eman ali

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

بسم اهللا الرحمن الرحيم

قـالوا سبحانك ال علم لنـا إال ما علمتنـا ( ) إنك أنت العليم الحكيم

صدق اهللا العظيم

)32:البقرة(

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 GOD who has sustained me throughout this

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.

i

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 (8-

9 ) . .

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. .

vii

TABLE OF CONTENTS Subject Page ACKNOWLEDGEMENT…………………………………………i 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 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 DISCUSSIONS…………………53 4-1 Introduction…………………….……………………….………..53 4-2 Prepared Gasoline Pool .....…………………………….........…53 4-3 Octane Number Measurement…………………………………57 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 Conclusions……………………………………………………73 5-2 Suggestions………………………………………………….…..74 REFRENCES……………………..………………………………….75 ABSTRACT IN ARABIC……………………………………...……80

ii

iii

v

v

NOMENCLATURE

Symbol Description AKI Antiknock Index ASTM American Society for Testing Material bc bottom center CFR Cooperative Fuel Research CI Compression Ignition CO Carbon Monoxide CO Carbon Dioxide 2 DCI Di Cyclo Pentadienyl Iron DME Di Methyl Ether EDB Ethylene Di Bromide ETBE Ethyl Tertiary Butyl Ether

HC Hydrocarbon

HGO Heavy Gas Oil HSRN Heavy Straight Run Naphtha HUCR Highest Units Compression Ratio IPC Iron Penta Carbonyl IREDS Near Infrared Emitting Diodes LGO Light Gas Oil LPG Liquefied Petroleum Gas LSRN Light Straight Run Naphtha MMT Methylcyclopentadienyl Manganese Tricarbonyl MON Motor Octane Number MTBE Methyl Tertiary Butyl Ether NIR Near Infrared NOx Nitrogen Oxides PONA Paraffin, Olefin, Naphthene, and Aromatic RDON Road Octane Number RFC Reformulated Gasoline RON Research Octane Number

iix

Symbol Description RVP Reid Vapor Pressure SAE Society of Automotive Engine SI Spark Ignition TAME Tetra Amyl Methyl Ether tc top center TEL Tertiary Ethyl Lead USEPA United State Environmental Public Agency USPHS United State Public Health Service ZX 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

v

1

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 anti-

knocking (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, hydro-

cracked 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]

.

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]

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 230P

oPC and

a carbon number distribution of CR4R-CR12R P

[3]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 rheniumP

[4, 5]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 P

[4, 6]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,

4

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]

. .

5

.

Table (1-1) Physical and Chemical Properties of Gasoline

Reference

[9]

Information Property [10] 108P0F

a Molecular weight [11,12] Colorless to pale brown or pink Color [11] Liquid Physical state No data Melting point

[11,13,14]

Initially, 39P

oPC

After 10% distilled, 60P

oPC


oPC


oPC

Final boiling point, 204P

oPC

Boiling point

[15] 0.7-0.8 g/cmP

3 1F

b Density [12] Gasoline odor Odor [12] 0.025 ppmP2F

c Odor threshold Solubility: [11,14] Insoluble Water at 20P

oPC

[11,13] Absolute alcohol, ether, chloroform, benzene Organic solvent

Partition coefficients: [16] 2.13-4.87P

d Log KRow

[16] 1.81-4.56P

d Log KRoc

[17] Vapor pressureP3F

d

465 mmHg At 60P

oPC

518mmHg At 56P

oPC

593mmHg At 51P

oPC

698mmHg At 47P

oPC

773mmHg At 41P

oPC

[16] 4.8*10P

-4P-3.3 mP

3P/molP4F

e HenryP

’Ps law constant; at 20P

oPC

[11,12,18] 280-486P

oPC Autoignition temperature

[11] -46P

oPC Flashpoint

[12] 1.4-7.4% Flammability limits No data Conversion factors [11,13] 1.3-6.0% Explosive limits

.

a Average molecular weight. b 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

6

Table (1-2) Major Components of Gasoline

[16]

Component Percentage Composition wt% Component

Other possible components n-paraffins Octane enhancers 3.0 CR5

Methyl t-butyl ether(MTBE) 11.6 CR6

t-butyl alcohol(TBA) 1.2 CR7

ethanol 0.7 CR9

methanol 0.8 CR10R-CR13

Antioxidants 17.3 Total of n-paraffins N,Ndialkylphenylenediamine Branched paraffins 2,6-dialkyl and 2,4,6-trialkylphenols 2.2 CR4

