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Dedicated to: My Parents,
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ACKNOWLEDGMENT ,VWDUWP\VHQWHQFHZLWK³,QWKHQDPHRI$OODKDRIWKHPRVW0HUFLIXODQGPRVW *UDFLRXVWKH&UHDWRURIDOOFUHDWXUHV´3UDLVHEHWR*RGIRU+LVFRXQWOHVVHQGOHVV and infinite blessings. I am grateful to Prof. Dr. Abdel-Monem A. El-Bassiouny, Professor of Chemical Engineering, Faculty of Engineering, Minia University, and Dr. Tarek M. Aboul-Fotouh, Lecturer of Petroleum Engineering, Faculty of Engineering, AlAzhar University for their assistance, continuous support, constructive discussion, great help, precious continuous guidance, and kind encouragement during carrying out this thesis. Their talents have contributed inestimably towards the success of this thesis and without their efforts it would not have been possible for the author of this thesis to take up the present research. My deepest gratitude and sincere appreciation goes to Middle East Oil Refinery (MIDOR) Company for providing the raw materials required for the experimental work and does the analysis of the samples. I wish to express my deepest thanks to Dr. Mohammed Abdelaziz, Head of Midor Company, and Eng. Mohammed El Metwaally Nasr, Assistant of Head of Midor Company for their sincere efforts and great help. Thanks are extended to all the staff members of Chemical Engineering Department, Faculty of Engineering, Minia University, for making an undergraduate study a memorable and a rich experiences. And finally, I like to express my deepest sincere appreciation and gratitude to my brother, Chem. Eng. Essam Mohammed Abdellatif Production Engineer at Misr Specialty Fertilizer Company (YARA International group), for his continuous encouragement and great help.
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ABSTRACT Gasoline produced in Egypt is a low-grade gasoline that contains a high concentration of harmful components that are having a bad effect on our environment. In addition, those pollutants cause countless diseases and deaths annually to the Egyptian population. There are two main targets in this research, the first is the production of new blends of environmental and clean gasolines A98 and A95 with high octane numbers which have less amount of benzene and aromatic contents according to all specifications of Euro-6 and thus it is the best solution for long run. Obviously, straight run naphtha, isomerate, reformate, Coker naphtha and hydrocracked naphtha produced from crude distillation unit, isomerization process, catalytic reforming and conversion processes respectively are blended with an oxygenated compound; ethanol which has many advantages such as friendly environmental, highly octane number and easily obtained by different methods. When gasoline-ethanol blends combust, the pollutants will reduce. The physicochemical characteristics have been studied such as density, Reid Vapor Pressure, ASTM distillation, Research Octane Number, Motor Octane Number, posted Octane Number, PIONA and benzene content to select the optimum samples of environmental gasolines. The compositions of optimum samples are N17 R31 I18 H27.5 C4 E2.5 and N16 R30 I18 H27 C4 E5 and thus these samples are satisfied to the Standard European regulations Euro-6 (EN 228) for transportation and emissions. Therefore, these samples contain 31.3 vol. % aromatics for gasoline A95 and 30.9 vol. % aromatics for gasoline A98. Moreover, the benzene content of them is 0.6 vol. %. In addition, these samples have isoparrafins with the percentages of 29.1 vol. % and 28.9 vol. % for gasoline A95 and A98 respectively. Upgrading gasoline A80 is the second aim to produce environmental gasoline in order to serve our country (Egypt). By using blends of gasoline A80 and products from upgrading units and conversion units, the Environmental gasoline is produced to approach to the standard European regulations of gasoline A92. Clearly, three samples of reformate, isomerate, Coker ŝŝŝ
naphtha and hydrocracked naphtha are blended separately with gasoline A80. The composition of the optimum sample, a new blend of environmental gasoline, is E7.5 C3.75 H14 R27.5 I2.5 G44.75. This sample contains mainly 39.5 vol. % aromatic content, 28.9 vol. % isoparaffins and 1.1 vol. % benzene content. Therefore, this optimum sample in the overall case exactly meets the conditions of Euro-3 and approach to Euro-6 regulations. Finally, upgrading for gasoline A80 is achieved to obtain gasoline A92 as an environmental gasoline and thus it is the best solution in the short run.
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ABBREVIATIONS AND ACRONYMS ASTM
American Standard for Testing and Materials.
API
American Petroleum Institute.
BTEX
Benzene, Toluene, Ethyl Benzene and xylene.
C
Coker Naphtha.
CFR
Cooperative Fuel Research.
Co
Carbon Mono oxide.
Co2
Carbon Di oxide.
DIPE
Di-iso Propyl Ether.
E5
Gasoline blended with 5% (by volume) ethanol.
EU
European Union.
ETBE
Ethyl Tertiary Butyl Ether.
EPA
Environmental Protection Agency.
FBP
Final Boiling Point.
FCC
Fluidized Catalytic Cracking.
G
Gasoline A80.
H
Hydrocracked Naphtha.
H.N
Heavy Naphtha.
HSRN
Heavy Straight Run Naphtha.
I
Isomerate.
IBP
Initial Boiling Point.
IPA
Iso Propyl Alcohol.
Kg/cm3
Kilo Gram per Cubic Centimeter.
KPa
Kilo Pascal.
LSRN
Light Straight Run Naphtha.
MON
Motor Octane Number.
