EDS from models
of gasoline (N. Farzin Nejad a b, 2012.).

Natural gas is typically separated into a gaseous fraction and a liquid fraction using
a separator vessel. The gaseous fraction leaving the separator, which may contain the
impurities such as mercury, carbon dioxide and hydrogen sulfide, is sent to a gas
treatment and the liquid fraction called ‘‘gas condensate’’ which contains sulfur
contents, is fed into a reactor containing a catalyst along with a stream of hydrogen
gas. The product leaving the reactor contains a mixture of hydrogen, hydrogen sulfide,
and natural gas condensate having a reduced amount of sulfur (Javad Ahmadpour,
2018).

2
1.2 Gasoline

1.2.1 Definition

Gasoline, also called gas (United States and Canada), or petrol (Great Britain) or benzene
(Europe) is a mixture of volatile, flammable liquid hydrocarbons derived from petroleum
and used as fuel for internal combustion engines. It is also used as a solvent for oils and
fats. Originally a by-product of the petroleum industry (kerosene being the principal
product), gasoline became the preferred automobile fuel because of its high energy of
combustion and capacity to mix readily with air in a carburetor. Gasoline is a mixture of
hydrocarbons that usually boil below 180 oC (355 oF or, at most, below 200oC (390 oF)
(El-Naggar, 2014). The hydrocarbon constituents in this boiling range are those that have
4 to 12 carbon atoms in their molecular structure and fall in to three general types: paraffins
(including the cyclo paraffins and branched materials), olefins, and aromatics. Gasoline is
still in great demand as a major product from petroleum. The network of interstate high
ways that links towns and cities in the United States are dotted with frequent service centers
where motorists can obtain refreshment not only for themselves but also for their vehicles
(Bellis, 2012).

1.2.2 SOURCES OF GASOLINE

From crude oil in the distillation column under atmosphere pressure each component of
petroleum will production one-by-one, gasoline and other petroleum products from crude
oil and other liquids produced in petroleum refineries (Angela O. Mamudu, 2019), though
this might take many repetitive distillation operations as fig(1.1). However, to do so would
be both very wasteful and prohibitively expensive. On the other hand, 20% of a good crude
oil might yield gasoline on simple distillation Making 1,000,000 gallons of gasoline would
require only 119,000 barrels of crude oil. The major chemical components of straight-run
gasoline are straight-chain paraffin in the range of pentane to nonane (Energy, 1991/1992).

3
 Fig (1.1):- Schematic representation of a petroleum refinery (Skipper, 2001).

From Condensate wells produce free natural gas along with a semi-liquid hydrocarbon
condensate. Whatever the source of the natural gas, once separated from crude oil (if
present), it commonly exists in mixtures with other hydrocarbons, principally ethane,
propane, butane, and pentanes (Devold, OIL AND GAS PRODUCTION HANDBOOK,
2006). While the ethane, propane, butane, and pentanes must be removed from natural gas,
this does not mean that they are all waste products. In fact, associated hydrocarbons, known
as natural gas liquids (NGL), can be very valuable byproducts of natural gas processing.
NGLs include ethane, propane, butane, iso-butane, and natural gasoline as fig (1.2). These
are sold separately and have a variety of different uses such as raw materials for oil
refineries or petrochemical plants (Devold, Oil and gas production handbook, 2013).

4
 Fig (1.2):- NGL Consumption by Sector (Skipper, 2001)

1.3 SULFUR AND ITS EFFECT

Sulfur it’s a chemical element that belongs to group 16 of the periodic table, along with
O, Se and Te. Sulfur is present in many raw industrial gases and natural gas in the form of
hydrogen sulfide. Sulfur is a natural component in crude oil that is present in gasoline and
diesel unless removed. Sulfur in gasoline impairs the effectiveness of emission control
systems and contributes to air pollution. Reducing the sulfur content in gasoline enables
advanced emission controls and reduces air pollution (Jianhua Ge, 2011). The sulfur
compounds in the gasoline are converted to sulfur oxide SOx by combustion at a high
temperature, which causes not only corrosion of car engines but also serious harm to the
environment and human health (ZHANG Cun, 2011).Concentration levels of H2S vary
significantly depending upon their source. H2S produced from absorption processes, such
as amine treating of natural gas or refinery gas, can contain 50-75% H2S by volume or
higher. Many other processes can produce H2S with only ppm concentration (GROUP,
1998) .