Butylated methyl, ethyl and dimethyl phenols 15.1 CR5

Triethyene tetramine di(monononylphenolate) 8.0 CR6

Metal deactivators 1.9 CR7

N,N-disalicylidene-1,2ethanediamine 1.8 CR8

N,N-disalicylidene-propanediamine 2.1 CR9

N,N-disalicylidene-cyclohexanediamine 1.0 CR10R-CR13

Disalicylidene-N-methyl-dipropylene-triamine 32.0 Total of branched

Ignition controllers cycloparaffins Tri-o-cresylphosphate(TOCP) 3.0 CR6

Icing inhibitors 1.4 CR7

Isopropyl alcohol 0.6 CR8

Detergents/dispersants 5.0 Total of cycloparaffins Alkyl amine phosphates olefins

Poly-isobutene amines 1.8 CR6

Long chain alkyl phenols 1.8 Total of olefins Long chain alcohols aromatics Long chain carboxylic acids 3.2 benzene Long chain amines 4.8 toluene Corrosion inhibitors 6.6 xylenes Carboxylic acids 1.4 ethyl benzene Phosphoric acids 4.2 CR3R-benzene Sulfonic acids 7.6 CR4R-benzene 2.7 others 30.5 Total aromatics

7

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.

8

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 four-

stroke 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

9

products are forced outside the cylinder through the open exhaust valve by

the upward moving pistonP

[19]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 engineP

[20,21,22,23]P

.

Fig (2-1) The Basic Structure of a Spark Ignition EngineP

[19]

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

10

combustion process sets up shock waves which impinge upon the cylinder

walls and pistons to produce the characteristic metallic knocking noiseP

[7]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 gasolineP

[24]P. The motor octane number and Research

octane number conditions are listed consequently in tables (2-1) and (2- 2).

Table (2-1) Motor Octane Number Test ConditionsP

[24]P

Motor Octane Test engine condition

ASTM D2700-92(104) Test Method

Cooperative Fuels Research(CFR) Engine

900 RPM Engine RPM

38P

oPC Intake Air Temperature

3.56-7.12 g HR2RO/kg dry air Intake Air Humidity

149P

oPC Intake Mixture Temperature

100P

oPC Coolant Temperature

57P

oPC Oil Temperature

11

Table (2-2) Research Octane Number Test ConditionsP

[24]P

Research Octane Test engine condition

ASTM D2699-92(102) Test Method

Cooperative Fuels Research(CFR) Engine

600 RPM Engine RPM

Varies with Barometric

Pressure(88kpa=19.4P

oPC,101.6kpa=52.2P

oPC)

Intake Air Temperature

3.56-7.12 g HR2RO/kg dry air Intake Air Humidity

Not Specified Intake Mixture Temperature

100P

oPC Coolant Temperature

57P

oPC Oil Temperature

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

12

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 CanadaP

[25]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 elevationsP

[25]P .

13

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 owner’s 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

performanceP

[25]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

14

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 knockP

[26]P . They used a Dobbie-McInnes manograph to demonstrate

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 knockP

[27]P . Ricardo had developed an

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 quantityP

[28]P . These were "normal heptane",

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 commercially-

available 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

15

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-OctaneP

[29]

Property Melting Point

Boiling Point

Density Heat of Vaporization

Units P

oPC P

oPC g/ml MJ/Kg

Normal Heptane -90.7 98.4 0.684 0.365@25P

oPC

Isooctane -107.45 99.3 0.6919 0.308 @25P

oPC

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 occurP

[30,31]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

16

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 destructionP

[32,33]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 HOR2R), and O and H atoms. The strength of carbon-

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 iso-

octaneP

[30,31]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

17

unburnt "end gases" ahead of the flame front encounter temperatures up to

about 700 P

oPC due to compression and radiant and conductive heating, and

commence a series of pre-flame reactions. These reactions occur at different

thermal stages, with the initial stage (below 400 P

oPC) commencing with the

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 HOR2R radical during the intermediate temperature

stage (400-600 P

oPC), mainly through the production of OH radicals. Above

600 P

oPC, the most important reaction that produces chain branching is the

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 sequenceP

[30,31]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

18

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

thus preventing very high sensitivity fuelsP

[34]P . Recent changes in European

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 specificationP

[35]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 depositsP

[36]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 P

[37]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:

http://www.answers.com/topic/carbon-monoxide�

http://www.answers.com/topic/soot-1�

http://www.answers.com/topic/sulfur�

19

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 Rx R); these are generated when nitrogen in

