Republic of Iraq Ministry of Higher Education & Scientific Research University Of Technology

Improvement of Gasoline Octane Number by Blending Gasoline with Selective Components

A Thesis Submitted to the Department of Chemical Engineering of the University of Technology in Partial Fulfillment of the Requirements for the Degree of Master of Science in Chemical Engineering/Oil Refinery & Petrochemical Industry

By

Eiman Ali Eh. Sheet

(B.Sc. in Chem. Eng.,H.D in Gas &Oil Refinery)

Supervised By Dr. Adel Sharif Hamadi

May 2008

) (

) :23(

Dedicated to My Parents, My Husband, And My Two Girls

SUPERVISOR CERTIFICATION
I certify that this thesis was prepared under my supervision as a partial fulfillment of the requirements for the degree of Master of Science in Chemical Engineering at the Chemical Engineering Department, University of Technology.

Signature Supervisor: Dr. A.Sh. Hamadi Date:

In view of the available recommendations I forward this thesis for debate by the examination committee.

Signature: Name: Dr. Khalid Ajmi Sukkar Head of the Post Graduate Committee Department of Chemical Engineering Date:

COMMITTEE CERTIFICATION
We certify that we have read this thesis, and as an Examining Committee examined the student in its contents and that in our opinion it meets the standard of a thesis for the degree of Master of Science in Chemical Engineering.

Signature: Name: Dr. Adel. Sh. Hamadi (Supervisor)

Signature: Name: Dr. Neran K. Ibrahim (Member)

Signature: Name: Dr. Adnan A.J. Abdul Razak (Member)

Signature: Name: Prof. Dr. Abdul Halim A.K Mohammed (Chairman)

Approved by the University of Technology-Baghdad.

Signature: Name: Dr. Mumtaz A. Zablouk Head of Chemical Engineering Department Date:

ACKNOWLEDGEMENT
Above all, praise is to work. I would like to acknowledge my gratitude to my supervisor Dr. Adel Sharif Hamadi for his guidance, advice and support. Special thanks expressed to Mr. Dathar Al Khashab, Mr. Lateef Wahab, Mr. Kerim Thamer, Mr. Tarik Talib, Mrs. Inaam Mahmood, Mr. Yosif Tawfeeq, Mr. Sabah Abd Alzahra, and Al Doura Refinery Laboratory Staff for their assistance in providing the required equipments and materials to complete this work. I would like to express my special thanks to Dr. Jehad Yamin/University of Jordon/Mechanical Department, for providing me with references to enrich this work. I would like to express my special thanks to chemical engineer Safaa Alden Alsalehy/Al Doura Refinery. I would like to express my thanks to all Al Doura Refinery staff who helped me in this work. I would like to express my thanks to all the Chemical Engineering Dep. /University of Technology staff for their care and scientific outstanding performance during the period of this work. Finally, I extend my grateful thanks to all who helped me.

GOD who has sustained me throughout this

ABSTRACT
The main objective of this project was preparation of premium gasoline, by blending of different gasoline cuts produced in Al Doura Refinery. Alternative additives were prepared from blending of some selective components (alcohol, aromatic) to enhancing octane number of Al Doura gasoline pool.
.

Various petroleum streams were investigated including Light Straight Run Naphtha (LSRN), Reformate, and Power Formate, and tested by ASTM standard methods, such as RVP, Distillation temperatures, Sulfur content, Water content, Gum existent, PONA content, and octane number measuring by CFR engine and ZX analyzer.
.

Gasoline pool was prepared by blending 30% vol LSRN, 45% vol Reformate, and 25% vol Power Formate, RON was recorded (84.5). Selective components were added to the gasoline pool (in different vol %) to improving it octane, such as Ethanol, Methanol, Toluene, Benzene, Xylene, Aniline ...etc. Octane number of blends was measured by CFR engine.
.

The best was selected and mixing with each other in various vol% to preparing alternative additives of TEL&MMT to enhancing octane number of Al Doura gasoline pool.
.

Mixtures of eleven alternative additives were prepared and adding in 10.7%vol to the prepared gasoline pool, increasing RON was (3-11.5). The best (E10, E11, E9, and E6). However, added (E10, E11, E9, and E6) in 10.7%vol to LSRN, RON increasing was (89).
vi
.

(E10) was booster octane, added in 7.4%vol to the two different samples of gasoline pool, which tested by ASTM standard methods before and after adding (E10), octane number increasing for the first sample was recorded (5.7), and (3.7) for the second, however adding 7.4% vol of (E10) to prepared gasoline pool, increasing RON to (9.1) was achieved.
.

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TABLE OF CONTENTS Subject Page ACKNOWLEDGEMENTi TABLE OF CONTENTS...ii LIST OF FIGURES.....iv LIST OF TABLES....v ABSTRACT....vi NOMENCLATURE...............................................................................iix CHAPTER 1: INTRODUCTION................1 1-1 Gasoline Blending........2 1-2 Physical and Chemical Properties of Gasoline...4 1-3 Scope of the Present Work.....7 CHAPTER 2: LITERATURE SURVEY.....8 2 - 1 I n t e r n a l C o m b u s t i o n Engines......8 2-1-1 Anti-Knock Performance......9 2-1-2 Octane Rating...13 2-1-3 Octane Number Sensitivity..18 2-2 Gasoline Engine Emission.....18 2-3 Gasoline Additives.....20 2-3-1 Gasoline Anti-Knock Additives ..20 2-3-1-1 History and Background.........22 2-3-1-2 Octane Booster .............................................................27 2-3-2 Oxidation Inhibitors......29 2-3-3Corrosion Inhibitors .......29 2-3-4 Metal Deactivators .....30 2-3-5 Demulsifies.....30 2-3-6 Antirust Additives....31 2-3-7 Dyes....31 2-3-8 Upper Cylinder Lubricants.....32 2-3-9 Antipreigaition Agents....32 2-3-10 Deicing and Antistall Agent..33 CHAPTER 3: EXPERIMENTAL WORK ... ..34 3-1 Gasoline Specification....34 3-2 Al Doura Refinery Gasoline Production ................34 3-2-1 Standard Test Method for Vapor Pressure of Petroleum P Products............................................................................37 3-2-1-1 Summary of Test Method........37

3-2-2 Standard Test Method for Distillation of Petroleum Products at Atmospheric Pressure ........................................................38 Subject Page 3-2-2-1 Summary of Test Method.......38 ii 3-2-3 Standard Test Method for Sulfur in Gasoline By Energy Dispersive X-ray Fluorescence Spctrometry.........................39 3-2-3-1 Summary of Test Method..39 3-2-4 Standard Test Method for Determination of Water in Petroleum Product.....40 3-2-4-1 Summary of Test Method..40 3-2-5 Standard Test Method for Gum Content in Fuels ..........41 3-2-5-1 Summary of Test Method..41 3-2-6 IROX 2000 .......42 3-2-6-1 Principle.................................43 3-2-7 Cooperative Fuel Research Engines (CFR)........44 3-2-7-1 Summary of Test Method...................44 3-2-8 ZELTX Measurements...................46 3-3 Preparation Gasoline Pool ...............................................................49 3-4 Antiknock Agents............................................................................49 3-5 Reformulated Antiknock Agents.....................................................51 CHAPTER 4 : RESULTS AND DISCUSSIONS53 4-1 Introduction....53 4-2 Prepared Gasoline Pool ..............53 4-3 Octane Number Measurement57 4-4 Additives for Al Doura Gasoline Pool ..58 4-4-1 First Stage.....................................................58 4-4-1-1 Metallic Additives .................................................58 4-4-1-2 Alcohol Components ................................................61 4-4-1-3 Aromatic Components ............................................65 4-4-1-4 Other Components .66 4-4-2 Reformulated of Additives (Second Stage) ..67 CHAPTER 5: CONCLUSIONS & SUGGESTIONS.73 5-1 Conclusions73 5-2 Suggestions...74 REFRENCES...75 ABSTRACT IN ARABIC...80

iii

NOMENCLATURE
Symbol AKI ASTM bc CFR CI CO CO 2 DCI DME EDB ETBE HC HGO HSRN HUCR IPC IREDS LGO LPG LSRN MMT MON MTBE NIR NOx PONA RDON RFC RON Description Antiknock Index American Society for Testing Material bottom center Cooperative Fuel Research Compression Ignition Carbon Monoxide Carbon Dioxide Di Cyclo Pentadienyl Iron Di Methyl Ether Ethylene Di Bromide Ethyl Tertiary Butyl Ether Hydrocarbon Heavy Gas Oil Heavy Straight Run Naphtha Highest Units Compression Ratio Iron Penta Carbonyl Near Infrared Emitting Diodes Light Gas Oil Liquefied Petroleum Gas Light Straight Run Naphtha Methylcyclopentadienyl Manganese Tricarbonyl Motor Octane Number Methyl Tertiary Butyl Ether Near Infrared Nitrogen Oxides Paraffin, Olefin, Naphthene, and Aromatic Road Octane Number Reformulated Gasoline Research Octane Number
iix

Symbol RVP SAE SI TAME tc TEL USEPA USPHS ZX

Description Reid Vapor Pressure Society of Automotive Engine Spark Ignition Tetra Amyl Methyl Ether top center Tertiary Ethyl Lead United State Environmental Public Agency United State Public Health Service Zeltex

ix

LIST OF TABLES Tables Title Page (1-1) Physical and Chemical Properties of Gasoline........................................... 5 (1-2) Major Components of Gasoline...................................................... 6 (2-1) Motor Octane Number Test Conditions.............................................10 (2-2) Research Octane Number Test Conditions........................................11 (2-3) Properties of Normal Heptane and Iso-Octane..................................15 (2-4) Estimated Consumption of Gasoline Additives...........................20 (2-5) Properties of some Active Additives..................................................29 (3-1) Comparison between Power Former &Reformer Units in Al Doura Refinery..............................................................................................36 (3-2) Summarized Laboratory Testing of Al Doura Refinery Petroleum Cuts....................................................................................................48 (3-3) Physical and Chemical Properties of Selective Components....50 (4-1) Preparation Gasoline Pool Formulation ....................................54 (4-2) Summarized Laboratory Testing of Preparation Pool ..............56 (4-3) Octane Number of Petroleum Cuts, Pool, Leaded Gasoline and Commercial Gasoline by Different Methods .........................57 (4-4) Octane Number of Al Doura Refinery Unleaded Gasoline(Pool) with Metallic Additives in Different Vol% ..................................59 (4-5) Blended RON for a Mixture of 75% MMT and 25% TEL with Pool in Different Vol% ..............................................................60 (4-6) Octane Number of Al Doura Refinery Unleaded Gasoline(Pool) with Alcohol Components in Different Vol% .............................................61 (4-7) RON of Blending Pool with Oxygenol, Methanol, and Tert.Butanol in Different Vol%.................................................................64 (4-8) Octane Number of Al Doura Refinery Unleaded Gasoline(Pool) with Aromatic Components in Different Vol%...............................................65 (4-9) Octane Number of Al Doura Refinery Unleaded Gasoline(Pool) with Selective Components in Different Vol%..............................................66 (4-10) Octane Number of Prepared Gasoline(Pool) with 10.7% Vol Preparation Component Mixtures ..................................................................................68 (4-11) RON Increasing of Al Doura Refinery LSRN with 10.7% Vol Preparation Component Mixtures (E10,E11,E9 & E6)............................69 (4-12) Summarized Lab. Testing for two Samples Gasoline Pool with 7.4% Vol (E10) ........................................................................................71

CHAPTER ONE INTRODUCTION

Gasolines are primarily divided between regular and premium and in many countries in three types according to the different octane number. Gasolines come primarily from petroleum cuts with a range of boiling points from 38 to 150-205oC and they are usually blended with components to promote antiknocking (higher octane), ease of starting, low tendency to vapor lock, etc. Many of these gasoline types are obtained through proper blending of light straight run gasoline, catalytic reformate, catalytically cracked gasoline, hydrocracked gasoline, alkylate and n-butane. In addition, oxygenates like MTBE are also added[1]. With the elimination of lead from the gasoline pool, refiners now rely on oxygenates like Methyl Tertiary Butyl Ether(MTBE), Ethyl Tertiary Butyl Ether(ETBE), Tetra Amyl Methyl Ether(TAME), Di Methyl Ether (DME), Methanol, and Ethanol, to increase octane of the gasoline pool to achieve acceptable octane levels. New metallane additives are now being introduced, such as Iron Penta Carbonyl (IPC), Di Cyclo Pentadienyl Iron (DCI), and Methylcyclopentadienyl Manganese Tricarbonyl (MMT), which will be blended with Tertiary Ethyl Lead (TEL), oxygenates, and hydrocarbons[2] .

1-1 GASOLINE BLENDING Streams of gasoline blending are refined from petroleum, or crude oil, an extremely complex substance. The hydrocarbon molecules in crude oil may include from one to 50 or more carbon atoms. At room temperature, hydrocarbons containing one to four carbon atoms are gases; those with five to 19 carbon atoms are usually liquids; and those with 40 or more carbon atoms are typically solids. Figure (1-1) below shows the typical carbon chain lengths found in the proposed HPV test plans and demonstrates the overlap that occurs[3] .