5
 The main environmental concerns related to sulfur emissions are acid rain and the
formation of particulate matter. When sulfur dioxide (SO2) is emitted and combines with
water it forms sulfuric acid, or acid rain. Acid rain has many negative environmental
impacts including the acidification of aquatic systems, increasing soil acidity and damage
to vegetation. Acid rain can also cause the degradation of buildings and other human
infrastructure. Sulfur is also emitted from vehicles in the form of sulfate particles (SO4)
(Full, 2000 ). Along with nitrogen oxides (NOx), these particles contribute to particulate
matter (PM) formation. Airborne lead is highly toxic and can impact human development
and the nervous system. Sulfur is emitted as sulfur dioxide (SO2) and sulfate particulate
matter—pollutants which damage human health, impair visibility, and lead to the
acidification of ecosystems (X.Pan, 2011).Sulfur compounds are responsible for major
damage to materials. Sulfur oxides generally accelerate metal corrosion by first forming
sulfuric acid either in the atmosphere or on the metal surface. Sulfur dioxide is the most
detrimental pollutant with regard to metal corrosion [28]. Temperature and relative
humidity also significantly influence the rate of corrosion (Miller, 2005).

The acid rain as a result of this emission dissolves the calcium carbonate in monuments
and buildings that are made with limestone and marble. Sulfuric acid can cause huge
economic losses owing to the occurrence of metal corrosion in machineries and vehicles in
oil plants (Olawumi O. Sadare F. O., 2017).

Hydrogen sulfide is especially dangerous when it occurs in low-lying areas or confined

workspaces or when it exists in high concentrations under 1 pressure (Roth, 2004). As a
result, work practices, such as continuous monitoring and the use of specified respiratory
protective equipment in certain work situations, are of great importance.it is either the
gaseous or liquid forms of the compound. Synonyms for hydrogen sulfide include

6
hydrosulfuric acid, sulfurated hydrogen, sulfur hydride, rotten-egg gas, and stink damp
(Joh n F. Finklea, 1977).

Human health effects of exposure to Hydrogen Sulfide, an irritant and an

asphyxiant, depends on the concentration of the gas and the length of exposure.
Background ambient levels of H 2S in urban areas range from 0.11 to 0.33 ppb,
while in undeveloped areas concentrations can be as low as 0.02 to 0.07 ppb. A
rotten egg odor characterizes H 2 S at low concentrations, and some people can
detect the gas by its odor at concentrations as low as 0.5 ppb. About half of the
population can smell H2S at concentrations as low as 8 ppb, and more than 90%
can smell it at levels of 50 ppb. Hydrogen Sulfide, however, is odorless
at concentrations above 150 ppb, because it quickly impairs the olfactory senses
(Rao, 2014). Some of the Health effects of H2S on human are given in the table(1.1)

Table1.1: Health Effects of H2S (Somasekhara, 2014).

7
1.4 DESULFURIZATION OF GASOLINE METHOD
desulfurization methods of liquid fuels such as Hydrodesulfurization, Oxidative
desulfurization (Rashad Javadli, 2012), Biodesulfurization, Absorption desulfurization,
Extraction desulfurization and Supercritical water desulfurization (Fatemeh Boshagh,
October 2016).each of them have different condition and catalyst for removing sulfur ,
Clean and environmental friendly transportation fuels are the need of an hour. It can be
achieved by removing undesirable compounds/elements in fuel oil. Most prominent among
these are sulfur compounds. Thus removal of sulfur compounds from fuel oils has become
very significant and gained maximum attention worldwide to produce better quality fuels
(Mohammad Nahid Siddiqui, 2013).
The presence of sulfur-containing compounds in fossil fuels leads to corrosion
problems and inactivation of the pollution control catalysts in internal combustion engines.
Furthermore, sulfur oxides (SOx), produced during the combustion of untreated fossil
fuels, are the main source of acid rain and air pollution. Due to these environmental
concerns, very stringent standards on the sulfur content of transportation fuels have been
legislated in different countries. Therefore, different methods for removal of the sulfur-
containing compounds from fuels have been studied by many researchers (Mohammad
Dana, 2019).