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 R2 R); Emission of carbon dioxide are an

increasing concern as its role in global warming as a

greenhouse gas has because more apparent P

[38]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 pipeP

[36]P . C.M.Larson has estimated the annual

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

20

Table (2-4) Estimated Consumption of Gasoline Additives P

[39]

Million of

dollars Millions of

pounds Approximate

dosage Additive type

250 400-450 0-3 ml/gal Tetraethyl lead 7 6.0 2-16 lb/1000bbl Antioxidant 2 1.5 1-3 lb/1000bbl Metal deactivators 1 5 10-50 ppm Corrosion inhibitors 3 8 0.01-0.02% Preignition preventers 10 190 0.5-1% Anti-icing 5 140 A few 0.1% Upper-cylinder lubes 1 1 trace Dyes and decolorizer

279 776 Totals

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 compoundsP

[36]P.

The relative effectiveness of compounds of these classes is shown in

figure (2-2).

21

Fig(2-2) Relative Effectiveness of Antiknock CompoundsP

[36]

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,

22

tetraethyl lead, the original selection, is now the accepted standard antiknock

agent for commercial use in motor and aviation gasolinesP

[36]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 P

[40]P . During his search for chemicals

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

23

operation in Dayton, Ohio that produced about 600Lof TEL per day.

One liter of TEL was enough to treat 1150L of gasoline P

[40]P .The

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 P

[40]P.Around the time of TEL

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

24

leaded gasoline for highway vehicles was banned in the United States

as of January 1, 1996 P

[41]P . The comprehensive national Health and

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 P

[41]P . Due to lack of

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 P

[41]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

25

this transition period, automobile makers adjusted the engines of

vehicles to run with the newly introduced unleaded gasoline by

United States refineries P

[42]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

26

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 P

[43]P . The

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 P

[44]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).

27

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 toxicityP

[45]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

28

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 AdditivesP

[47]

RVP(kpa) MON RON %OR2R(wt) Sp.gr

250 100 130 49.9 0.796 Methanol

130 100 115 34.7 0.794 Ethanol

70 100 117 26.6 0.789 IPA

65 90 100 21.6 0.791 TBA

55 100 110 18.2 0.744 MTBE

28 100 112 15.7 0.770 ETBE

7 100 105 15.7 0.770 TAME

29

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 stressP

[25]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 tankP

[25]P .

30

2-3-4 Metal Deactivators

Metal Deactivators are chelating agent’s 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 activityP

[25]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 emulsionsP

[25]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.

31

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 waterP

[36]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 useP

[36]P . The important properties

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 solutionP

[36]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 notP

[36]P .

32

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 mileageP

[48]P . The earliest

of these compounds to be used were aryl or alkyl phosphates. More recently

alkyl phosphines and alkyl borinates have been usedP

[49]P . The phosphorus

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 enginesP

[36]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 30P

oPF(-1P

oPC). These conditions are found when the atmospheric

temperatures are from 22 to 50P

oPF(-5.5 to 10P

oPC) and when humidity is 65% or

higher

33

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

-20P

oPF(-29P

oPC). These gasoline deicing agents prevent finely divided ice

crystals from forming and plugging fuel filters or screens and water from

freezing and plugging the fuel line.

Isopropanol, freezing at -126P

oPF(-88P

oPC), when used as deicing fluid, is

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 annoyanceP

[36]P .

34

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 StandardsP

[50]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.

35

Fig (3-1) Gasoline Production in Al Doura Refinery P

[51]

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).

Cru

de d

istil

latio

n un

it

Reformer Unit

LPG Unit

Power Former

Unit

Kerosene HDS

Hyd

rode

sulp

huriz

atio

n un

it

Gas

olin

e B

lend

ing

OFF Gases + LPG LPG

LSRN RON (69 2)

Unleaded gasoline

RON (83)

LSR.N

Reformate RON (90.5)

30%LSR.N

+

Power formate

RON (89.3)

Leaded gasoline

RON (83.5)

Kerosene

Jet fuel

RON(56.5)

HSRN

HSRN

RC

Crude oil

LGO

HGO

36

Table (3-1) Comparison between Power Former &Reformer Units in Al

Doura Refinery P

[52]

Reformer Unit Power Former Unit

Feed 30% LSRN+70%HSRN HSRN

Catalyst High purity of alumina

balls impregnated by

platinum and promotors

High purity of alumina

balls impregnated by

platinum and promotors

Catalyst bulk density

kg/mP

3

960 752

Catalyst size and shape

mm

4.7*4.7 4.7*2.3

Reactor temperature P

oPC 495-525 500-540

Reactor pressure atm. 5-45 30

No. of reactor uses 3 5

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:-

37

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 37.8°C in a bath. The assembled apparatus is immersed in a

bath at 37.8°C 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 P

[17]P .