Fig (1-1) Typical Carbon Chain Lengths[3]

Petroleum refining was distillation as well as chemical treatment. Catalysts and pressure are used to separate and combine the basic types of hydrocarbon molecules into petroleum streams which have the characteristics needed for blending commercial petroleum products. However streams used in the blending of gasoline must generally fall in a boiling rang -20 to 230oC and
P P

a carbon number distribution of C4-C12 [3] .

R R R R P P

Gasolines are blended from several petroleum refinery process streams that are derived by the following methods: direct distillation of crude oil, catalytic and thermal cracking, hydrocracking, catalytic reforming, alkylation, and polymerization. Hydrocracking, which consists of cracking in the presence of added hydrogen, permits wide variations in yields of gasoline and furnace oils to meet seasonal demand changes and can effectively process hand to crack stocks. However since hydrocracked stocks lack the high octane olefins present in catalytically cracked stocks, they must be reformed
P

[4]
P

. Reforming process

convert low octane gasoline range hydrocarbons into higher octane ones. Thermal reforming has been almost completely replaced by catalytic reforming. Most reforming catalysts are bimetallic catalysts consisting of platinum with another promoting metal, such as rhenium[4, 5] .
P P

Alkylation converts refinery gases into gasoline range liquids of exceptionally high antiknock quality. However, the process is costly and is not commonly used in gasoline production [4, 6].
P P

Polymerization combines two or more low molecular weight olefin gases into higher molecular weight olefin liquids suitable for gasoline blending or for use as chemical feed stocks. However, because olefinic liquids have low antiknock quality and the reactants, olefin gases, are valuable chemical feeds,

the polymerization process is no longer widely used to produce gasoline blend streams [4, 6]. In view of lead phase out schedules adopted, various options for octane enhancement have been explored [3] . The need for high quantity fuels, having increased resistance to knock over a wide range of engine operating conditions is of paramount significance in current engine operation. Careful refining and blending of fuel components can produce a fuel of sufficiently increased knock resistance to satisfy engine requirements under certain stressed conditions[7] . Oxygenates are added into gasoline in order to increase the overall octane numbers and improve combustion efficiency[8] .

1-2 PHYSICAL AND CHEMICAL PROPERTIES OF GASOLINE Information regarding the physical and chemical properties for the gasoline mixture is located in table (1-1). In cases where data are not available for gasoline, ranges are given to indicate the different values for the individual components[9].
.

Table (1-1) Physical and Chemical Properties of Gasoline [9]

Property
Molecular weight Color Physical state Melting point

Information
108
a
P0F

Reference
[10] [11,12] [11]

Colorless to pale brown or pink Liquid No data Initially, 39oC After 10% distilled, 60oC After 50% distilled, 110oC After 90% distilled, 170oC Final boiling point, 204oC
P P P P P P P P P P

Boiling point

[11,13,14]

Density Odor Odor threshold Solubility: Water at 20oC

P P

0.7-0.8 g/cm
P

3b
1F

[15] [12] [12] [11,14] [11,13]

Gasoline odor 0.025 ppm Insoluble Absolute alcohol, ether, chloroform, benzene 2.13-4.87d
P

P2F

Organic solvent Partition coefficients: Log K ow

R

[16] [16] [17]

Log K oc
R

1.81-4.56
P P3F

Vapor pressured At 60 C
P P

465 mmHg 518mmHg 593mmHg 698mmHg 773mmHg

P P

At 56oC
P P

At 51 C
P P

At 47oC
P P

At 41 C
P P

Henrys law constant; at 20oC

P P

4.8*10-4-3.3 m3/mole
P P P P P4F

[16] [11,12,18] [11] [12] [11,13]

Autoignition temperature Flashpoint Flammability limits Conversion factors Explosive limits .

280-486 C
P P

-46oC
P P

1.4-7.4% No data 1.3-6.0%

Average molecular weight. Temperature not specify c Not specified whether data for air or water d The American Society for Testing and Materials(ASTM) has established guidelines on compositions of gasoline that will permit satisfactory performance under varying condition. These guidelines define five volatility classes that vary by seasonal climatic changes. The values given for vapor pressure at the given temperatures are based on volatility classes e Since data are not available for gasoline, ranges are given indicating different values for the individual components
b

Table (1-2) Major Components of Gasoline[16]

Component n-paraffins C5 C6 C7 C9 C 10-C 13 Total of n-paraffins Branched paraffins C4
R R R R R R R R

Percentage Composition wt% 3.0 11.6 1.2 0.7 0.8 17.3 2.2 15.1 8.0 1.9 1.8 2.1 1.0 32.0

Component Other possible components Octane enhancers Methyl t-butyl ether(MTBE) t-butyl alcohol(TBA) ethanol methanol Antioxidants N,Ndialkylphenylenediamine 2,6-dialkyl and 2,4,6-trialkylphenols Butylated methyl, ethyl and dimethyl phenols Triethyene tetramine di(monononylphenolate) Metal deactivators N,N-disalicylidene-1,2ethanediamine N,N-disalicylidene-propanediamine N,N-disalicylidene-cyclohexanediamine Disalicylidene-N-methyl-dipropylenetriamine Ignition controllers Tri-o-cresylphosphate(TOCP) Icing inhibitors Isopropyl alcohol Detergents/dispersants Alkyl amine phosphates Poly-isobutene amines Long chain alkyl phenols Long chain alcohols Long chain carboxylic acids Long chain amines Corrosion inhibitors Carboxylic acids Phosphoric acids Sulfonic acids

C5
R

C6
R

C7 C8 C9 C 10-C 13
R R R R R R

Total of branched cycloparaffins C6 C7 C8 Total of cycloparaffins olefins

R R R

3.0 1.4 0.6 5.0 1.8 1.8 3.2 4.8 6.6 1.4 4.2 7.6 2.7 30.5

C6
R

Total of olefins aromatics benzene toluene xylenes ethyl benzene C 3-benzene C 4-benzene others Total aromatics
R R R R

1-3 SCOPE OF THE PRESENT WORK.

The lead additives to gasoline are no longer used in many countries around the world. Many other countries are now phasing out the lead in gasoline. Although the lead fuel is still in use in Iraq, several plans are considered to phase out the lead. The use of oxygenates to replace the lead additives in gasoline is considered now as an option in Iraqi refineries. This current experimental study is aimed to help in understanding the effect of the most popular oxygenates on enhancing octane number of Al Doura Refinery gasoline.
.

The main aim of this study is to provide gasoline blend which can be used without the need to modify the engine by two ways: 1.Blending of petroleum cuts produced in Al Doura Refinery to produce a desired octane rating.
.

2. Provide a compound or mixture of compounds which can be added to, or combined with, gasoline to produce high antiknock fuel mixture.
.

Another aim is measuring octane number by different methods, CFR engine and ZX analysis.

CHAPTER TWO LITERATURE SURVEY

2-1 INTERNAL COMBUSTION ENGINES The internal combustion engines are the driving force in most today's automotive application. In these engines, the combustion of mixture of air and fuel takes place in a confined area called the combustion chamber. Heat energy is released as a result of the oxidation of fuel molecules during the combustion process. The released heat energy causes the combustion gases to expand forcing the piston downward and thus exerting a rotational force on the crankshaft of the engine. The process of converting the fuel energy into mechanical work through combustion takes place in very fast repeating cycles. The cycle usually involves five processes: the induction, the compression, the combustion, the expansion, and the exhaust. In the fourstroke engine, the cycle is performed in four piston movements (two upward and two downward), called stroke, completed in two crankshaft revolution. In the first stroke, the piston moves from the uppermost position, called the top center (tc), to the lowermost position, called the bottom center (bc), inducting the air/fuel mixture (or the air only depending on the type of the engine) through the open intake valve. In the second stroke, the piston moves upward compressing the mixture (or air only) whiles the valves are closed. Before the end of the compression stroke, the combustion process starts and continues well in the next stroke where the heat release from combustion expands the gases and forces the piston downward. In the last stroke, the combustion

products are forced outside the cylinder through the open exhaust valve by the upward moving piston[19].
P P

Since only one stroke of the cycle produces power, a smooth rotation of the crankshaft requires the engine to be built with several cylinders performing the cycle processes at different intervals. The commencement of the combustion process is triggered either by an external spark as in the case of spark-ignition (SI) engines or by the injection of the fuel into a highly compressed air as in the case of compression-ignition (CI) engines. Figure (2-1) shows the basic structure of a spark-ignition engine[20,21,22,23]
P P

Fig (2-1) The Basic Structure of a Spark Ignition Engine[19]

P

2-1-1 Anti-Knock Performance Knock in spark ignition engines is generally considered to be caused by an abnormally rapid combustion of an unburned fuel air mixture in front of the normal flame front. A severe pressure unbalance due to this rapid

combustion process sets up shock waves which impinge upon the cylinder walls and pistons to produce the characteristic metallic knocking noise[7] .
P P

Knock-free engine performance is as important as good driveability. Octane number is a measure of a gasoline's antiknock performance, its ability to resist knocking as it burns in the combustion chamber. There are two laboratory test methods to measure the octane number of a gasoline. One yields the Research octane number (RON); the other, the Motor octane number (MON). RON correlates best with low speed, mild-knocking conditions; MON correlates best with high-speed and high-temperature knocking conditions and with part-throttle operation. For a given gasoline, RON is always greater than MON. The difference between the two is called the sensitivity of the gasoline[24]. The motor octane number and Research
P P

octane number conditions are listed consequently in tables (2-1) and (2- 2). Table (2-1) Motor Octane Number Test Conditions[24]
P P

Test engine condition

Test Method Engine Engine RPM Intake Air Temperature Intake Air Humidity Intake Mixture Temperature Coolant Temperature Oil Temperature

Motor Octane
ASTM D2700-92(104) Cooperative Fuels Research(CFR) 900 RPM 38oC
P P

3.56-7.12 g H2 O/kg dry air

R R

149oC
P P

100oC
P P

57oC
P P

10

Table (2-2) Research Octane Number Test Conditions[24]

P P

Test engine condition

Test Method Engine Engine RPM Intake Air Temperature Intake Air Humidity Intake Mixture Temperature Coolant Temperature Oil Temperature

Research Octane
ASTM D2699-92(102) Cooperative Fuels Research(CFR) 600 RPM Varies with Barometric Pressure(88kpa=19.4oC,101.6kpa=52.2oC)
P P P P

3.56-7.12 g H2 O/kg dry air

R R

Not Specified 100oC

P P

57oC
P P

Because RON and MON are measured in a single-cylinder laboratory engine, they do not completely predict antiknock performance in multicylinder engines. There is a procedure to measure the antiknock performance of a gasoline in vehicles. The resulting value is called Road octane number (RdON). Since vehicle testing is more involved than laboratory testing, there have been a number of attempts to predict RdON from RON and MON. The equations take the form: RdON = a (RON) + b (MON) + c
.........................................................................................