1.4.1 HYDRODESULFURIZATION
HDS is a catalytic chemical process widely used to remove sulfur (S) from natural gas and
from refined petroleum products such as gasoline or petrol, jet fuel, kerosene, diesel fuel,
and fuel oils. The purpose of removing the sulfur is to reduce the sulfur dioxide (SO2)
emissions that result from various combustion practices (Bose, 2015). Hydrogenation of
the sulfur compounds results in the formation of undesirable, toxic gaseous hydrogen
sulfide. The industrial hydrodesulfurization processes include facilities for the capture and
removal of the hydrogen sulfide gas (Thanh Tung NGUYEN, 2017). In petroleum
refineries, the hydrogen sulfide gas is then subsequently converted into byproduct

8
elemental sulfur. In fact, the vast majority of the 68,000,000 metric tons of sulfur produced
worldwide in 2010 was byproduct sulfur from petroleum refining and natural gas
processing plants. It requires either severe process conditions such as temperature, pressure

and space velocity or the use of novel effective catalysts that able to convert the less
reactive-non-desirable compounds at an acceptable rate (Amin, 2011).

1.4.2 OXIDATIVE DESULFURIZATION

ODS process is remarkably successful in the removal of sulfur under mild reaction
conditions (Muhammad Nobi Hossain, 2019). Which the sulfur compounds can be
oxidized into their corresponding sulfoxides and sulfones (Dan Xu, 2009). Appears to be
particularly promising and is currently receiving increasing attention because it avoids the
use of hydrogen and allows the process to be conducted at ambient conditions. Although
this process is effective, there are still some problems such as cross-contamination between
extractant and fuel and loss of fuel. ILs have been examined for effective removal of S-
containing aromatic compounds, and these liquids are easy to handle because of
nonvolatility, nonflammability, and high thermal stability (ZHAO Di-shun, 2009).

1.4.3 BIODESULFURIZATION

Biodesulfurization is described as the process by which the use of a catalyst of biological

nature enables the removal of sulfur content in oil fractions at moderate pressure and
temperature conditions. Given its specificity, it is presented as a promising alternative for
the removal of organic-sulfured molecules resistant to conventional technologies, such as
dibenzothiophenes and their substituted forms (Julia Acero, 2003). It’s involving the use
of specific microorganisms to the removal of sulfur present in the carbon chain, using the
oxidation pathway “4S”, in which there is cleavage of carbon–sulfur bond, and maintaining
the calorific value of the organic molecule. The BDS is a low-cost technique when
compared with HDS. For this process to occur, activation of specific enzymes is needed
(Santos, 2014).

9
1.4.4 ABSORPTION DESULFURIZATION
Is typically per-formed in wet scrubbers, where the absorption mean is a water slurry
containing fine particles of limestone (or other alkaline absorbent species). In this way, Sox
absorption rate is enhanced by reaction with dis-solved particles, which provide a
continuous alkaline reagent supply. However, it has been suggested that in areas close to
the sea seawater scrubbing is an economically attractive solution rather than a slurry, where
scrubbing performance relies on seawater natural alkalinity. The advantages of using
seawater involve simple plant design, no addition of chemicals and no solid by-products.
The acidified effluent can be discharged directly into the sea, after a further neutralization
step obtained by mixing with fresh sea-water and additional forced oxidation of sulfite ions
by air blowing (Giuseppe Caiazzo, 2011).

1.4.5 SUPERCRITICAL WATER DESULFURIZATION

(SCW) desulfurization was investigated for both model sulfur compounds and Arab
Heavy crude. In part 1, the reactions of alkyl sulfides in SCW were studied. During hexyl
sulfide decomposition in SCW, pentane and CO+CO2 were detected in addition to the
expected six-carbon products (Kida, 2014). A multi-step reaction sequence for hexyl
sulfide reacting with SCW is proposed which explains the surprising products.
Intermediate studies were performed to confirm that the key intermediate hexanal forms
and rapidly decomposes to pentane and CO (Pushkaraj R. Patwardhan, 2013). In part 2,
Arab Heavy crude was treated with SCW and analyzed with comprehensive gas
chromatography (GCxGC) coupled with two detectors, sulfur chemiluminescence detector
(SCD) and a flame ionization detector (FID). SCD is a sulfur specific detector that allowed
detailed analysis of the reactions that occur during SCW treatment of real fuel mixtures
(Demirbas, 2016).