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

38

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 curveP

[17]P .

39

Fig (3-3) Distillation Apparatus Assembly Using Electric Burner P

[17]

3-2-3 Standard Test Method for Sulfur in Gasoline by Energy-

Dispersive X-ray Fluorescence Spectrometry (D6445)


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 sulfurP

[17]P .

40

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)


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 Faraday’s Law.

2- The sample injection can be done either by mass or volume.

41

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 gasP

[17]P .

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

in gasoline .

Fig (3-5) Karl Fischer Apparatus for Measuring Water ContentP

[53]

3-2-5-Standard Test Method for Gum Content in Fuels by Jet

Evaporation (D381)


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

42

100 mL. For motor gasoline, the residue is weighed before and after

extracting with heptane and the results reported as milligrams per 100mlP

[17]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 Mid-

FTIR 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 PCP

[54]P .

43

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

44

evaluated. The concentration of the various components is calculated

using a matrix transformation of 962 x 32 points P

[54]P.

Fig (3-8) Principle of IROX OperationP

[54]

3-2-7 Cooperative Fuel Research Engines (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:

45

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 rateP

[17]P .

Fig (3-9) Research Method Test Engine

A- Air humidifier tube B- Intake air heater C- Coolant condenser D- Four bowl carburetor E- C.R.change motor F- CFR-48 crankcase G- Oil filter H- Ignition Detonation meter I- Knockmeter J- C.R.digital counter

46

3-2-8 ZELTX Measurements [ZX-101C Portable Octane Analyzer]

The ZX 101C (Zeltex, Inc., Hagerstown, MD) is a portable, battery-

powered 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 nondestructiveP

[55]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

47

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 P

[55]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 P

[55]P .

Fig (3-11) Schematic Diagram of ZX101C Optical SystemP

[55]

The results of testing LSRN, HSRN, (30%LSRN+70%HSRN),

Reformate, and Power Formate were appeared in table (3-2).

48

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

Petroleum Cuts

properties items

Test methods

LSRN HSRN 30% LSRN+

70% HSRN

Reformate Power Formate

Sp.gr. IROX test 0.659 0.733 0.71 0.755 0.757

RVP bar ASTM D323 0.94 0.4 0.56 0.38 0.37

Distillation Temp.P

oPC I.BP

ASTM D86 32 62 45 43 40

10% 43 75 66 68 58

20% 52 89 80 82 77

30% 58 105 88 98 95

40% 63 122 97 110 117

50% 68 141 106 121 135

60% 74 155 113 134 152

70% 80 169 120 146 168

80% 86 178 127 161 186

90% 97 188 134 182 198

EBP 115 203 174 215 219

T.D.ml 98 98.5 98 98 98.5

Max.S.content ppm

ASTM D4294

74.90 32.00 45 91.40 34.80

Water content ppm

ASTM D4928

35.60 43.00 40 67.22 42.00

Existent gum mgm/100ml

ASTM D381 0.60 Nill Nill Nill Nill

Calorific value kcal/kgmP0F

1 11488 11272 11341 11203 11197

MON ASTM D2700

64.60 51.20 55.71 86.00 84.80

RON ASTM D2699

69.20 56.50 60.31 90.50 89.30

Aromatics vol%

IROX test 4.30 10.80 8.85 41.66 39.23

Olefins vol%

IROX test 0.00 2.70 1.89 0.00 0.00

Paraffins & Naphthenes vol%

IROX test 95.70 86.50 89.26 58.34 60.77

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

49

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

chemistryP

[25]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).

50

Table (3-3) Physical and Chemical Properties of Selective ComponentsP

[56]P

M

etal

lic

Components Chemical structure

Molecular weight

Density gm/cmP

3 Boiling point P

oPC

Melting point P

oPC

RON

TEL (CHR3RCHR2R)R4RPb 323.44 1.653 85 -136 MMT CR9R HR 7R MnOR3 218.09 1.38 233 -1

Alc

ohol

Tert_ Butanol

(CHR3R)R3RCOH 74.12 0.789 82.3 25.5 107

2_Methyl, 2-Butanol

CR5RHR12RO 88.15 0.806 102 -8.1

3_Methyl, 1-Butanol

CR5RHR12RO 88.15 0.809 128.5 ـــــــــ

1_Butanol CR4RHR9R(OH) 74.12 0.810 117.2 -89.5 96 2_Butanol CR4RHR9R(OH) 74.12 0.807 99.5 ـــــــــ Methanol CHR3ROH 32.04 0.791 65 -93.9 113