(2-1)

A good approximation for RdON sets a = b = 0.5 and c = 0, yielding (RON + MON)/2, commonly written (R + M)/2. This is called the Antiknock Index (AKI). The U.S. Federal Trade Commission requires dispensing pumps to be labeled (posted) with the gasoline's AKI. Footnotes. The gasoline being dispensed must have an antiknock index equal to or greater than the posted

11

value. Rounding the number upward is not permitted. Owner's manuals in the U.S. also must indicate the octane number recommendation for vehicles Footnotes Older owner's manuals of some foreign cars specify RON; some more recent ones specify both RON and AKI. by AKI. (R + M)/2 are voluntarily posted in Canada[25] .
P P

Neither the AKI nor the several other single-value indices that have been developed work for all vehicles. The performance of some vehicles correlates better with RON or MON alone than with a combination of the two. And for a given vehicle, the correlation can vary with driving conditions. As the formula indicates, gasolines with the same AKI can have different RONs and MONs. This may explain why a vehicle knocks with some fill-ups of the same brand but not with others; or why it knocks with one brand of gasoline but not with another. Of course, for a comparison to be valid, the vehicle must be operated under identical conditions, which is not easy for the typical driver. Generally, three grades of unleaded gasoline with different AKIs are available in the U.S. regular, midgrade, and premium. At sea level, the posted AKI for regular grade is usually 87 and for midgrade, 89. The AKI of premium grade varies more, ranging from 91 to 94. The posted AKIs are lower in the Rocky Mountain States. These altitude gasolines historically provided the same antiknock performance as higher-AKI gasolines at sea level. The octane requirement of older-model engines decreases as air pressure (barometric pressure) decreases. Barometric pressure is lower at higher elevations[25] .
P P

12

Since 1984, vehicles have been equipped with more sophisticated control systems, including sensors to measure, and engine management computers to adjust for changes in air temperature and barometric pressure. These vehicles are designed to have the same AKI requirement at all elevations and the owners manuals specify the same AKI gasoline at all elevations. Outside the U.S. and Canada where an octane number is posted, RON is generally used. The owner's manuals also specify the minimum octane grade recommended in terms of RON. It is difficult for a driver to know whether a gasoline has the antiknock performance the engine requires when the engine is equipped with a knock sensor system. These systems, which temporarily retard spark timing to eliminate knocking, are installed on many late-model engines. Retarding the spark reduces power and acceleration. The knock sensor responds so quickly that the driver never notices the knock. Loss of power and acceleration will be the only clues that the antiknock quality of the gasoline does not meet the vehicle's octane requirement. Using gasoline with an antiknock rating higher than that required to prevent knock or to prevent spark retardation by the knock sensor will not improve a vehicle's performance[25] .
P P

2-1-2 Octane Rating Since 1912 the spark ignition internal combustion engine's compression ratio had been constrained by the unwanted "knock" that could rapidly destroy engines. "Knocking" is a very good description of the sound heard from an engine using fuel of too low octane. The engineers had blamed the "knock" on the battery ignition system that was added to cars along with the
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electric self-starter. The engine developers knew that they could improve power and efficiency if knock could be overcome. Kettering assigned Thomas Midgley, Jr. to the task of finding the exact cause of knock[26] . They used a Dobbie-McInnes manograph to demonstrate
P P

that the knock did not arise from preignition, as was commonly supposed, but arose from a violent pressure rise after ignition. The monograph was not suitable for further research, so Midgley and Boyd developed a high-speed camera to see what was happening. They also developed a "bouncing pin indicator that measured the amount of knock[27] . Ricardo had developed an
P P

alternative concept of HUCR (Highest Useful Compression Ratio) using a variable-compression engine. His numbers were not absolute, as there were many variables, such as ignition timing, cleanliness, spark plug position, engine temperature, etc. In 1927 Graham Edgar suggested using two hydrocarbons that could be produced in sufficient purity and quantity[28] . These were "normal heptane",
P P

that was already obtainable in sufficient purity from the distillation of Jeffrey pine oil, and an octane, named 2, 4, 4-trimethyl pentane that he first synthesized. Today we call it iso-octane or 2, 2, 4-trimethyl pentane. The octane had a high antiknock value, and he suggested using the ratio of the two as a reference fuel number. He demonstrated that all the commerciallyavailable gasolines could be bracketed between 60:40 and 40:60 parts by volume heptane: iso-octane. The properties of n-heptane and iso-octane are shown in table (2-3). The reason for using normal heptane and iso-octane was because they both have similar volatility properties, specifically boiling point, thus the

14

varying ratios 0:100 to 100:0 should not exhibit large differences in volatility that could affect the rating test. Table (2-3) Properties of Normal Heptane and Iso-Octane[29]
P

Property
Units

Melting Point
o
P P

Boiling Point
o
P P

Density
g/ml 0.684 0.6919

Heat of Vaporization
MJ/Kg 0.365@25oC
P P

Normal Heptane Isooctane

-90.7 -107.45

98.4 99.3

0.308 @25oC
P P

Having decided on standard reference fuels, a whole range of engines and test conditions appeared, but today the most common are the Research Octane Number (RON) and the Motor Octane Number (MON). To obtain the maximum energy from the gasoline, the compressed fuel-air mixture inside the combustion chamber needs to burn evenly, propagating out from the spark plug until all the fuel is consumed. This would deliver an optimum power stroke. In real life, a series of pre-flame reactions will occur in the unburnt "end gases" in the combustion chamber before the flame front arrives. If these reactions form molecules or species that can auto ignite before the flame front arrives, knock will occur[30,31] .
P P

Simply put, the octane rating of the fuel reflects the ability of the unburnt end gases to resist spontaneous auto ignition under the engine test conditions used. If auto ignition occurs, it results in an extremely rapid pressure rise, as both the desired spark-initiated flame front, and the undesired auto ignited end gas flames are expanding. The combined pressure peak arrives slightly ahead of the normal operating pressure peak, leading to a loss

15

of power and eventual overheating. The end gas pressure waves are superimposed on the main pressure wave, leading to a sawtooth pattern of pressure oscillations that create the "knocking" sound. The combination of intense pressure waves and overheating can induce piston failure in a few minutes. Knock and preignition are both favored by high temperatures, so one may lead to the other. Under high-speed conditions knock can lead to preignition, which then accelerates engine destruction[32,33] .
P P

The fuel property the octane ratings measure is the ability of the unburnt end gases to spontaneously ignite under the specified test conditions. Within the chemical structure of the fuel is the ability to withstand pre-flame conditions without decomposing into species that will auto ignite before the flame-front arrives. Different reaction mechanisms, occurring at various stages of the pre-flame compression stroke, are responsible for the undesirable, easily autoignitable, and end gases. During the oxidation of a hydrocarbon fuel, the hydrogen atoms are removed one at a time from the molecule by reactions with small radical species (such as OH and HO2), and O and H atoms. The strength of carbonR R

hydrogen bonds depends on what the carbon is connected to. Straight chain HCS such as normal heptane have secondary C-H bonds that are significantly weaker than the primary C-H bonds present in branched chain HCS like isooctane[30,31] .
P P

The octane rating of hydrocarbons is determined by the structure of the molecule, with long, straight hydrocarbon chains producing large amounts of easily-autoignitable pre-flame decomposition species, while branched and aromatic hydrocarbons are more resistant. This also explains why the octane ratings of paraffins consistently decrease with carbon number. In real life, the

16

unburnt "end gases" ahead of the flame front encounter temperatures up to about 700 oC due to compression and radiant and conductive heating, and
P P

commence a series of pre-flame reactions. These reactions occur at different thermal stages, with the initial stage (below 400 oC) commencing with the
P P

addition of molecular oxygen to alkyl radicals, followed by the internal transfer of hydrogen atoms within the new radical to form an unsaturated, oxygen-containing species. These new species are susceptible to chain branching involving the HO2 radical during the intermediate temperature
R R

stage (400-600 oC), mainly through the production of OH radicals. Above

P P

600 oC, the most important reaction that produces chain branching is the
P P

reaction of one hydrogen atom radical with molecular oxygen to form O and OH radicals. The addition of additives such as alkyl lead and oxygenates can significantly affect the pre-flame reaction pathways. Antiknock additives work by interfering at different points in the pre-flame reactions, with the oxygenates retarding undesirable low temperature reactions, and the alkyl lead compounds react in the intermediate temperature region to deactivate the major undesirable chain branching sequence[30,31] .
P P

2-1-3 Octane Number Sensitivity RON - MON = Sensitivity.......................................................................... (2-2) Because the two test methods use different test conditions, especially the intake mixture temperatures and engine speeds, then a fuel that is sensitive to changes in operating conditions will have a larger difference between the two rating methods. Modern fuels typically have sensitivities around 10. The US

17

87 (RON+MON)/2 unleaded gasoline is recommended to have a 82+ MON,

R R

thus preventing very high sensitivity fuels[34] . Recent changes in European

P P

gasolines has caused concern, as high sensitivity unleaded fuels have been found that fail to meet the 85 MON requirement of the EN228 European gasoline specification[35] .
P P

Trace quantities in the fuel of unidentified sulfur, nitrogen, oxygen, and reactive hydrocarbon compounds influence the sensitivity of the fuel to knock, affect the action of the TEL component, and contribute to gum and sludge formation and in part to combustion chamber deposits[36] .
P P

2-2 GASOLINE ENGINE EMISSION Automobiles powered by gasoline are a major source of air pollution because it contains lead alkyls, which are normally added to gasoline in order to increase its octane number and, thus, increase the performance of the engine. The intense search for an effective and economical octane boosting alternative to lead has continued[37].
P P

Generally, internal combustion engines produce moderately high pollution levels, due to incomplete combustion of carbonaceous fuel, leading to carbon monoxide and some soot along with oxides of nitrogen , sulfur and some unburnt hydrocarbons, depending on the operating conditions and the fuel/air ratio. The primary causes of this are the need to operate near the stoichiometric ratio for gasoline engines in order to achieve combustion (the fuel would burn more completely in excess air) and the quench of the flame by the relatively cool cylinder walls. The major pollutants emitted include:

18

1- Hydrocarbons; this class is made up of unburned or partially burned fuel, as is a major contributor to urban smog as well as being toxic. They can cause liver damage and even cancer. 2- Nitrogen Oxides (NO x ); these are generated when nitrogen in
R R

the air reacts with oxygen under the high temperature and pressure conditions inside the engine. NOx emissions

contribute to both smoke and acid rain. 3- Carbon Monoxide (CO); A product of incomplete combustion, carbon monoxide reduces the bloods ability to carry oxygen and is dangerous to people with heart disease. 4- Carbon Dioxide (CO 2 ); Emission of carbon dioxide are an
R R

increasing concern as its role in global warming as a greenhouse gas has because more apparent[38] .
P P

2-3 GASOLINE ADDITIVES The introduction of a new additive in gasoline is no hit or miss proposition. In each instance it is preceded by months, sometimes years, of research and development work and exhaustive testing in the laboratory and in fleets on the road before the additive becomes a commercial reality. Not only must the additive do the job for which it is intended, but it must be trouble free from the time it enters the fuel tank of the vehicle until the exhaust gases pass out the tail pipe[36] . C.M.Larson has estimated the annual
P P

consumption of these additives as shown in table (2-4).

19

Table (2-4) Estimated Consumption of Gasoline Additives [39]

P

Additive type
Tetraethyl lead Antioxidant Metal deactivators Corrosion inhibitors Preignition preventers Anti-icing Upper-cylinder lubes Dyes and decolorizer Totals

Approximate dosage
0-3 ml/gal 2-16 lb/1000bbl 1-3 lb/1000bbl 10-50 ppm 0.01-0.02% 0.5-1% A few 0.1% trace

Millions of pounds
400-450 6.0 1.5 5 8 190 140 1 776

Million of dollars
250 7 2 1 3 10 5 1 279

2-3-1 Gasoline Anti-Knock Additives These are compounds which, when added to a gasoline fuel for spark ignition engines, raise its antiknock quality, which is expressed by octane numbers. There are three broad classes of compounds from which antiknock additives are selected: 1-Hydrocarbons of natural high octane number. 2- The aromatic amines. 3-The organometallic compounds[36].
P P

The relative effectiveness of compounds of these classes is shown in figure (2-2).

20

Fig(2-2) Relative Effectiveness of Antiknock Compounds[36]

P

The hydrocarbon class of antiknock compounds should be regarded as fuel components rather than considered for their antiknock effectiveness as additives. The usefulness of the amines appears to be confined to special cases, such as to supplement the tetraethyl lead in aviation gasoline. Of the organometallics, there are many which exhibit antiknock value. The lack of one or more of the other essential qualities in additives, such as solubility, volatility, and low cost, has ruled out all but two, the lead alkyl and iron carbonyl. The later is lower in cost but increases engine wear because of its abrasive combustion products, thus making its impractical. Of the lead alkyls,

21

tetraethyl lead, the original selection, is now the accepted standard antiknock agent for commercial use in motor and aviation gasolines[36] .
P P

2-3-1-1 History and Background In the early 20th century, automotive engineers discovered that engines with no knock would operate smoother and more efficient. In 1916 Thomas Midgely a research scientist working for the Dayton Research Laboratories of Dayton, Ohio discovered that addition of iodine to gasoline substantially reduced engine knocks. He related engine knocks to low quality of fuel combustion "Later known as octane" Iodine raised octane and eliminated the knocks. Iodine had two major drawbacks; it was corrosion and prohibitively expensive. In a joint research work in 1917, Charles Kettering (inventor of electric self-starter) and Midgley blended ethyl alcohol (grain alcohol) with gasoline and concluded that alcohols mixed with gasoline could produce a suitable motor fuel. At the society of Automotive Engineers in Indianapolis , Thomas Midgley told the audience that alcohol had many advantages over gasoline additives it burned clean and free from any deposits it produced higher compression ratio inside the engines without knocking and produced more horse-power due to increase in the octane number. In February 1920, Thomas Midgley filed a patent application for blend of alcohol and gasoline as an antiknock fuel[40] . During his search for chemicals
P P

that could be added to gasoline and reduce engine knocks, Midgley discovered the antiknock properties of tetraethyl lead (TEL) in December 1921. Manufacturing of TEL began in 1923 with small
22

operation in Dayton, Ohio that produced about 600Lof TEL per day. One liter of TEL was enough to treat 1150L of gasoline[40] .The
P P

research on ethanol-blended gasoline continued until August of 1925, when Kettering announced anew fuel called "Synthol", a mixture of alcohol and gasoline that would double gas mileage. Oil companies preferred TEL to ethanol because addition of ethanol to gasoline would have reduced vehicles use of gasoline by 20-3-%, thus making cars less dependable on petroleum products, TEL did not have a significant effect on gasoline consumption of vehicles. In 1923, some well known public health and medical authorities at leading

universities including Reid Hunt of Harvard, Yandell Henderson of Yale and Erik Krause of the Institute of Technology, Postdam, Germany wrote letters to Midgley, expressing grave concerns over TEL and its poisonous characteristic[40].Around the time of TEL
P P

production, William Mansfield Clark, a laboratory director in the United States Public Health Service (USPHS), wrote to A.M.Stimson, assistant Surgeon General at USPHS and warned him of widespread use of TEL usage in gasoline. He stated that each liter of gasoline burned would emit 1 g of lead oxide that would build up to dangerous level along heavily traveled roads. The divisions' director suggested that USPHS should rely on industry to supply the relevant investigation data because it would be too time consuming for USPHS to conduct such studies. Making such a poor decision at that time did not allow a comprehensive understanding of the real dangers posed by TEL and lack of scientific research and evidence allowed the use of TEL for a few decades after its discovery. The use of