10
1.4.5 EXTRACTION DESULFURIZATION
Liquid-liquid extraction has been applied industrially for many years for the production
of lubricating oils, pharmaceutical preparation, natural product isolation, etc. Liquid ion
exchange, however, was not developed until the middle fifties when it was rapidly applied
in the recovery of uranium from low-grade ore. Its use in copper production only started
two years ago and large-scale use only in the last five (Dr. D.S. Flett, SEPTEMBER 9th -
16th 1977).
Solvent extraction techniques have a broad field of applications in inorganic and
organic chemistry and large-scale industrial separations, in analytical chemistry, in
pharmaceutical and biochemical industries, and in waste treatment. In addition, solvent
extraction is a good instrument for studying fundamental understanding of equilibrium and
kinetics of complex formation processes. Extraction methods have now become a routine
procedure in separation technologies (El-Nadi, 2017).
In analytical chemistry, solvent extraction has come to the forefront in recent years as a
popular separation technique because of its elegance, simplicity, speed and applicability to
both tracer and macro amounts of metal ions. The aspects and basic principles of solvent
extraction are very well explained. In analytical chemistry, solvent extraction has come to
the forefront in recent years as a popular separation technique because of its elegance,
simplicity, speed and applicability to both tracer and macro amounts of metal ions. The
aspects and basic principles of solvent extraction are very well explained (Fifield F. W.,
1975).

1.4.5.1 PROCESS DESCRIPTION

Treating of petroleum products by washing with solutions of alkali (caustic or lye) is almost
as old as the petroleum industry itself. Early discoveries that product odor and color could
be improved by removing organic acids (naphthenic acids and phenols) and sulfur
compounds (mercaptans and hydrogen sulfide) led to the development of caustic washing
(Speight, 1978).

Solvent extraction refers to the process of selectively removing a solute from a liquid
mixture with a solvent. As a separation technique, it is a partitioning process based on the
unequal distribution of the solute (A) between two immiscible solvents, usually water (aq)
and an organic liquid (org):

11
 Aaq Aorg
NaOH is extensively used in a variety of sweetening processes like caustic treatment,
Merox process, chelate sweetening, inhibitor sweetening etc. which shows that NaOH has
greater affinity for the sulfur compounds in the petroleum fractions. This is probably due
to the acidic character of the certain sulfur compounds like mercaptans, which readily
distributes from the oil phase in to the alkaline layer of NaOH and converts to sulphides
(MOHAMMAD SHAKIRULLAH, 2010).

The process consists of mixing a water solution of lye (sodium hydroxide or caustic
soda) with a petroleum fraction. The treatment is carried out as soon as possible after the
petroleum fraction is distilled, as contact with air forms free sulfur, which is very corrosive
and difficult to remove. The lye reacts with any hydrogen sulfide present to form sodium
sulfide, which is soluble in wate

1.4.5.2 ADVANTAGE OF EXTRACTION BY CAUSTIC TREATMENT

(FDA, 2004)
 Lends itself to rapid and very selective separations that are usually highly efficient.
 Partition coefficients are often approximately independent of concentration down to tracer
levels and, therefore, can be applied to a wide range of concentrations.
 Can usually be followed by back-extraction into aqueous solvents or, in some cases, the
solution can be used directly in subsequent procedures. This also provides significant
preanalysis concentration of the analyte.
 Wide scope of applications the composition of the organic phase and the nature of
complexing or binding agents can be varied so that the number of practical combinations
is virtually unlimited.
 Can be performed with simple equipment, but can also be automated.

12
1.4.5.3 DISADVANTAGE OF EXTRACTION BY CAUSTIC
TREATMENT (FDA, 2004)

 Cumbersome for a large number of samples or for large samples.

 Often requires toxic or flammable solvents.
 Can be time consuming, especially if attainment of equilibrium is slow.
 Can require costly amounts of organic solvents and generate large volumes of organic
waste.
 Can be affected by small impurities in the solvent(s).
 Multiple extractions might be required, thereby increasing time, consumption of materials,
and generation of waste.

1.5 THE PROBLEM AND OBJECTIVE

In general, air pollution is caused by both natural and man-made sources. Major man-
made sources include automobiles, power generation and the industrial activities, which
represent the main source of air pollution, especially oil industry activities using huge
amount of consumable fuel like power plants and oil refineries; due the high rate emission
of fume, solid particulates and toxic gases in quantity more than every other industry. These
industries will be more hazardous upon its existence inside the limits of the cities, or its
existence inside urban area, such as Kirkuk oil refinery (Moutaz A. Al-Dabbas, 2012). In
Iraq, oil refineries were already a local source of pollution due to inadequate governance
and control measures. However, the recent conflict has turned oil and gas industry facilities
into a major source of health and environmental risks. Both militant groups and local
people have tapped refineries, tanks, pipelines and oil fields for their income potential
(Price, 2018).