Ethanol CR2RHR5ROH 46.07 0.789 78.5 -117.3 116

Iso-propanol

CR3RHR7ROH 60.11 0.804 97.4 -126.5 118

Aro

mat

ics

Xylene CR6RHR4R(CHR3R)R2 106.17 0.861 138.3 13.3 117

Benzene CR6RHR6 78.12 0.877 80.1 5.5 101

Toluene CR6RHR5RCHR3 92.15 0.867 110.6 -95 114

Aniline CR6RHR5RNHR2 93.13 1.022 184 -6.3

Oth

ers

Acetone CR3RHR6RO 58.08 0.790 56.2 -95.4 N_N_ Dimethyl aniline

CR2RHR11RN 121.18 0.956 194.8 2.5

Ethyl Methyl Ketone

(CHR3R)R2RCHR2R

O 72.12 0.805 79.6 -86

2_2_4 Trimethyl pentane

CR8RHR18 98.19 0.695 83.4 -127.7 100

Isopropyl Ether

(CHR3R)R4R(CH)R2ROH

102.18 0.724 68 -85.9

Diethyl Ether

(CR2RHR5R)R2RO 74.12 0.714 34.3 -116.2

51

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 contaminationP

[47]P . The use of higher alcohols (propanol, butanol) will

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:

52

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.

53

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

• Reformate (1224m

/D). 3

• Power Formate (670m

/D). 3

The percentage of each cut was determined:-

/D).

716+1224+670=2610 m3

LSRN= (716/2610)*100=27.4%

/D total

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)).

54

Expected RON was calculated by equation (4-1).

B

n

t (RON)t= ∑ Bi(RON)i

................................................................. (4-1)

Where: i=1

Bt

(RON)

: total gasoline blended.

t

B

: desired octane number of blend.

i

(RON)i: blending octane number of component i.

: vol% of component i.

100(RON)t

(RON)

=30*69.2+45*90.5+25*89.3

t

= 84.8

= 8480/100

Table (4-1) Preparation Gasoline Pool Formulation

Component RON Vol% Expected RON LSRN 69.2 30 20.8 Reformate 90.5 45 40.7 Power Formate 89.3 25 23.3 Total 100 84.8

Prepared pool is represented in figure (4-1). Figure (4-2) shows a simple

model of prepared gasoline pool[51] .

Fig (4-1) Preparation Gasoline Pool Composition

30%LSRN

45%Reformate

25%Power Formate

55

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.

Reformer unit

Power former

unit

Cru

de O

il D

istil

latio

n U

nit

30%

LSR

N

Pool RON (84.5)

45%Reformate RON (90.5)

70%Reformate Blend RON (89.9)

25%Power Formate RON (89.3)

(30%LSRN+70%HSRN)

HSRN RON (56.5)

LSRN RON (69.2)

LSRN (69.2)

HSR

N R

ON

(56.

5)

56

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

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

............................ (4-2)

properties items Test methods Al Doura Pool

Sp.gr. IROX 0.715 RVP bar ASTM D323 0.6 Distillation Tempo ASTM D86 C I.BP 36

10% 54 20% 64 30% 72 40% 82 50% 92 60% 102 70% 115 80% 129 90% 148

EBP 187 T.D.ml 98.5 Max.S.content ppm ASTM D4294 43.8 Water content ppm ASTM D4928 131.95 Existent gum mgm/100ml ASTM D381 1.2 Calorific value kcal/kg 11326 MON ASTM D2700 80 RON ASTM D2699 84.5 Vol% Aromatics IROX 24.25 Olefins IROX 0 Paraffins and Naphthenes IROX 75.75

57

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 CFR(digital) CFR(Research) ZX

RON MON RON MON RON MON Light Naphtha 69.2 64.6 68.9 64.3 69.0 60.5 Heavy Naphtha 56.5 51.9 56.8 52.2 57.0 51.8

Reformate 90.5 86.0 90.6 86.1 90.0 85.5

Power Formate 89.3 84.8 89.2 84.7 88.6 84.3

Pool 84.5 80.0 84.1 79.6 80.0 76.0

Leaded gasoline 85.0 80.4 85.1 80.5 82.3 78.3

Commercial gasoline 94.0 89.0 94.1 89.1 89.8 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.

58

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 octane-

increasing 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 metalsP

[57]P . Obviously the most well

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 carbonylsP

[58,59]P.