23

leaded gasoline for highway vehicles was banned in the United States as of January 1, 1996[41] . The comprehensive national Health and
P P

Nutrition Examination survey by the US Center for Disease Control and Prevention confirm that the average blood lead levels in the United States decreased from 16mg dl-1 to 3 mg dl-1 from 1976 to 1990. This is the period when the use of leaded gasoline fell from its peak to near zero in the United Stares [41] . Due to lack of
P P

infrastructure and sufficient capital, leaded gasoline is still being used in many countries throughout the world. Experience in developed and developing countries has shown that the cost increase of transition to unleaded gasoline is about $0.011[41].
P P

The Clean Air Act was signed into law by President Nixon in December 1970. Phase out of leaded gasoline began in December 1973 in the United States and the primary phase out of leaded gasoline was completed in 1986. In July 1974 catalytic converters were being introduced in automobiles and in the same period, unleaded gasoline was required to be sold nationwide. For a brief period (early 1970s) ethylene dibromide (EDB) was added to leaded gasoline to reduce the damaging effect of lead to car engines. Due to the outlaw of leaded gasoline EDB manufacturers found a new use for the chemical, as a pesticide. The United States Environmental Public Agency (USEPA) banned the use of EDB in 1974 because of its carcinogenic and mutogenic effects on laboratory animals. Transition from leaded gasoline to unleaded gasoline was slow and took many years to accomplish Leaded gasoline had an octane rating of 89. Unleaded gasoline had an octane rating of 87. During

24

this transition period, automobile makers adjusted the engines of vehicles to run with the newly introduced unleaded gasoline by United States refineries[42] .
P P

Widespread use of oxygenates in gasoline dates to 1979, when methyl tert-butyl ether (MTBE) was added to gasoline to substitute TEL and to increase the octane rating of the fuel. As part of the Clean Air Act Amendments of 1990, and through an intensive negotiation between the USEPA, state officials, oil and automobile industry representatives, gasoline retailers, oxygenate suppliers, environmental organizations, and consumer groups, the federal government introduce the reformulated gasoline (RFG) program in two phases into United States most polluted cities. Both phases of the program require that RFG contain 2% by weight oxygen. This program was aimed at reducing the level of highly toxic aromatics (such as benzene, toluene, ethyl benzene and xylenes) from gasoline and increasing the oxygen content of gasoline by adding larger quantities of oxygenates. The US Congress mandated the use of a minimum 2.0% oxygenate in RFG. This requirement would be met by the addition of either 11% (MTBE) or 5.7% ethanol by volume. In conventional gasoline, benzene levels were as high as 5vol%, but in RFG, benzene levels were limited to no more than 1.0% by volume. In conventional gasoline, aromatic levels reached as high as 50vol%. In RFG, aromatic levels were limited to 27vol%.Addition of oxygen to gasoline had a two-fold objective, to enhance the octane rating of internal combustion engines and to reduce air pollution (summertime

25

smog, wintertime carbon monoxide, and year-round air toxics) with provision of more complete fuel combustion in the engines. Oxygen, have proven to be an effective way of reducing the levels of harmful aromatics in gasoline, maintain octane levels, extend the life of a barrel of oil (5%less crude oil needs to be refined to produce base gasoline for oxygenated gasoline ) and assist rural America through the increased use of ethanol from corn[43] . The
P P

addition of oxygenates to gasoline offers many advantages, among which: 1- More complete combustion and reduction of carbon monoxide emission. 2- Being a renewable energy source 3- Increased octane number 4- Increased volatility There are also disadvantages in adding oxygenates to gasoline among which: 1- Corrosion. 2- Lower energy content. 3- Increased cost. 4- Increased volatility[44] .
P P

2-3-1-2 Octane Booster Octane boosters usually contain one active ingredient, sometimes diluted in a solvent (like toluene). Typical active ingredients for octane improves are alcohol, either s manganese (MMT), or tetraethyl lead (TEL).

26

Alcohols: Methanol and ethanol are alcohols which have been used as octane booster. They work since both have a higher octane number than typical street gasoline. They are more effective in low octane gasoline than in high octane gasoline. Alcohol has an affinity for water. This means that if there is a slight amount of water in the bottom of your gas tank, the alcohol can grab hold of the water and separate from the gasoline, leaving you with a water /alcohol mix at the bottom of your tank with gasoline floating on top. This is not good. And the last thing, even if you mix octane improvers containing alcohols with your gasoline, you will still not know what octane you end up with. Ethanol has been known as a fuel for many decades. Indeed, when Henry Ford designed the Model T, it was his expectation that ethanol, made from renewable biological materials, and would be major automobile fuel. However, it is not widely used because of its high price. But as fuel for spark ignition (SI) engines, ethanol has some advantages over petrol, such as better antiknock characteristics and less of CO and HC emission. Although having these advantages, due to limitation in technology, economic and regional considerations, it can be considered as a renewable source of energy. Under the environmental consideration, using ethanol blended with petrol is better than pure petrol, because of its renewability and less toxicity[45] .
P P

Ether: MTBE, TAME, and ETBE are the most common ethers available for gasoline use. They have higher octane values than typical gasoline so like the alcohol they will increase the octane quality of street gasoline. Ethers do not have an affinity for water will not separate from gasoline, and blend like a hydrocarbon. When ether is used as additives the enthusiast still does not know what his final octane number is. Manganese (MMT): sometimes

27

referred to as manganese or more correctly Methyl Cyclopentadienyl Manganese Tricarbonyl (MMT). This can be an effective octane improver at very low concentrations. You can gain one or two octane numbers using the recommended treat rate. Problems with emissions, injections, spark plugs, oxygen sensors, and catalytic converters have all been traced to the use of MMT, which is not legal to use by U.S. Refiners in reformulated Gasoline. As indicated above with the alcohols and the others, it is tough to know what octane number you have attained TEL (Lead): Lead Tetraethyl Lead or TEL is known to be a very effective octane improver used in many racing gasolines and aviation gasoline. It is extremely toxic in its pure form. And is illegal to use in any street driven vehicle in the U.S. since 1/1/96. It will poison oxygen sensors and catalytic converters. It is sold in a much diluted form by atleast one vendor but not in California because of restrictions on metallic additives. Again one still does not know the octane number of the final blend[46] . Table (2-5) shows properties of some active additives . Table (2-5) Properties of some Active Additives[47]
P

Sp.gr
Methanol Ethanol IPA TBA MTBE ETBE TAME 0.796 0.794 0.789 0.791 0.744 0.770 0.770

%O2(wt)
R R

RON
130 115 117 100 110 112 105

MON
100 100 100 90 100 100 100

RVP(kpa)
250 130 70 65 55 28 7

49.9 34.7 26.6 21.6 18.2 15.7 15.7

28

2-3-2 Oxidation Inhibitors Also called anti-oxidants, are aromatic amines and hindered phenols. They prevent gasoline components from reacting with oxygen in the air to form peroxides or gums. They are needed in virtually all gasolines, but especially those with high olefins content. Peroxide can degrade anti-knock quality, cause fuel pump wear, and attack plastic or elastomeric fuel system parts, soluble gums can lead to engine deposits, and insoluble gums can plug fuel filters. Inhibiting oxidation is particularly important for fuels used in modern fuel injected vehicles, as their fuel recirculation design may subject the fuel to more temperature and oxygen exposure stress[25] .
P P

2-3-3Corrosion Inhibitors Corrosion Inhibitors are carboxylic acids and carboxylates. The facilities tanks and pipelines of the gasoline distribution and marketing system are constructed primarily of uncoated steel. Corrosion inhibitors prevent free water in the gasoline from rusting or corroding these facilities. Corrosion inhibitors are less important once the gasoline is in the vehicle. The metal parts in the fuel systems of today's vehicles are made of corrosion resistant alloys or of steel coated with corrosion resistant coatings. More plastic and elastomeric parts are replacing metals in the fuel system. In addition service station systems and operations are designed to prevent free water from being delivered to vehicles fuel tank[25] .
P P

29

2-3-4 Metal Deactivators Metal Deactivators are chelating agents chemical compounds that capture specific metal ions. The more active metals like copper and zinc effectively catalyze the oxidation of gasoline. These metals are not used in most gasoline distribution and vehicle fuel systems. But when they are present, metal deactivators inhibit their catalytic activity[25] .
P P

2-3-5 Demulsifies Demulsifies are polyglycol derivatives. An emulsion is a stable mixture of two mutually insoluble materials. A gasoline water emulsion can be formed when gasoline passes through the high shear field of a centrifugal pump if the gasoline is contaminated with free water. Demulsifiers improve the water separating characteristics of gasoline by preventing the formation of stable emulsions[25] .
P P

2-3-6 Antirust Additive Rust and corrosion inhibitors are widely used in all types of gasoline and light distillate fuels, especially where product pipeline transportation and storage conditions are encountered. They are effective in small concentrations, and their cost is quite low. In making the cutting fluid compounds, soluble oils should always be added to the water, the water should never be added to the oil. The oil water mixture should assume a while milky appearance with only a trace of oil coming to the surface on standing. Lean mixtures of soluble oils are used for grinding, as excessive oil in the richer mixtures will clog the pores of the grinding wheels and cause them to skid instead of grind.

30

Algae, bacteria, and other organic matter found frequently in natural waters can affect the cutting oil mixture in an objectionable manner. Bad odor, separation, and rusting are frequently traceable to these sources. Germicides can be added to soluble oils in the cutting machines, generally in the ratio of 1 part germicide to 600 parts water[36] .
P P

2-3-7 Dyes The dyes used in gasoline are of the oil soluble type. They are present in finished gasoline only to the extent of about 5 ppm. There seem to be no operational problems connected with their use[36] . The important properties
P P

of gasoline dyes are uniform color strength, good solubility, free flow, rapid rate of solution, and nonextractability with distilled water, sea water, or weak caustic solution[36] .
P P

2-3-8 Upper Cylinder Lubricants For a long time it has been the practice of many refineries to incorporate into their motor gasoline about 0.2 to 0.5 percent of a light lubricating oil or some other material for the purpose of providing extra lubrication for the intake valves and the top ring belt area. The oil also serves to prevent the deposition of gummy deposits in the intake system. Since oil contributes to combustion chamber deposits, refiners are not agreed as to whether the advantages of such practice outweigh this disadvantage. Therefore, some gasolines are so treated and some are not[36] .
P P

31

2-3-9 Antipreigaition Agent This class of additives is also referred to as deposit modifiers. They act set in some way to change the character of the combustion chamber deposits so as to give less tendency to induce preignition. They thus reduce the tendency of the engine to knock as the car builds up mileage[48] . The earliest
P P

of these compounds to be used were aryl or alkyl phosphates. More recently alkyl phosphines and alkyl borinates have been used[49] . The phosphorus
P P

compounds are also effective in reducing spark plug fouling and the accompanying loss of power. Investigations have shown that they tend to increase the total amount of deposits formed in the combustion chamber and also that they have some effect toward increasing exhaust valve burning under severe heavy duty operating conditions. The popularity of the phosphorus compounds is increasing, particularly in the premium and super premium fuels designed for high compression engines[36] .
P P

2-3-10 Deicing and Antistall Agents Formation of ice in fuel lines and carburetors has long been recognized as the cause of engine stalling during cool, wet weather, especially when the car owner attempts to idle his cold engine before it is thoroughly warmed up. The vaporizing action of the volatile gasoline produces maximum refrigeration of the carburetor throttle plate when the throttle is mostly closed, such as at light loads. Carburetor icing beings when the carburetor parts are chilled below 30oF(-1oC). These conditions are found when the atmospheric
P P P P

temperatures are from 22 to 50oF(-5.5 to 10oC) and when humidity is 65% or

P P P P

higher

32

Various specially selected and treated alcohols, in concentrations as high as 2%, are introduced in gasoline as anti-icing and antistalling agents. Their value is due to their ability to mix with water and dissolve ice. They work on the same principle as radiator antifreeze mixture, given protection at -20oF(-29oC). These gasoline deicing agents prevent finely divided ice
P P P P

crystals from forming and plugging fuel filters or screens and water from freezing and plugging the fuel line. Isopropanol, freezing at -126oF(-88oC), when used as deicing fluid, is
P P P P

claimed to have less refrigerating action than ethanol or methanol additives. Dimethyl formamide also is used in concentrations as low as 0.1 volume% to provide protection from this type of driving hazard and annoyance[36] .
P P

33

CHAPTER THREE EXPERIMENTAL WORK

3-1 GASOLINE SPECIFICATION Gasolines are usually defined by government regulation, where properties and test methods are clearly defined. In the US, several government and state bodies can specify gasoline properties, and they may choose to use or modify consensus minimum quality standards, such as American Society for Testing Materials (ASTM). The US gasoline specifications and test methods are listed in several readily available publications, including the Society of Automotive Engineers (SAE) , and the Annual Book of ASTM Standards[50].
P P

3-2 AL DOURA REFINERY GASOLINE PRODUCTION Figure (3-1) shows the block diagram of Al Doura atmospheric distillation unit products, which contain light product include butane and lighter, which is part of LPG. In addition the naphtha generated needs to be spilt into two parts, one of that can be sent to a Reformer unit, where octane is improved and the other should be used as is, because its octane cannot be improved. Their names are LSRN and HSRN or Reformer feed. The other products are kerosene, LGO, HGO, jet fuel, and residue crude.