13
 The main objective of this project is to study the desulfurization of fuels by using
liquid ‫ــ‬liquid extraction. In particular, petroleum product is going to be tasted, during
desulfurization of gasoline

• Being a part of reducing atmospheric pollution and derived effects such as acid rain.

• Minimizing the negative health and environmental effects of automobile exhaust.

14
C h a p t e r 2

Experimental Section

15
This chapter contains a description of the apparatus, chemical substance, and analysis
measurement method of sulfur, which were used in the test of experiment work.

The experimental work was performed in preparing the chemical and testing sulfur content
in the gasoline model.

2.1 ANALYSIS TEST AND APPARATUS

The test analyses of sulfur content in gasoline would be

1- Doctor test this is a qualitative test for the presence of hydrogen sulfide, or
mercaptans in the absence of hydrogen sulfide, in gasoline, jet fuel, kerosene and
similar petroleum products. ASTM Test Method D 4952, Qualitative Analysis for
Active Sulfur Species in Fuels and Solvents (Doctor Test)
2- Auto titration for the determination of sulfur compounds as hydrogen sulfide and
mercaptan sulfur in liquid hydrocarbons and oils.
3- Total sulfur are measured with an elemental combustion analyzer according to UV-
Fluorescence detection technique or Microcoulometric detection technique. These
measurements are carried out mainly in the Oil & Gas Industry. Petroleum products
like gasoline.

Also, other equipments were used in analysis test such as:-

1- Cylinder
2- Dark volumetric flask
3- Beaker
4- The balance of chemical
5- Auto titration device
6- Total sulfur device

16
2.2 THE MATERIALS THAT USED ARE:-
1- Gasoline
2- NaOH
3- AgNO3
4- Pure sulfur S
5- Distilled water
6-
2.4 SAMPLES OF GASOLINE
The gasoline sample was taken from North Gas Company (N.G.C) in Kirkuk. It was
consist as shown in table (2.1)

COMPONENTS PERCENTAGE %
C3 WT% ‫ـــــــــــ‬
IC4 WT% ‫ـــــــــــ‬
NC4 WT% 0.23
IC5 WT% 30.23
NC5 WT% 30.14
C6 WT% 39.40

Table (2.1) gasoline components

2.4 PREPARATION OF IONIC LIQUIDS NAOH

The ionic liquid NaOH was prepared (0.1N, 100 g, and 98%) was dissolved in water (1000
mL).

17
2.5 PROCESS DESCRIPTION
The feed of gasoline treatment section is the residue product depropanizer unit. Gasoline
desulfurization unit performs on four main processes to remove sulfur compounds from
gasoline and prepare it for the end user., the first process, the pre-alkalization, removes
hydrogen sulfide, carbon dioxide and a small portion of carbonyl sulfide from the
propane stream using an alkaline solution by the following reactions:

H2S + 2NaOH Na2S + 2H2O

CO2 + 2NaOH Na2CO3 + H2O
COS + 4 NaOH Na2S + Na2CO3 + 2 H2O
From the top of the pre-alkalization vessel, the feed of the second process,
Extraction, enters the bottom of an extraction column, after being heated through a heat
exchanger. Mercaptans and Carbonyl Sulfide are removed from the Propane Stream in
presence of an aqueous caustic solution and a small amount of catalyst, according
to the following reactions:

RSH + NaOH RSNa + H2O

Activator
COS + 4 NaOH Na2S + Na2CO3 + 2 H2O
The caustic solutions are from caustic solution regeneration stage and Tanks
improvised in the Plant for storing materials. Water washing Stage, performed by
bubbling the Propane streams through the Water, to remove caustic traces from the bulk
of Propane. Finally, the Water droplets are adsorbed by a salt filter and flows to
the Propane Treatment section.