59

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%

1.5 1 0.8 0.5 0

vol% selective additives

94.0 91.5 90.0 88.0 83.0 TEL 90.0 88.5 87.6 86.0 83.0 MMT

82

84

86

88

90

92

94

96

0 0.5 1 1.5 2

vol%

RON

RON of TELRON of MMT

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

60

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)

Blended RON

0.0 83.0 0.5 85.1 0.8 88.2 1.0 89.5 1.5 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.

61

83

85

87

89

91

93

95

TEL MMT 75%MMT+25%TEL

RON

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).


(Pool) with Alcohol components in Different vol%

10.7

8.3

5.7

2.9

0

vol% Alcohol components

85.8 85.2 84.6 83.8 83 Tert Butanol.

86.1 85.2 84.6 84.0 83 2-Methyl, 2-Butanol 84.4 84.2 84.1 83.9 83 3-Methyl, 1-Butanol 86.3 85.9 85.2 84.3 83 1-Butanol 87.2 86.4 85.6 84.5 83 2-Butanol 86.9 85.8 84.9 83.9 83 Methanol 88.0 87.3 86.2 84.7 83 Ethanol 90.5 88.0 86.5 84.9 83 Isopropanol

62

82838485868788899091

0 5 10 15

vol%

RON

RON of 2-Methyle,2-ButanolRON of 3-Methyl,1-ButanolRON of 1-Butanol

RON of 2-Butanol

RON of Tert-Butanol

RON of Methanol

RON of Ethanol

RON of Isopropanol


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. .

63

Figure (4-6) illustrates a comparison between the effects of selected

alcohol components on the blending gasoline RON at 10.7%vol.

0

1

2

3

4

5

6

7

8

RO

N In

crea

sing

RON Increasing 3.1 1.4 3.3 4.2 2.8 3.9 5.8 7.5

2-Methyl,2-Butanol

3-Methyl, 1-Butanol

1-Butanol 2-ButanolTert

Butanol.Methanol Ethanol

Isopropanol.

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).

64

Table (4-7) RON of Blending Pool with Oxygenol, Methanol,

and Tert. Butanol in Different vol%

vol% Alcohol components

0 2.9

5.7

8.3

10.7

Oxygenol 83 84.7 85.9 87.1 88.5 Methanol 83 83.9 84.9 85.8 86.9 Tert Butanol 83 83.8 84.6 85.2 85.8

82

83

84

85

86

87

88

89

0 5 10 15

vol%

RO

N

RON of OxygenolRON of MethanolRON of Tert Butanol

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).

65

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).


(Pool) with Aromatic Components in Different vol%

10.7

8.3

5.7

2.9

0

Vol%

Aromatic components

86.3 86.0 85.4 84.4 83 Benzene 88.0 87.8 86.7 85.4 83 Toluene 91.0 90.0 88.7 86.3 83 Xylene 115.8 109.7 103.3 94.2 83 Aniline

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.

66

80

8590

95100

105

110115

120

0 5 10 15

vol%

RON

RON of BenzeneRON of TolueneRON of XyleneRON 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).


(Pool) with Selective Components in Different vol%

10.7

8.3

5.7

2.9

0

Vol%

Selective components

87.3 86.0 84.6 83.5 83 Acetone 85.8 84.8 84.0 83.4 83 N,N-Dimethylamine 87.7 86.3 85.2 83.5 83 Ethyl Methyl Ketone

84.4 84.4 84.2 83.3 83 2,2,4- Trimethylpentane

85.6 84.5 84.2 83.4 83 Isopropyl Ether 75.7 76.0 78.5 81.4 83 Diethyl Ether

67

74

7678

8082

84

8688

90

0 5 10 15

vol%

RON

RON of Acetone

RON of N,N-DimethylamineRON of Ethyl MethyleKetoneRON of 2,2,4-TrimethylpentaneRON of Isopropyl Ether

RON of Diethyl Ether

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).