34

OFF Gases + LPG

LPG Unit

LPG LSRN

30%LSR.N LSR.N Hydrodesulphurization Reformer + Unit

Reformate RON (90.5) Gasoline Blending

RON (69 2) Unleaded gasoline RON (83) Leaded gasoline RON (83.5)

unit

Crude distillation unit

Crude oil

HSRN

HSRN RON(56.5)

Power Former Unit

Power formate RON (89.3)

Kerosene HDS

Kerosene

LGO HGO
RC

Jet fuel

Fig (3-1) Gasoline Production in Al Doura Refinery[51]

P

Two units operated in Al Doura Refinery to improving octane number of gasoline, one is called Reformer unit, feed for this unit is a mixture of 30%LSRN and 70% HSRN, and the product is Reformate. The other unit is Power Former, feed is HSRN and the product is Power Formate. The comparison between these two units shows in table (3-1).

35

Table (3-1) Comparison between Power Former &Reformer Units in Al Doura Refinery [52]
P

Reformer Unit
Feed Catalyst 30% LSRN+70%HSRN High purity of alumina balls impregnated by platinum and promotors Catalyst bulk density kg/m3
P

Power Former Unit

HSRN High purity of alumina balls impregnated by platinum and promotors 752

960

Catalyst size and shape mm Reactor temperature oC

P P

4.7*4.7

4.7*2.3

495-525 5-45 3

500-540 30 5

Reactor pressure atm. No. of reactor uses

Gasoline production in Al Doura Refinery included many streams they are: LSRN (RON =69.2). Reformate (RON= 90.5) (from Reforming a mixture of 30%LSRN and 70%HSRN). Power Formate (RON=89.3) (from Reforming HSRN). All feeds and products of Reformer and Power Former units were tested by ASTM standard and IROX analyzer. ASTM standard methods which used for testing petroleum cuts in this project are:-

36

3-2-1 Standard Test Method for Vapor Pressure of Petroleum Products (Reid Method) (D323) 3-2-1-1 Summary of Test Method 1-The liquid chamber of the vapor pressure apparatus is filled with the chilled sample and connected to the vapor chamber that has been heated to 37.8C in a bath. The assembled apparatus is immersed in a bath at 37.8C until a constant pressure is observed. The reading, suitably corrected, is reported as the Reid vapor pressure.
2-All procedures utilize liquid and vapor chambers of the same internal

volume. Utilizes a semiautomatic apparatus immersed in a horizontal bath and rotated while attaining equilibrium. Either a Bourdon gauge or pressure transducer may be used with this procedure[17] .
P P

Fig (3-2) Vapor Pressure Apparatus in Al-Doura Refinery

37

3-2-2 Standard Test Method for Distillation of Petroleum Products at Atmospheric Pressure (D86) 3-2-2-1 Summary of Test Method 1- Based on its composition, vapor pressure, expected IBP or expected EP, or combination there of, the sample is placed in one of five groups. Apparatus arrangement, condenser temperature, and other operational variables are defined by the group in which the sample falls. 2- A 100-mL sample is placed in a round bottom flask and heated at a rate specified for samples with its vapor pressure characteristics. Temperatures are recorded when the first drop is collected(initial boiling point), at recorded volumes of 5ml, 10ml, every subsequent 10ml interval to 90ml, 95ml and at the end of the test(end point). For gasoline samples, the temperatures associated with each incremental volume percentage recovered are converted to temperatures for each incremental volume percentage evaporated by correcting for any sample loss during the test. 3- At the conclusion of the distillation, the observed vapor temperatures can be corrected for barometric pressure and the data are examined for conformance to procedural requirements, such as distillation rates. The test is repeated if any specified condition has not been met. 4- Test results are commonly expressed as percent evaporated or percent recovered versus corresponding temperature, either in a table or graphically, as a plot of the distillation curve[17] .
P P

38

Fig (3-3) Distillation Apparatus Assembly Using Electric Burner[17]

P

3-2-3 Standard Test Method for Sulfur in Gasoline by EnergyDispersive X-ray Fluorescence Spectrometry (D6445) 3-2-3-1 Summary of Test Method The sample is placed in the beam emitted from an X-ray source. The resultant excited characteristic X radiation is measured, and the accumulated count is compared with counts from previously prepared calibration standards to obtain the sulfur concentration in mg/kg. One group of calibration standards is required to span the concentration 5 to 1000 mg/kg sulfur[17] .
P P

39

Fig (3-4) Sulfur Content Apparatus in Al Doura Refinery

3-2-4 Standard Test Method for Determination of Water in Petroleum Products, Lubricating Oils, and Additives by Coulometric Karl Fischer Titration (D6304)

3-2-4-1 Summary of Test Method

1- An aliquot is injected into the titration vessel of a coulometric Karl Fischer

apparatus in which iodine for the Karl Fisher reaction is generated coulometrically at the anode. When all of the water has been titrated, excess iodine is detected by an electrometric end point detector and the titration is terminated. Based on the stoichiometry of the reaction, 1 mol of iodine reacts with 1 mol of water; thus, the quantity of water is proportional to the total integrated current according to Faradays Law. 2- The sample injection can be done either by mass or volume.

40

3- The viscous samples can be analyzed by using a water vaporizer accessory that heats the sample in the evaporation chamber, and the vaporized water is carried into the Karl Fischer titration cell by a dry inert carrier gas[17] .
P P

Figure (3-5) shows Karl Fischer Apparatus for measuring water content in gasoline .

Fig (3-5) Karl Fischer Apparatus for Measuring Water Content[53]

P

3-2-5-Standard Test Method for Gum Content in Fuels by Jet Evaporation (D381)

3-2-5-1 Summary of Test Method A measured quantity of fuel is evaporated under controlled conditions of temperature and flow of air or steam. For aviation gasoline and aviation turbine fuel, the resulting residue is weighed and reported as milligrams per

41

100 mL. For motor gasoline, the residue is weighed before and after extracting with heptane and the results reported as milligrams per 100ml[17] .
P P

Fig (3-6) Gum Content Apparatus of Al Doura Refinery 3-2-6 IROX 2000 IROX 2000 is an extremely compact, robust and user friendly MidFTIR spectrometer for the automatic measurement of the concentration of the most important components of gasoline. Improved mathematical model and use for a built-in density meter the instrument additionally provides most reliable results for key properties such as Octane Numbers, Distillation Properties and Vapor Pressure. A large number of country specific calibration samples are stored. Outlier fuels can be easily added even without a PC[54] .
P P

42

Fig (3-7) IROX 2000

3-2-6-1 Principle The light of an infrared source (1) is collimated by the mirror (2) and is divided into two equivalent beams with the beam splitter (3). One beam is reflected by the fixed mirror (4) and the second beam is reflected by the scanning mirror (5). Both beams are recombined in the beam splitter and travel through the measuring cell (6), which is filled with the unknown sample. The combined beam is collimated onto the infrared-detector (8). The two beams can interfere after the beam splitter and make a constructive interference for all wavelengths if the two path lengths are equal. If the scanning mirror is shifted, constructive interference is possible only for a wavelength which is a multiple of the shift. The intensity on the detector varies like the cosine-Fourier transform of the spectrum. These values are stored for later evaluation. Performing a Fourier-transform of the stored values after the scan, the absorption spectrum of the unknown mixture is

43

evaluated. The concentration of the various components is calculated using a matrix transformation of 962 x 32 points[54].
P P

Fig (3-8) Principle of IROX Operation[54]

P

3-2-7 Cooperative Fuel Research Engines 3-2-7-1 Summary of Test Method

(CFR) (D2699, D2700)

1- The Research RON of a spark-ignition engine fuel is determined using a standard test engine and operating conditions to compare its knock characteristic with those of PRF blends of known RON.

Compression ratio and fuel-air ratio are adjusted to produce standard AKI for the sample fuel, as measured by a specific electronic detonation meter instrument system. A standard AKI. guide table relates engine CFR. to RON level for this specific method. The fuel-air ratio for the sample fuel and each of the primary reference fuel blends is adjusted to maximize AKI for each fuel. 2- The fuel-air ratio for maximum AKI. may be obtained:

44

a-By making incremental step changes in mixture strength, observing the equilibrium AKI value for each step, and then selecting the condition that maximizes the reading . b-By picking the maximum AKI as the mixture strength is changed from either rich-to-lean or lean-to-rich at a constant rate[17] .
P P

Fig (3-9) Research Method Test Engine

ACEGIAir humidifier tube Coolant condenser C.R.change motor Oil filter Knockmeter BDFHJIntake air heater Four bowl carburetor CFR-48 crankcase Ignition Detonation meter C.R.digital counter

45

3-2-8 ZELTX Measurements [ZX-101C Portable Octane Analyzer] The ZX 101C (Zeltex, Inc., Hagerstown, MD) is a portable, batterypowered octane analyzer for use with gasoline. It consists of three primary components: the analyzer, a sample container, and a light shield. The entire package in a carrying case weighs less than 5 kg. The instrument performs an octane number determination in less than I min and does not require the use of standard samples. The measurement is completely nondestructive[55] .
P P

Fig (3-10) ZX-101 The analyzer measures octane number via near-infrared (NIR) transmission spectroscopy. The instrument contains a patented solid-state optical system comprising 14 near-infrared emitting diodes (IREDS) with narrow bandpass filters, a silicon detector system, and a fully integrated

46

microprocessor. Figure (3-11) shows a schematic representation of the analyzer. The sample holder is a scaled, flat-sided, reusable glass container with an optical pathlength of 75 mm. The sample volume is approx. 225 Ml[55] .
P P

To make an octane number determination, the user acquires a background signal from the empty sample chamber, measures the absorption spectrum of the sample twice, then acquires a second background signal. The entire process requires less than I min and can be performed by untrained, unskilled personnel[55] .
P P

Fig (3-11) Schematic Diagram of ZX101C Optical System[55]

P

The results of testing LSRN, HSRN, (30%LSRN+70%HSRN), Reformate, and Power Formate were appeared in table (3-2).

47

Table (3-2) Summarized Laboratory Testing of Al Doura Refinery Petroleum Cuts

properties items Test methods LSRN HSRN 30% LSRN+ 70% HSRN
0.71 0.56 45 66 80 88 97 106 113 120 127 134 174 98 45 40 Nill 11341 55.71 60.31 8.85 1.89 89.26

Reformate

Power Formate

Sp.gr. RVP bar Distillation Temp.oC I.BP

P P

IROX test ASTM D323 ASTM D86

0.659 0.94 32 43 52 58 63 68 74 80 86 97 115 98

0.733 0.4 62 75 89 105 122 141 155 169 178 188 203 98.5 32.00 43.00 Nill 11272 51.20 56.50 10.80 2.70 86.50

0.755 0.38 43 68 82 98 110 121 134 146 161 182 215 98 91.40 67.22 Nill 11203 86.00 90.50 41.66 0.00 58.34

0.757 0.37 40 58 77 95 117 135 152 168 186 198 219 98.5 34.80 42.00 Nill 11197 84.80 89.30 39.23 0.00 60.77

10% 20% 30% 40% 50% 60% 70% 80% 90% EBP T.D.ml Max.S.content ppm Water content ppm Existent gum mgm/100ml Calorific value kcal/kgm 1
P0F

ASTM D4294 ASTM D4928 ASTM D381

74.90 35.60 0.60 11488

MON RON Aromatics vol% Olefins vol% Paraffins & Naphthenes vol%

ASTM D2700 ASTM D2699 IROX test IROX test IROX test

64.60 69.20 4.30 0.00 95.70

Calorific value (Cp) kcal/kgm=12400-2100(sp.gr)2

48

3-3 PREPARATION GASOLINE POOL Gasoline pool included 30%vol LSRN and 70%vol Reformate blend which content 45%vol Reformate and 25%vol Power Formate, the procedure to prepared 10L gasoline pool are as follow: 1- 3L of LSRN with 4.5L Reformate and 2.5L Power Former were blended in a container with stirring at refrigerator temperature, to reducing vaporize of volatile components. 2- Prepared gasoline pool was tested by ASTM stander and IROX analyzer, and then measured octane number by using CFR engine and ZX measurement. 3-4 ANTIKNOCK AGENTS Antiknock additives are gasoline soluble chemicals mixed with gasoline to enhance octane number of gasoline. Typically, they are derived from petroleum based raw materials and their fractions, chemistry are highly specialized. Antiknock compounds increase the antiknock quality of gasoline, because the amount of additive needed is small, they are the lowest cost method for increasing octane number compared with changing gasoline chemistry[25].
P P

Selective components were used as antiknock agent to improve octane number of unleaded gasoline divided to many groups:1- Metallic. 2- Alcohols. 3- Aromatics. 4- Others.