18
2.6 PROCEDURE OF ANALYSIS
2.6.1 DOCTOR TEST
The sample is shaken with a sodium plumbite solution in a test tube. If hydrogen sulfide is
present the following reaction occurs:

Na2PbO2 + H2S → PbS + 2NaOH

The lead sulfide is black and readily visible. If this reaction does not appear, sulfur is
added to the test tube and the mixture shaken again. If mercaptans are present, on shaking
they undergo a series of reactions, coloring the hydrocarbon layer first orange, then red and
brown, and finally a black precipitate of lead sulfide appears as shown in fig (2.1) . The
overall reaction may be written:

Na2PbO2 + 2RSH → (RS)2Pb + 2NaOH

(RS)2Pb + S → RSSR + PbS

The sodium plumbite (Doctor) solution may be prepared or purchased.

Fig (2.1) Dr.Test

19
2.6.2 AUTO TITRATION FOR THE DETERMINATION OF SULFUR
COMPOUNDS

2.6.2.1 PERPRATION OF AgNO3

Dissolve 8.495 gm of AgNO3 in 500 ml of distilled water, it kept in dark volumetric

flask because AgNO3 affected by light.

2.6.2.2 PROCEDURE OF THE TEST

1- Take 100 ml of gasoline titration solution by cylinder
2- Empty it in a beaker and put it on the balance
3- Zero the balance and add (50-70) gm. of gasoline
4- Record the final weight
5- Put the sample in Auto titration device as fig (2.2)
6- Write H2S , RSH percentage(2.3)

Fig (2.2):- Auto titration device

20
 Fig (2.3) gasoline curve

𝐍𝐀𝐠𝐍𝐎𝟑 × 𝐕𝐀𝐠𝐍𝐎𝟑 × 𝟏. 𝟔
𝐍𝐚𝟐 𝐒 =
𝐖𝐒𝐚𝐦𝐩𝐥𝐞

𝐍𝐀𝐠𝐍𝐎𝟑 × 𝐕𝐀𝐠𝐍𝐎𝟑 × 𝟑. 𝟐
𝐍𝐚𝐒𝐑 =
𝐖𝐒𝐚𝐦𝐩𝐥𝐞

Na2S = H2S

NaSR = RSH

NAgNO3 = normality of AgNO3

V AgNO3 = volume of AgNO3

W sample = weight of gasoline sample

21
2.6.3 TOTAL SULFUR
(TS) Stands for the sum parameter of all organic and inorganic sulfur compounds. Trace
levels (0.02 – 10.000 mg/kg or ppm by weight) of Total Sulfur are measured with an
elemental combustion analyzer according to UV-Fluorescence detection technique or
Microcoulometric detection technique. These measurements are carried out mainly in the
Oil & Gas Industry.

DESCRIPTION

It consists of three main parts

1- Furnace which contains Florence lamp to sense SO2
2- Detector
3- Injector
a- Gas injector
b- Liquid injector
4- Laptop to connect with the device and read the result.

1.3.6.2 MEASUREMENT OF SULFUR IN GASOLINE

A hydrocarbon liquid sample (gasoline) is directly injected by a completely automated
liquid sampler into a high-temperature, dual-temperature zone combustion tube wherein
sulfur components are combusted and vaporized. The released sulfur is oxidized to sulfur
dioxide (SO2) in an oxygen-rich atmosphere.

A stream of inert gas (argon or helium) carries the reaction products after the produced
water vapor is removed into a reaction chamber. In this chamber, the SO2 molecules are

converted to excite through the absorption of energy of a UV lamp and emitting light
(fluorescence) while it settles into a stable state.

22
The emitted light signal is measured by a Photomultiplier tube.

To calculate the area, the response signal is integrated. The linear regression function of
the concentration of standard mixtures versus integrated area can be used to calculate the
sulfur concentration of an unidentified product.

Fig (2.4) total sulfur chart

2.6.3.2 CALIBRATION
Calibration curves are generated using tert-Butyl-di-Sulfide in o-Xylene standards. Each
of the calibration solutions and blanks (o-Xylene) are measured three times. The average
response of the blank injections is subtracted from each calibration standard response
conform method. Although the ElemeNtS system is linear in response, ranging from 0 –

23
1000 ng/µL (figure 6), separate calibration curves have been produced according to the
proposed ranges in ASTM D5453 (Figures 2.6, 2.7, 2.8).