68

Table (4-10) Octane Number of Prepared Gasoline (Pool) with 10.7%

vol Preparation Component Mixtures

RON increasing

RON of Blends

RON of Prepared Gasoline(pool)

Component Mixtures Symbol

6.0 90.5 84.5 E1 3.1 87.6 84.5 E2 3.0 87.5 84.5 E3 6.7 91.2 84.5 E4 5.1 89.6 84.5 E5 9.1 93.6 84.5 E6 8.1 92.6 84.5 E7 5.7 90.2 84.5 E8 9.7 94.2 84.5 E9 11.5 96 84.5 E10 10.1 94.6 84.5 E11

84.5

86.5

88.5

90.5

92.5

94.5

96.5

98.5

RO

N

RON 90.8 87.9 87.8 92 90.4 94.4 93.4 91 94.2 96 94.6

E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 E11

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

69

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)

RON Increasing RON Component 0.0 69.2 LSRN 9.0 78.2 LSRN+10.7%E10 8.5 77.7 LSRN+10.7%E11 8.8 78.0 LSRN+10.7%E9 8.6 77.8 LSRN+10.7%E6

69.2

71.2

73.2

75.2

77.2

79.2

RO

N

RON 69.2 78.2 77.7 78 77.8

LSRN LSRN+10.7%E10

LSRN+10.7%E11

LSRN+10.7%E9

LSRN+10.7%E6

Fig (4-11) Octane Number for Blended of Al Doura LSRN with

10.7%vol Preparation Component Mixtures (E10, E11, E9, and E6)

70

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).

71

Table (4-12) Summarized Lab. Testing for Two Samples Gasoline Pool

with 7.4%vol (E10)

Properties items

Test methods

Sample 1

Sample1+ 7.4%E10

Sample 2

Sample 2+ 7.4%E10

Sp.gr. IROX 0.733 0.744 0.75 0.756

RVP bar ASTM D323 0.44 0.48 0.42 0.46

Distillation Tempo

ASTM C I.BP D86

49 47 51 50

10% 63 57 71 66

20% 67 67 81 73

30% 79 77 90 83

40% 89 90 101 95

50% 99 104 111 109

60% 113 116 122 121

70% 126 129 132 133

80% 138 140 143 144

90% 152 152 155 156

EBP 179 179 184 180

T.D.ml 98 99 98 98

Max.S.content ppm

ASTM D4294 44-5 34-3 40-2 36-3

Water content ppm

ASTM D4928 45-4 58-4 39-4 35-9


ASTM D381 Nill Nill Nill Nill

Calorific value kcal/kgm

11272 11238 11219 11200

MON ASTM D2700 85-1 90-9 85-0 88-8 RON ASTM D2699 89.7 95.4 89.6 93.3

Aromatics vol%

IROX 32.99 33.63 38.67 39.12

Olefins vol%

IROX 0 0 0 0

Paraffins and Naphthenes vol%

IROX 67.01 66.37 61.33 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

72

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).

0123456789

10

RO

N in

crea

sing

RON increasing 9.1 5.7 3.7

Prepared gasoline pool

Sample 1+E10 Sample 2+E10

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

73

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

74

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.

75

REFRENCES 1. Hmadi A. Sh., Training Course, Petroleum Refining, August

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

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.

ed. New York, NY: Van Nostrand Reinhold Company, 491-493,

1973.

7. 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 issues. Available

from: : http://www.cnie.org/NLE/CRSre

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.

http://www.cnie.org/NLE/CRSreports/energy/eng.59.cfn�

http://www.cnie.org/NLE/CRSreports/energy/eng.59.cfn�

76

11. Sax NI, Lewis RJ, eds. 1989. Dangerous properties of industrial materials.

7th ed. New York, NY: Van Nostrand Reinhold, 1795-1796.

12. Weiss G., ed. Hazardous chemicals data book. 2nd ed. Park Ridge, NJ:

Noyes Data Corporation, 542, 1986.

13. Budavari S, O’Neil MJ, Smith A, et al. The Merck index: An encyclopedia of

chemicals, drugs, and biologicals. Rahway, NJ: Merck and Co., Inc, 4269.,

eds. 1989.

14. OHM/TADS. 1991. Oil and Hazardous Materials/Technical Assistance

Data System. Batimor, MD: Chemical Information System, Inc.

September, 1986.

15. IARC monographs on the evaluation of carcinogenic risks to humans. Vol.

45: Occupational exposures in petroleum refining; crude oil and major

petroleum fuels. Lyon, France: World Health Organization, International

Agency for Research on Cancer, 159-201, 1989.

16. Air Force. Gasoline. In: The installation restoration program toxicology guide.

Volume 4.Contract no. DE-AC05-840R21400. Wright-Patterson Air Force

Base, OH. Document no. 65-l-65-46, 1989.

17. Annual book of ASTM Standards, American Society for Testing and

Materials, Petroleum products, lubricants, and fossil fuels. Vol 1-14, 1989.

18. Manual for Classification of Gases, Vapors, and Dusts for electrical

equipment in hazardous (classified) locations.Quincy, MA:National Fire

Protection Association, NFPA Publication No. 497M,1986.