The chemical and physical properties of selective components are listed in table (3-3).

49

Table (3-3) Physical and Chemical Properties of Selective Components[56]

P P

Metallic

Components TEL MMT Tert_ Butanol 2_Methyl, 2-Butanol

Chemical structure
(CH 3 CH 2 ) 4 Pb
R R R R R R

C 9 H 7 MnO 3 (CH 3 ) 3 COH

R R R R R R R R R

Molecular weight 323.44 218.09 74.12 88.15 88.15 74.12 74.12 32.04 46.07 60.11

Density gm/cm3 1.653 1.38 0.789

P

Boiling point oC 85 233 82.3

P P

Melting point oC -136 -1 25.5

P P

RON

107

C 5 H 12 O
R R R R

0.806 0.809 0.810 0.807 0.791 0.789 0.804 0.861 0.877 0.867 1.022 0.790 0.956

102 128.5 117.2 99.5 65 78.5 97.4 138.3 80.1 110.6 184 56.2 194.8

-8.1 -89.5 -93.9 -117.3 -126.5 13.3 5.5 -95 -6.3 -95.4 2.5 96 113 116 118 117 101 114

Alcohol

3_Methyl, 1-Butanol 1_Butanol 2_Butanol Methanol Ethanol Isopropanol

C 5 H 12 O
R R R R

C 4 H 9 (OH) C 4 H 9 (OH) CH 3 OH C 2 H 5 OH C 3 H 7 OH
R R R R R R R R R R R R R R R R R R

Aromatics

Xylene Benzene Toluene Aniline Acetone N_N_ Dimethyl aniline

C 6 H 4 (CH 3 ) 2 C6H6
R R R R R R R R R R

106.17 78.12 92.15 93.13 58.08 121.18

C 6 H 5 CH 3 C 6 H 5 NH 2 C3H6O C 2 H 11 N
R R R R R R R R R R R R R R R R R R

Others

Ethyl Methyl Ketone 2_2_4 Trimethyl pentane Isopropyl Ether Diethyl Ether

(CH 3 ) 2 CH 2 O
R R R R R

72.12

0.805

79.6

-86

C 8 H 18
R R R

98.19

0.695

83.4

-127.7

100

(CH 3 ) 4 (CH) 2 O H
R R R R R R

102.18 74.12

0.724 0.714

68 34.3

-85.9 -116.2

(C 2 H 5 ) 2 O
R R R R R R

50

All selective components are added to the Al Doura gasoline pool at different vol% as follow: 1- 300ml pool was prepared at refrigerator temp. in glass container had fitting cover. 2- Octane number of pool was measured by CFR engine. 3- Four glass container were filled with 300ml of pool and added one of selective components to these containers with shaking by using pipette in different concentrations. 4- Octane number of these blend were measured by CFR engine. 5-Repeat the 3 and 4 with another selective component.

3-5 REFORMULATED ANTIKNOK AGENTS Because toxicity of TEL, health damage caused by lead and harmless of automobile emission control system by using MMT, of the alcohols, methanol is to be avoided, however there are serious issues with the use of ethanol, which remain to be addressed. These include air toxicity and water contamination[47] . The use of higher alcohols (propanol, butanol) will
P P

be constrained by supply but may be able to make an occasional contribution in selected instances. For these reasons, many additives will be prepared from selective components which used at different vol%, eleven prepared additives are prepared by blending components which appeared activity to enhancement octane of preparation pool like alcohols, and aromatics in different vol%. All prepared additives were tested by added to the prepared pool in 10.7%vol and measured octane number of the blends as follows:

51

1- 300 ml preparation pool must be prepared for measuring octane number by CFR engine. 2-36 ml prepared additives were taken by using pipette to blend with 300 ml preparation pool in glass container with shaking. 3-Octane number of blended gasoline is measured by CFR engine. 4-Steps 2 and 3 were repeated for another prepared additive. From the above results, the best four additives are (E10, E11, E9, and E6). To make sure taking 10.7%vol from the best four prepared additives and blended with LSRN (assigned RON 69.2) from Al Doura Refinery, blended RON was measured by CFR engine, and the procedure is as follow: 1- 300 ml LSRN has RON (69.2) must be prepared. 2-36 ml preparation additives(E10, E11, E9, AND E6) were taken by using pipette to blending with 300 ml Al Doura LSRN in glass container with shaking. 3-Octane number of blended is measured by CFR engine. 4-Steps 1, 2, and 3 are repeated for another preparation additive. The best was (E10) added to the two samples of gasoline pool in7.4%vol and the blends tested by ASTM standard, measured octane number by CFR engine and PONA content by IROX analyzer.
.

52

CHAPTER FOUR RESULTS AND DISCUSSIONS

4-1 INTRODUCTION In this thesis gasoline pool was produced from blending LSRN, reformate and power formate, selected components were added to the gasoline pool which was produced in Al Doura Refinery to improving octane number. Mixtures of some selective components (aromatics and alcohols) were prepared and added to prepared gasoline pool to enhancing octane number.

4-2 PREPARED GASOLINE POOL Gasoline pool was obtained from the following petroleum cuts: LSRN (716m3/D). Reformate (1224m3/D). Power Formate (670m3/D). The percentage of each cut was determined:716+1224+670=2610 m3/D total LSRN= (716/2610)*100=27.4% Reformate= (1224/2610)*100=46.9% Power Formate= (670/2610)*100=25.7 % Prepared pool was included mixing of 30%LSRN with 70%Reformate blend, RON measuring (84.5) and expected RON (84.8) as shown in table (4-1). Reformate blend was formed from 25%Power Formate (Reforming of HSRN) and 45%Reformate (Reforming of (30%LSRN and 70% HSRN)).

53

Expected RON was calculated by equation (4-1). Bt (RON)t= Bi(RON)i................................................................. (4-1)

i=1 n

Where: Bt: total gasoline blended. (RON)t: desired octane number of blend. Bi: vol% of component i. (RON)i: blending octane number of component i. 100(RON)t=30*69.2+45*90.5+25*89.3 (RON)t= 8480/100 = 84.8 Table (4-1) Preparation Gasoline Pool Formulation
Component
LSRN Reformate Power Formate Total

RON
69.2 90.5 89.3

Vol%
30 45 25 100

Expected RON
20.8 40.7 23.3 84.8

Prepared pool is represented in figure (4-1). Figure (4-2) shows a simple model of prepared gasoline pool[51] .
45%Reformate 30%LSRN

25%Power Formate

Fig (4-1) Preparation Gasoline Pool Composition

54

LSRN RON (69.2)

(30%LSRN+70%HSRN) LSRN (69.2)

45%Reformate RON (90.5) 30%LSRN 70%Reformate Blend RON (89.9) Pool RON (84.5) 25%Power Formate RON (89.3)

Reformer unit

Crude Oil Distillation Unit

HSRN RON (56.5)

HSRN RON (56.5)

Power former unit

Fig (4-2) Model of Preparation Gasoline Pool[51]

As shown in figure (4-2) prepared pool included 30% vol LSRN and 70% vol Reformate Blend which contain ((45%vol Reformate, product of reforming unit) and (25%vol Power Formate, product of power former unit)). The preparation pool testing is listed in table (4-2) by using ASTM standard testing and IROX.

55

Table (4-2) Summarized Laboratory Testing of Preparation Pool

properties items
Sp.gr. RVP bar Distillation Temp C I.BP 10% 20% 30% 40% 50% 60% 70% 80% 90% EBP T.D.ml Max.S.content ppm Water content ppm Existent gum mgm/100ml Calorific value kcal/kg MON RON Vol% Aromatics Olefins Paraffins and Naphthenes
o

Test methods
IROX ASTM D323 ASTM D86

Al Doura Pool
0.715 0.6 36 54 64 72 82 92 102 115 129 148 187 98.5

ASTM D4294 ASTM D4928 ASTM D381 ASTM D2700 ASTM D2699 IROX IROX IROX

43.8 131.95 1.2 11326 80 84.5 24.25 0 75.75

Calorific value (kcal/kg) =12400-2100(sp.gr.)2............................ (4-2)

56

4-3 Octane Number Measurement Octane number was measured for petroleum cuts, prepared pool (unleaded gasoline), leaded gasoline, and commercial gasoline (Irani gasoline) by CFR engine and ZX measurement. The results of measuring octane number by different methods appear in table (4-3).

Table (4-3) Octane Number of Petroleum Cuts, Pool, Leaded Gasoline and Commercial Gasoline by Different Methods
Components
Light Naphtha Heavy Naphtha Reformate Power Formate Pool Leaded gasoline Commercial gasoline

CFR(digital) RON MON

69.2 56.5 90.5 89.3 84.5 85.0 94.0 64.6 51.9 86.0 84.8 80.0 80.4 89.0

CFR(Research) RON MON

68.9 56.8 90.6 89.2 84.1 85.1 94.1 64.3 52.2 86.1 84.7 79.6 80.5 89.1

ZX RON
69.0 57.0 90.0 88.6 80.0 82.3 89.8

MON
60.5 51.8 85.5 84.3 76.0 78.3 84.2

Octane number increased with increasing aromatics and paraffins branches, for this octane number of Reformate and Power Formate was larger than for LSRN and HSRN, because in the catalytic reforming of HSRN many chemical reactions occur, such as convertion of naphthenes to aromatics and paraffins to naphthenes and isoparaffins, or in other words catalytic reforming increase aromatics and isoparaffins content.

57

The ZX octane analyzer provides CFR engine accuracy with the new vital features of speed and portability. 4-4 ADDITIVES FOR AL DOURA GASOLINE POOL To find the optimum dosage of chemical components that enhance the octane number of the gasoline pool produced in AI-Doura Refinery, chemical components were used as in the first stage. 4-4-1 First Stage It is thus only possible to produce high-octane gasolines without isomerization capability if high-octane additives are incorporated in them. We investigated the effectiveness of different components in Al Doura Refinery gasolines. The following were used as the octaneincreasing components in the studies: 1- Metallic. 2- Alcohols. 3- Aromatics. 4- Others.

Selective components are added to the Al Doura gasoline pool in various vol% and octane number is measured by CFR engine, as follows:

4-4-1-1 Metallic Additives Metallanes include many different types of organometallic in which the carbon atoms are bonded directly to the metals[57] . Obviously the most well
P P

known of these is tetraethyl lead (TEL) and methylcyclopentadienyl manganese tricarbonyl (MMT). Many of the metallanes are toxic, often due to the toxicity of the metal itself, or the toxicity of the ligand group, as is true of all the metal carbonyls[58,59].
P P

58

Metallic additives added to the Al Doura Refinery pool in various vol%, octane number was measured by CFR engine and the results appear in table (4-4), and represented in figure (4-3). Table (4-4) Octane Number of Al Doura Refinery Unleaded Gasoline (Pool) with Metallic Additives in Different vol%
vol% selective additives TEL MMT
0 0.5 0.8 1 1.5

83.0 83.0

88.0 86.0

90.0 87.6

91.5 88.5

94.0 90.0

96 94 92

RON of TEL RON of MMT

RON

90 88 86 84 82 0 0.5 1 vol% 1.5 2

Fig (4-3) Comparison between RON of Blended Al Doura Refinery Pool with Selected Metallic Additives in Different vol%

Tetra Ethyl Lead (TEL) is an excellent antiknock additive as shown in table (4-4), but it is not in use now because of its toxicity and bad effect on human health, and Methylcyclopentadienyl Manganese Tricarbonyl (MMT) is also a good antiknock additive but causes manganese precipitation in the

59

engine. Also from result above, TEL appeared to be a better octane enhancer than MMT at the same vol%. In addition to above result, MMT works better with TEL for increasing RON of gasoline than added alone[60] . Table (4-5) shows the result of measuring octane number for blending a mixture of MMT and TEL in a ratio of 75:25 with pool at different vol%.

Table (4-5) Blended RON for a Mixture of 75%MMT and 25%TEL with Pool in Different vol%
vol% of additive (75%MMT+25%TEL)
0.0 0.5 0.8 1.0 1.5

Blended RON
83.0 85.1 88.2 89.5 91.6

The above result illustrated that the research octane number gain by addition of MMT in a base leaded gasoline is higher than with a base unleaded gasoline, eg., RON (91.6) of blended 1.5% vol MMT and TEL mixture with pool, while RON (90) of blended 1.5% vol MMT only with pool. Figure (4-4) illustrates this case.