Table (2.1) Response values

Fig (2.5) Full range Calibration curve covering typical range of

ASTM D5453
24
Fig (2.6) Curve I (0.5-10 ng/µL)

Fig (2.7) Curve II (5-100 ng/µL)

25
Fig (2.8) Curve III (100-1000 ng/µL)

Fig (2.9) total sulfur device

26
2.6.3.3. FIND THE CONCENTRATION OF THE STANDARD
SOLUTION
To find the concentrations of the standard liquid injected we have calculate the
concentration of the standard liquid. Choose more than one concentration to drew the curve

Vs ×SP.GR ×106 ×M.WT

N=
Vt ×ρ×M.WT

N= concentration of standard solution

Vs= inject sample volume

Sp.gr = specific gravity of the standard solution

M.wt = molecular weight of sulfur

Vt = total volume of solution

ρ = density of o-Xylene

M.wt = molecular weight of standard

27
 C h a p t e r 3

Results, Calculation, and Discussion

28
This chapter contains results and conclusion

3.1 THE RESULTS BEFORE TREATING

AUTO
SAMPLE Dr.test TITRATION T.S
H2S RSH

NO.1 +VE NIL 198 245

NO.2 +VE NIL 175 224

NO.3 +VE NIL 150 235

Table (3.1) analysis of determine sulfur content before treating

AUTO TITRATION
SAMPLE Dr.test T.S
H2S RSH

NO.1 +VE NIL 190 230

NO.2 +VE NIL 185 257

NO.3 +VE NIL 165 255

Table (3.2) analysis of determine sulfur content before treating

29
3.2 THE RESULT AFTER TREATING

AUTO TITRATION
SAMPLE Dr.test T.S
H2S RSH

NO.1 -VE NIL 25 201

NO.2 -VE NIL 12 220

NO.3 -VE NIL 11 225

Table (3.3) analysis of determine sulfur content after treating

AUTO TITRATION
SAMPLE Dr.test T.S
H2S RSH

NO.1 -VE NIL 17 212

NO.2 -VE NIL 26 215

NO.3 -VE NIL 20 219

Table (3.4) analysis of determine sulfur content after treating

30
3.3 DISCUSSION
The treatment proses was by using NaOH and mixing it with natural gasoline to remove
sulfur compounds in it.

3.3.1 THE SULFUR COMPOUND BEFORE TREATING

After taking the sample of natural gasoline and analyzing it, the sulfur compound was as
fig. (3.1) &(3.2).

300

250

200

150

100

50

0
Dr.test RSH T.S

no. 1 no. 2 no. 3

Fig (3.1) sulfur compound before treating

31
 300

250

200

150

100

50

0
Dr.test RSH T.S

NO.1 NO.2 NO.3

Fig (3.2) sulfur compound before treating

3.3.2 THE SULFUR COMPOUND AFTER TREATING

After treating with NaOH it appears that the sulfur compound decrease and Dr.test be free
of sulfur contents .The total sulfur level was decreased from 255 to 212 ppm as shown in
figures (3.3) & (3.4) & (3.5).

250

200

150

100

50

0
Dr.test RSH T.S

NO.1 NO.2 NO.3

Fig (3.3) sulfur compound after treating

32
250

200

150

100

50

0
Dr.test RSH T.S

NO.1 NO.2 NO.3

Fig (3.4) sulfur compound after treating

300

250

200

150

100

50

0
Dr.test RSH T.S

NO.1 NO.2 NO.3 NO.1 NO.2 NO.3

Fig (3.5) sulfur compound after and before treating

33
3.4 CONCLUSION
Desulfurization of petroleum fractions by extraction with NaOH is an economic, simple,
and efficient process. The sulfur contents of the nature gasoline can be lowered up to 60%.
The process has the advantage of easy handling and the use of less expensive reagents over
conventional hydrodesulfurization, oxidative desulfurization, and adsorptive
desulphurization, etc. which make use of expensive chemicals, equipments, difficult to
process and are more time-consuming.

34
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39
 ‫وزارة التعليم العالي و البحث العلمي‬
‫الجامعة التقنية الشمالية‬
‫كلية التقنية ‪ /‬كركوك‬
‫هندسة تقنيات الوقود و الطاقة‬

‫بحث تخرج‬
‫–ايلول ‪–1212‬‬
‫ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

‫ازالة الكبريت من الوقود النفطي باستخدام مذيب بعملية‬

‫االستخالص‬
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‫تم اعداده من قبل الطالبة‬

‫االء جعفر كاظم‬

‫المشرف على البحث‬

‫االستاذ حبيب عزيز حسن‬

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