19. Al Dawood A. M., Effects of Blending MTBE, Methanol, or Ethanol

with Gasoline on Performance and Exhaust Emission of SI Engines,

Dhahran, Saudi Arabia, December 1998.

20. Obert E.D. Internal Combustion Engines and Air Pollution, Harper and Raw

Publishers, 1973.

77

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

24. Downs D., and Walsh A.D., Knock in Internal Combustion Engines, Nature,

vol 163, p 370, 1949.

edition, 1992.

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 terms of

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

33. Owen K. and Coley T. Automotive Fuels Reference Book. 2

edition 1984. nd

34. Annual Book of ASTM Standard, Standard Specification for Automotive

Spark Ignition Engine Fuel, ASTM D4814-940. V. 05, 05.ISBN, 0-8031-

2218-7, 1995.

edition, SAE.

ISBAN 1-56091-589-7, 1995.

http://www.faqs.org/fags/autos/gasoline_faq/part�

78

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, 11-

45, 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.

79

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. P

1986عبد هللا مصلح التكريتي،اسماعيل رشيد اسماعيل،الرصاص في كازولين السيارات وطرق تخفيضه

61. Keller A.A. and Fernandz L, Beyond MTBE: Applying the Precautionary

Principle to Gasoline Additives 2001.

http://www.directindustry.com/�

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

Properties Items

Test Methods Al-Doura Leaded

Gasoline

Commercial Gasoline

Sp.gr. IROX 0.724 0.739 RVP bar ASTM D323 0.46 0.55 Distillation ASTM D86 Tempo C I.BP 35 40

10% 51 62 20% 61 67 30% 69 75 40% 77 85 50% 87 98 60% 100 114 70% 111 129 80% 128 143 90% 149 167 EBP 171 219 T.D.ml 98.5 98.5 Max.S.content ppm

ASTM D4294 102.1 648.6

Water content ppm

ASTM D4928 63 133.09


ASTM D381 2.2 3.4

Calorific value kcal/kgm

11299 11253

MON ASTM D2700 80.4 89 RON ASTM D2699 85 94 Aromatics vol% IROX 28.25 19.23 Olefins vol% IROX 0 22.6 Paraffins and Naphthenes vol%

IROX 71.75 58.17

144

LIST OF FIGURES 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 MON Different AKI82 77.4 4.6 79.783 78.5 4.5 80.7584 79.4 4.6 81.785 80.3 4.7 82.6586 81.5 4.4 83.75

86.5 82.1 4.4 84.386.8 82.2 4.6 84.587.4 83 4.4 85.287.8 83.5 4.3 85.6588 83.6 4.4 85.8

88.2 83.7 4.5 85.9588.5 84 4.5 86.2588.8 84.2 4.6 86.589 84.5 4.5 86.75

89.5 85 4.5 87.2589.8 85.3 4.5 87.5590 85.5 4.5 87.75

90.7 86.2 4.5 88.4591 86.5 4.5 88.75

91.5 86.6 5.1 89.0592 87 5.2 89.5

92.5 87.5 5.3 9093 88 5 90.5

93.5 88.5 5 9194 89 5 91.5

RON MON Different AKI 82 77.4 4.6 79.7 83 78.5 4.5 80.75 84 79.4 4.6 81.7 85 80.3 4.7 82.65 86 81.5 4.4 83.75

86.5 82.1 4.4 84.3 86.8 82.2 4.6 84.5 87.4 83 4.4 85.2 87.8 83.5 4.3 85.65 88 83.6 4.4 85.8

88.2 83.7 4.5 85.95 88.5 84 4.5 86.25 88.8 84.2 4.6 86.5 89 84.5 4.5 86.75

89.5 85 4.5 87.25 89.8 85.3 4.5 87.55 90 85.5 4.5 87.75

90.7 86.2 4.5 88.45 91 86.5 4.5 88.75

91.5 86.6 5.1 89.05 92 87 5.2 89.5

92.5 87.5 5.3 90 93 88 5 90.5

93.5 88.5 5 91 94 89 5 91.5

جمهورية العراق وزارة التعليم العالي والبحث العلمي

الجامعة التكنولوجية

خلطه مع مركبات منتقـاةبللكازولين تحسين العدد االوكتاني

رسالة مقدمة إلى بغداد –قسم الهندسة الكيمياوية في الجامعة التكنولوجية

/ كجزء من متطلبات نيل درجة الماجستير في علوم الهندسة الكيمياوية بتروكيمياوية الصناعات الو نفطالتكرير

من قبل

ايمان علي احسان شيت

باشراف عادل شريف حمادي. د

2008

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