60

95 93

RON

91 89 87 85 83 TEL MMT 75%MMT+25%TEL

Fig (4-4) Comparison between Effect of Using MMT alone and with TEL as Additive at 1.5%vol 4-4-1-2 Alcohol components Alcohols were used as antiknock agent to enhance octane value of unleaded gasoline. Alcohol components added to Al Doura pool in various vol%, octane number was measured by CFR engine, and the results are listed in table (4-6) and represented in figure (4-5). Table (4-6) Octane Number of Al Doura Refinery Unleaded Gasoline (Pool) with Alcohol components in Different vol%
vol% Alcohol components 0 2.9 5.7 8.3 10.7

Tert Butanol. 2-Methyl, 2-Butanol 3-Methyl, 1-Butanol 1-Butanol 2-Butanol Methanol Ethanol Isopropanol

83 83 83 83 83 83 83 83

83.8 84.0 83.9 84.3 84.5 83.9 84.7 84.9

84.6 84.6 84.1 85.2 85.6 84.9 86.2 86.5

85.2 85.2 84.2 85.9 86.4 85.8 87.3 88.0

85.8 86.1 84.4 86.3 87.2 86.9 88.0 90.5

61

91 90 89 88 87 86 85 84 83 82 0 5 vol% 10 15

RON of 2-Methyle,2Butanol RON of 3-Methyl,1Butanol RON of 1-Butanol RON of 2-Butanol RON of T ert-Butanol RON of Methanol RON of Ethanol RON of Isopropanol

RON

Fig (4-5) Comparison between RON of Blended Al Doura Refinery Pool with Selected Alcohol Components in Different vol%

The cause of the low effectiveness of tert butanol, 2-methyl, 2-butanol, and 3-methyl,1-butanol are unclear, although in the maximum concentration, it should increase the research octane number by 0.8-3.1 points. The low activity of the components is perhaps related to long storage. Alcohols were investigated as octane boosting additives. Of the alcohols, 1-butanol, 2- butanol, methanol, ethanol, and isopropanol in the amount of up to 10.7 vol% are most frequently used as octane booster. They are attractive because of their low cost in comparison to other components. On addition of 8.3 vol% alcohol components, the octane number of gasoline increased by 0.8-5 points. Isopropanol can thus be recommended as an octane booster for production of high octane unleaded gasoline. The oxygen ratio content in alcohol was an influence factor on RON of blended gasoline with alcohol components.
.

62

Figure (4-6) illustrates a comparison between the effects of selected alcohol components on the blending gasoline RON at 10.7%vol.

8 7
RON Increasing

6 5 4 3 2 1 0
2M ethy l,2Butanol 3.1 3-M ethyl, 1-Butanol 1.4 Tert Butanol. 2.8 Isopropanol . 7.5

1-Butanol 3.3

2-Butanol 4.2

M ethanol 3.9

Ethanol 5.8

RON Increasing

Fig (4-6) Comparison between RON Increasing of Blend Selected Alcohol Components with Al Doura Gasoline Pool at 10.7%vol

In addition, Oxygenol was a mixture of (50%vol methanol and 50%vol tert butanol), added to pool in different vol%, the RON result obtained of blending had large value compared with using methanol and tert butanol alone at the same vol%, as shown in table (4-7), and represented in figure (4-7).

63

Table (4-7) RON of Blending Pool with Oxygenol, Methanol, and Tert. Butanol in Different vol%
vol% Alcohol components
Oxygenol Methanol Tert Butanol

2.9

5.7

8.3

10.7

83 83 83

84.7 83.9 83.8

85.9 84.9 84.6

87.1 85.8 85.2

88.5 86.9 85.8

89 88 87
RON

RON of Oxygenol RON of Methanol RON of Tert Butanol

86 85 84 83 82 0 5 vol% 10 15

Fig (4-7) Comparison Between RON of Pool Blending with Oxygenol, Methanol, and Tert. Butanol in Different vol%

Table (4-7) shows that mixing of more than one component gives successful result for enhancing octane number of gasoline, as example oxygenol such as RON recorded of blending pool with 10.7%vol oxygenol was (88.5), while RON of blending pool with 10.7%vol methanol was (86.9), and with tert. butanol (85.8).

64

4-4-1-3 Aromatics Components Selected aromatics components added to Al Doura pool in various vol%, octane number was measured by CFR engine, the result appears in table (4-8), and is represented in figure (4-8).

Table (4-8) Octane Number of Al Doura Refinery Unleaded Gasoline (Pool) with Aromatic Components in Different vol%
Vol% Aromatic components
Benzene Toluene Xylene Aniline 83 83 83 83 84.4 85.4 86.3 94.2 85.4 86.7 88.7 103.3 86.0 87.8 90.0 109.7 86.3 88.0 91.0 115.8

2.9

5.7

8.3

10.7

From the above result it can be concluded that benzene, toluene and xylene had same effect for increasing octane value of blended Al Doura Refinery unleaded gasoline (pool) at the same vol%, while aromatic amine (aniline) in concentration up to 2.9 vol% allow increasing the octane number by 11.2 points, it is not expedient economically due to its high cost.

65

120 115 110 105 100 95 90 85 80 0 5 vol% 10 15

RON of Benzene RON of Toluene RON of Xylene RON of Aniline

Pool with Selected Aromatic Components in Different vol%

4-4-1-4 Other Components The results of blended RON of Al Doura Refinery pool with selective components in various vol% are listed in table (4-9) and represented in figure (4-9). Table (4-9) Octane Number of Al Doura Refinery Unleaded Gasoline (Pool) with Selective Components in Different vol%
Vol% Selective components
Acetone N,N-Dimethylamine Ethyl Methyl Ketone 2,2,4Trimethylpentane Isopropyl Ether Diethyl Ether 83 83 83 83 83 83 83.5 83.4 83.5 83.3 83.4 81.4 84.6 84.0 85.2 84.2 84.2 78.5 86.0 84.8 86.3 84.4 84.5 76.0 87.3 85.8 87.7 84.4 85.6 75.7

RON

Fig (4-8) Comparison between RON of Blended Al Doura Refinery

2.9

5.7

8.3

10.7

66

90 88 86 84 82 80 78 76 74 0 5 vol% 10 15

RON of Acetone RON of N,NDimethylamine RON of Ethyl Methyle Ketone RON of 2,2,4T rimethylpentane RON of Isopropyl Ether RON of Diethyl Ether

RON

Fig (4-9) Comparison Between RON of Blended Al Doura Refinery with Selective Components in Different vol% Table (4-9) shows that all selective components used had positive effect on increasing octane number of unleaded gasoline at various vol%, except Diethyl Ether in the indicated concentration negatively affected the knock rating of the gasoline, decreasing the research octane number by 1.6-7.3.

4-4-2 Reformulated of Additives (second stage) Optimum result may be obtained by using a mixture of additives so as to ameliorate the deficiencies of each the additives[47] . RON 90 was obtained from blending prepared unleaded gasoline (pool) with 10.7% vol preparation components mixture; blended RON was measured by CFR engine. The results of blended RON for blending prepared pool which include(30% vol LSRN +45%vol Reformate+25% vol Power Formate) with 10.7%vol of 11 preparation component mixtures which contain (alcohols and aromatics) appear in table (4-10) and represented in figure (4-10).
67

Table (4-10) Octane Number of Prepared Gasoline (Pool) with 10.7% vol Preparation Component Mixtures
Component Mixtures Symbol
E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 E11

RON of Prepared Gasoline(pool)

84.5 84.5 84.5 84.5 84.5 84.5 84.5 84.5 84.5 84.5 84.5

RON of Blends
90.5 87.6 87.5 91.2 89.6 93.6 92.6 90.2 94.2 96 94.6

RON increasing
6.0 3.1 3.0 6.7 5.1 9.1 8.1 5.7 9.7 11.5 10.1

98.5 96.5 94.5

RON

92.5 90.5 88.5 86.5 84.5 RON E1 90.8 E2 87.9 E3 87.8 E4 92 E5 90.4 E6 94.4 E7 93.4 E8 91 E9 94.2 E10 96 E11 94.6

Fig (4-10) Comparison Between RON of Preparation Gasoline Pool Blends with 10.7%vol Preparation Component Mixtures

From figure (4-10) it can be noticed that all prepared component mixtures had good effect on increasing octane number of prepared unleaded

68

gasoline(pool), but the best (E10, E11, E9, and E6), due to their high octane blend recommended . To make sure using the best prepared component mixtures and blended with LSRN (assigned 69.2 RON) from Al Doura Refinery at 10.7%preparation component mixtures (E10, E11, E9 and E6), blended RON was measured by CFR engine. The results appear in table (4-11), and represented in figure (4-11). Table (4-11) RON Increasing of Al Doura Refinery LSRN with 10.7% vol Preparation Component Mixtures (E10, E11, E9 & E6)
Component
LSRN LSRN+10.7%E10 LSRN+10.7%E11 LSRN+10.7%E9 LSRN+10.7%E6

RON
69.2 78.2 77.7 78.0 77.8

RON Increasing
0.0 9.0 8.5 8.8 8.6

79.2 77.2
RON

75.2 73.2 71.2 69.2 LSRN RON 69.2

LSRN+10.7 %E10 78.2

LSRN+10.7 %E11 77.7

LSRN+10.7 %E9 78

LSRN+10.7 %E6 77.8

Fig (4-11) Octane Number for Blended of Al Doura LSRN with 10.7%vol Preparation Component Mixtures (E10, E11, E9, and E6)

69

These component mixtures have the greatest effect in gasoline thane light straight run naphtha (LSRN). The excellent component mixtures gained from above results are (E10 & E9), due to their recommended large blend increasing RON. (E10) was an octane booster for prepared pool. It has now been found that the addition of (E10) to preparation Al Doura Pool, which recorded RON (84.5), in an amount of 7.4% vol, will increase the octane number of preparation pool to (93.6), or in other hand, increasing RON was (9.1), and when added 10.7% vol (E10) to the preparation pool RON was obtained (96), or increasing RON (11.5). Preparation component mixture (E10) was added to the two different samples of gasoline pool and all specification tested for two blended by ASTM standard and IROX, the result was appeared in table (4-12).

70

Table (4-12) Summarized Lab. Testing for Two Samples Gasoline Pool with 7.4%vol (E10)
Properties items
Sp.gr. RVP bar Distillation TempoC I.BP 10% 20% 30% 40% 50% 60% 70% 80% 90% EBP T.D.ml Max.S.content ppm Water content ppm Existent gum mgm/100ml Calorific value kcal/kgm MON RON Aromatics vol% Olefins vol% Paraffins and Naphthenes vol% ASTM D2700 ASTM D2699 IROX IROX IROX ASTM D4294 ASTM D4928 ASTM D381

Test methods
IROX ASTM D323 ASTM D86

Sample 1
0.733 0.44 49 63 67 79 89 99 113 126 138 152 179 98 44-5 45-4 Nill 11272 85-1 89.7 32.99 0 67.01

Sample1+ 7.4%E10
0.744 0.48 47 57 67 77 90 104 116 129 140 152 179 99 34-3 58-4 Nill 11238 90-9 95.4 33.63 0 66.37

Sample 2
0.75 0.42 51 71 81 90 101 111 122 132 143 155 184 98 40-2 39-4 Nill 11219 85-0 89.6 38.67 0 61.33

Sample 2+ 7.4%E10
0.756 0.46 50 66 73 83 95 109 121 133 144 156 180 98 36-3 35-9 Nill 11200 88-8 93.3 39.12 0 60.88

The result above show that RON of the sample 1 was (89.7) and for sample 1 with 7.4%vol (E10) was (95.4), increasing RON was (5.7). RON

71

for sample 2 was (89.6), and for sample 2 with 7.4%vol E10 was (93.3), increasing RON was (3.7). Aromatics content was increased when added (E10) to the gasoline samples, and the paraffins and naphthenes was decreased. While the distillation temperatures were decreased when added (E10) to the gasoline, due to the high volatile component content in (E10). For the same reason RVP was increased when added (E10) to the gasoline. RON of the blended of prepared gasoline pool with 7.4 %vol (E10) was (93.6), in other word increasing RON of (E10) with prepared gasoline pool was(9.1) , and with sample 1 was(5.7), at last with sample 2 was(3.7), figure(4-12) show the comparison between increasing RON for preparation gasoline and two samples of gasoline with 7.4% vol (E10).

10 9 8

RON increasing

7 6 5 4 3 2 1 0

Prepared gasoline pool 9.1

Sample 1+E10 5.7

Sample 2+E10 3.7

RON increasing

Fig (4-12) Comparison of Blended RON Increasing of Different Gasoline Types with 7.4%vol (E10)

72

CHAPTER FIVE CONCLUSIONS & SUGGESTIONS

5-1 CONCLUSIONS Based on the previously discussed analyses, the following conclusions may be drawn. Preparation gasoline pool (RON=84.5) include 30%vol LSRN,45%vol Reformate, and 25%vol Power Formate. The experimental results of this project for three RON measuring methods showed that ZX was fast, acuurecy, and reliable analysis of gasoline. All selective chemical components act positively to improved octane number of Al Doura Refinery pool, except Diethyl Ether had negative effect. The Octane Booster of this project was Aniline, which was recorded the largest RON. Eleven preparation component mixtures were prepared from active selective components; include alcohol, and aromatic group. The best four preparation component mixtures (E10, E11, E9, and E6) are better act with high octane gasoline than less (LSRN). (E10) is the best prepared component mixtures, and act better with preparation pool than two sample used. However, there is still a need to generate data and experience by running tests and analyzing the environmental effects of blending gasoline. Thus the need to apply the precautionary principle to any gasoline blending component, and insist on a thorough evaluation of implications of
73

such a decision. We must be much more certain of the toxicity, persistence and bioaccumulation of gasoline blending components, since it is given that these chemicals will be used in large amounts through out the world[61] .

5-2 SUGGESTIONS Following suggestion are put forward for future work: Measuring evaporative emissions from the combustion of different blends of preparation gasoline pool with prepared component mixtures and without. Blended distillation fractions of Al Doura Refinery petroleum cuts to producing premium gasoline. Study analysis of all Al Doura petroleum cuts and their fractions via GC analyzer to enhancement gasoline.

74

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5-9, 2006, Dohuk, Iraq. 2. Al Shahrani F. M. , Study of Octane Enhancers for Gasoline in the Kingdom of Saudi Arabia, King Fahad University of Petroleum &Minerals, Dhahran, Saudi Arabia, January 2003. 3. Gasoline blending streams test plane submitted to the USEPA by the American petroleum institute petroleum HPV Tosting Group 2001. 4. Lane GC. gasoline and other motor fuels. In Grayson M, Eckroth D, eds. Kirk Othmer encyclopedia of chemical technology. New York, NY: Gohn Willey and Sons, 652-676, 694-695, 1980. 5. Hood CB. Gasoline. In Hampel CA, Hawley GG, eds. The encyclopedia of chemistry 3rd ed. New York, NY: Van Nostrand Reinhold Company, 491-493, 1973. 6. Domask W.G. Introduction to petroleum hydrocarbons; Chemistry and composition in relation to petroleum derived fuels and solvents. In Mehiman M.A.Hemstreet GP. Thorpe GG, et al, eds, 1984.
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Henderson H.T., Creek W., Calif. Assignor to shell Oil Company. Gasoline Composition, Patent no. 3,179,506. 1965.

8. Yacobucci B.D.and Womach,J.(2006).Fuel ethanol background and puplic policy from: ports/energy/eng.59.cfn 9. Toxicological profiler for gasoline, U.S. department of health and human services (Public health service) June 1995. 10. Anonymous. Toxicology update: Gasoline. J Appl Toxico1 9:203-210, 1989. issues.
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Available http://www.cnie.org/NLE/CRSre

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21. Heywood J.B. Internal Combustion Engine Fundamentals, McGraw. Hill 1988. 22. Taylor C.F. The Internal Combustion Engine in Theory and Practice, Volume 1 and 2, MT Press., Second editions 1985. 23. Stone R. Introduction to Internal Combustion Engines, SAE International, 2nd edition, 1992. 24. Downs D., and Walsh A.D., Knock in Internal Combustion Engines, Nature, vol 163, p 370, 1949. 25. Gasoline Refining and Testing page 2, 3, and 4. 26. Midgley T., Jr.Ind.Eng.Chem. V.31 P.504-506, 1993. 27. Midgley: Saint or Serpent? .Kauffman G.B., Chemtech, December 1989. p.717-725. 28. Edgar G., Measurement of the knock characteristics of gasoline in a standard fuel. Ind.Eng.Chem. v.19 p.145-146(1927). 29. http://www.faqs.org/fags/autos/gasoline_faq/part 1/ 30. Westbrook C.K. , Pitz W.J. , Energy and Technology Review, The Chemical Kinetics of Engine knock.Feb/Mar (1991) P.1-13. 31. Westbrook C.K., Chemistry and Industry (UK), P. 562- 566. The Chemistry Behind Engine Knock,3 August 1992. 32. Hobson G.D., Wiley. (SBN 0471262498), Modern Petroleum Technology. 5th edition 1984. 33. Owen K. and Coley T. Automotive Fuels Reference Book. 2nd edition, SAE. ISBAN 1-56091-589-7, 1995. 34. Annual Book of ASTM Standard, Standard Specification for Automotive Spark Ignition Engine Fuel, ASTM D4814-940. V. 05, 05.ISBN, 0-80312218-7, 1995. terms of

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35. High Sensivity of Certain Gasolines Remains a Problem. Hydrocarbon Processing P.4 July 1994. 36. Virgil B.Guthrie, Petroleum Products Handbook, First Edition, New York, Toronto, London, Mc Gran-Hill Book Company Ing.1960. 37. Hamdan M.A., Al-Subaih T.A., Improvement of locally produced gasoline and studying its effects on both the performance of the engine and the environment 2001. 38. Automobile emission control, the free encyclopedia, from wikipedia. 39. Nelson W.L., Petroleum Refinery Engineering, fourth edition, International Student Edition. 40. Lincoln KJ. , The secret history of lead special report. The Nation March, 1145, 2000. 41. Thomas V.M., The elimination of lead in gasoline. Annual Review of Energy and Environment 20, 301-324, 1995. 42. Caldwell J., Personal Communications. United States. Environmental Protection Agency, Office of Transportation and Air Quality, 2000. 43. Nadim F., Zack P., Hoag G.E., et al .United States Experience with Gasoline Additives 2001. 44. McNair H.M., Chair, Marand H., et al. Extraction of Alcohols from Gasoline using solid phase microextraction (SPME), 2001. 45. Butkus A, Pukalskas S, The Research into the Influence of Ecological Petrol Additives in the Automobile Laboratory, 2004. 46. Rochett Brand Racing Fuel, 100 Octane Racing Gasolines vs. Octane Boosters. 47. Seddon D. & Ptyltd A, Octane Enhancing Petrol Additives/Products, 2000.

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48. Lovell W.G., Gibson H.J., and Jones B.A., Combustion Chamber Deposits in Automobile Engine, Proc. Fourth World Petro. Cong., sec.

V1/T.O.P.,pp,553-577,June,1955. 49. Bender R.O., Chemical Composition of Present and Future Gasoline, paper presented at Annual Meeting of Gasoline Pump Manufactures, White Sulfur Springs, W.V.,May 1957. 50. Automotive Gasolines- Recommended Practice, SAE. 1312 Jan. 93. SAE. Handbook, vol. 1 ISBN 1-56091-461-0 (1994). 51. Al Doura Refinery/Light Oil Unit. 52. Proj. 1390, Seorgi Baghdad Doura Refinery New Refining Complex Catalytic Reforming Unit Operating Manual. 53. http://www.directindustry.com/ 54. IROX 2000 Portable Gasoline Analysis with MID-FTIR. 55. Merberg G.N., Evaluation of an Octane Analyzer, Reprinted from American Laboratory, News August 1996. 56. Handbook of chemistry and physics, 61st editon, 1980-1981. 57. Hartley, Ftank R., Patai, et al, the Chemistry of the Metal Carbon Bond, vol.1, Wiley, New York; 1982. 58. Kitman, Lincoln J.. The Secret History of Lead. The Nation, March 30, 2000. 59. Kots, John C., Editor. Transition Organomitallic Compounds. Plenum Press, New York, 1986. 60.
1986
P

61. Keller A.A. and Fernandz L, Beyond MTBE: Applying the Precautionary Principle to Gasoline Additives 2001.

79

Table (1) Comparison between Al Doura Gasoline and Commercial Gasoline

Properties Items Test Methods Al-Doura Leaded Gasoline Commercial Gasoline

Sp.gr. RVP bar Distillation TempoC I.BP 10% 20% 30% 40% 50% 60% 70% 80% 90% EBP T.D.ml Max.S.content ppm Water content ppm Existent gum mgm/100ml Calorific value kcal/kgm MON RON Aromatics vol% Olefins vol% Paraffins and Naphthenes vol%

IROX ASTM D323 ASTM D86

0.724 0.46 35 51 61 69 77 87 100 111 128 149 171 98.5 102.1 63 2.2 11299

0.739 0.55 40 62 67 75 85 98 114 129 143 167 219 98.5 648.6 133.09 3.4 11253 89 94 19.23 22.6 58.17

144

ASTM D4294 ASTM D4928 ASTM D381

ASTM D2700 ASTM D2699 IROX IROX IROX

80.4 85 28.25 0 71.75

Figures

LIST OF FIGURES Title

Page

(1-1) Typical Carbon Chain Lengths.......................................................................2 (2-1) The Basic Structure of a Spark Ignition Engine...................................9 (2-2) Relative Effectiveness of Antiknock Compounds...............................21 (3-1) Gasolne Production in Al Doura Refinery ...................................................35 (3-2) Vapor Pressure Apparatus in Al-Doura Refinery................................37 (3-3) Distillation Apparatus Assembly Using Electric Burner.................39 (3-4) Sulfur Content Apparatus in Al Doura Refinery.................................40 (3-5) Karl Fischer Apparatus for Measuring Water Content ................41 (3-6) Gum Content Apparatus of Al Doura Refinery...................................42 (3-7) IROX 2000.........................................................................................43 (3-8) Principle of IROX Operation ...................................................44 (3-9) Research Method Test Engine ................................................................45 (3-10) ZX-101..............................................................................................46 (3-11) Schematic Diagram of ZX-101C Optical System .................................47 (4-1) Preparation Gasoline Pool Composition .................................54 (4-2) Model of Preparation Gasoline Pool .............................................55 (4-3) Comparison between RON of Blended Al Doura Refinery Pool with Selected Metallic additives in Different Vol%................59 (4-4) Comparison between effect of using MMT alone and with TEL as additive at 1.5%vol.......................................................................61 (4-5) Comparison between RON of Blended Al Doura Refinery Pool with Selected Alcohol Components in Different Vol%.....................................62 (4-6) Comparison Between RON Increasing of Blend Selected Alcohol Components with AL Doura Gasoline Pool at 10.7%Vol ........................63 (4-7) Comparison Between RON of Pool Blending with Oxygenol,Methanol, and Tert.Butanol in Different Vol%.................................64 (4-8) Comparison Between RON of Blended Al Doura Refinery Pool with Selected Aromatic Components in Different Vol%.................66 (4-9) Comparison Between RON of Blended Al Doura Refinery with Selective Components in different Vol%...................................................67 (4-10) Comparison Between RON of Preparation Gasoline Pool Blends with 10.7%vol Preparation Component Mixtures................................68 (4-11) Octane Number for Blended of Al Doura LSRN with 10.7%vol Preparation Component Mixtures(E10, E11, E9, and E6).......................69 (4-12) Comparison of Blended RON Increasing of Different Gasoline Types with 7.4% Vol (E10).................................................72

iv

RON 82 83 84 85 86 86.5 86.8 87.4 87.8 88 88.2 88.5 88.8 89 89.5 89.8 90 90.7 91 91.5 92 92.5 93 93.5 94

MON 77.4 78.5 79.4 80.3 81.5 82.1 82.2 83 83.5 83.6 83.7 84 84.2 84.5 85 85.3 85.5 86.2 86.5 86.6 87 87.5 88 88.5 89

Different 4.6 4.5 4.6 4.7 4.4 4.4 4.6 4.4 4.3 4.4 4.5 4.5 4.6 4.5 4.5 4.5 4.5 4.5 4.5 5.1 5.2 5.3 5 5 5

AKI 79.7 80.75 81.7 82.65 83.75 84.3 84.5 85.2 85.65 85.8 85.95 86.25 86.5 86.75 87.25 87.55 87.75 88.45 88.75 89.05 89.5 90 90.5 91 91.5

RON
82 83 84 85 86 86.5 86.8 87.4 87.8 88 88.2 88.5 88.8 89 89.5 89.8 90 90.7 91 91.5 92 92.5 93 93.5 94

MON
77.4 78.5 79.4 80.3 81.5 82.1 82.2 83 83.5 83.6 83.7 84 84.2 84.5 85 85.3 85.5 86.2 86.5 86.6 87 87.5 88 88.5 89

Different
4.6 4.5 4.6 4.7 4.4 4.4 4.6 4.4 4.3 4.4 4.5 4.5 4.6 4.5 4.5 4.5 4.5 4.5 4.5 5.1 5.2 5.3 5 5 5

AKI
79.7 80.75 81.7 82.65 83.75 84.3 84.5 85.2 85.65 85.8 85.95 86.25 86.5 86.75 87.25 87.55 87.75 88.45 88.75 89.05 89.5 90 90.5 91 91.5

. 8002