MTBE
Methyl Tertiary Butyl Ether. ǀ
N
Straight Run Naphtha.
PIONA
Parrafins, iso-paraffins, Olefins, Naphthenes and Aromatics.
PON
Posted Octane Number.
R
Reformate.
RON
Research Octane Number.
RVP
Reid Vapor Pressure.
SI Engine
Spark-Ignition Engine.
TAME
Tertiary Amyl Methyl Ether.
TBP
True Boiling Point.
TBA
Tertiary Butyl Alcohol.
UHC
Unburned Hydrocarbons.
ǀŝ
Table of Contents List of Publications ............................................................................................... i ACKNOWLEDGMENT ..................................................................................... ii ABSTRACT ....................................................................................................... iii ABBREVIATIONS AND ACRONYMS............................................................ v List of Figures...................................................................................................... x List of Tables .................................................................................................... xiii CHAPTER ONEINTRODUCTION .................................................................. 1 1.1 Gasoline ........................................................................................................1 1-2 Gasoline Grades ...........................................................................................2 1.3 Gasoline Octane Number .............................................................................2 1.4 Streams Used in Gasoline Blending.............................................................3 1-4 Problem statement........................................................................................5 1-5 Aim of the Work ..........................................................................................6 CHAPTER TWOLITERATURE REVIEW....................................................... 8 CHAPTER THREEEXPERIMENTAL WORK .................................................. 16 3.1 Chemicals and raw materials......................................................................16 3.2 Apparatus and equipment .............................................................................17 3.2.1 ASTM Distillation..................................................................................17 3.2.2 Density..................................................................................................20 3.2.3 Reid Vapor Pressure.............................................................................20 3.2.4 Gas chromatography.............................................................................22 3.2.5 Octane Number ......................................................................................24 3.3 Blendstock volumes......................................................................................24 3.4 Plan of experimental work..........................................................................28 CHAPTER FOURRESULTS AND DISCUSSION......................................... 34 Part 1: The Production of Environmental, Clean and High Octane Number Gasoline %OHQGV ,W¶VWKHEHVWVROXWLRQLQWKH/RQJ5XQ .................................... 34 4.1 Physico-chemical Characteristics of Refinery Gasoline-Blend Samples ..34 4.2 Physico-chemical Characteristics of three Samples Prepared for Euro-6..35 4.2.1 ASTM Distillation Curves of Selected Samples..................................35 4.2.2 Gas chromatography (PIONA &BTEX) ..............................................36 ǀŝŝ
4.3 Physico-chemical Characteristics of Gasoline-Ethanol Blend Samples ....43 4.3.1 The Effect of Ethanol Addition on Octane Number ............................46 4.3.2 The Effect of Ethanol Addition on Reid Vapor Pressure and Density 46 4.3.3 The Effect of Ethanol on ASTM Distillation .......................................48 4.3.4 Gas chromatography (PIONA &BTEX) ..............................................48 3DUW 8SJUDGLQJRI&RPPHUFLDO(J\SWLDQ*DVROLQH$ ,W¶VWKHEHVWVROXWLRQLQ the Short Run)........................................................................................ 53 4.4 Physico-chemical Characteristics of Gasoline A80-Ethanol Blends. ........53 4.4.1 Octane Number Measurement..............................................................55 4.4.2 Density and Reid Vapor Pressure.........................................................55 4.4.3 ASTM Distillation................................................................................55 4.4.4 Gas Chromatography (PIONA &BTEX) .............................................55 4.5 Physico-chemical Characteristics of Gasoline A80-Coker Naphtha Blend Samples........................................................................................................58 4.5.1 Octane Number Measurement..............................................................59 4.5.2 Density and Reid Vapor Pressure.........................................................60 4.5.3 ASTM Distillation................................................................................60 4.5.4 Gas Chromatography (PIONA &BTEX) .............................................63 4.6 Physico-chemical Characteristics of Gasoline A80-Hydrocracked Naphtha Blend Samples ....................................................................................... 64 4.6.1 Octane Number Measurement..............................................................65 4.6.2 Density and Reid Vapor Pressure.........................................................66 4.7 Physico-chemical Characteristics of Gasoline A80 -Reformate Blend Samples........................................................................................................70 4.7.1 Octane Number Measurement..............................................................70 4.7.2 Density and Reid Vapor Pressure.........................................................71 4.7.3 ASTM Distillation................................................................................71 4.8 Physico-chemical Characteristics of Gasoline A80- Isomerate Blend Samples .....................................................................................................................75 4.8.1 Octane Number Measurement..............................................................76 4.8.2 Density and Reid Vapor Pressure.........................................................76 4.8.4 Gas Chromatography (PIONA &BTEX) .............................................79 4.9 Optimum Sample relative to gasoline A80 ................................................80 ǀŝŝŝ
4.9.1 Physico-chemical Characteristics of the Optimum Sample relative to Gasoline A80 .........................................................................................80 4.9.2 ASTM Distillation................................................................................82 CHAPTER FIVECONCLUSIONS AND RECOMMENDATIONS .............. 84 Conclusions ......................................................................................... ϴϰ Recommendations ................................................................................ ϴϱ REFERENCES .................................................................................................. 86 Appendix A........................................................................................................ 92
ŝdž
List of Figures
Fig.1. 1Typical Carbon Chain Lengths[2]. ........................................................... 2
Fig.3. 1 Atmospheric Distillation Apparatus. ..................................................... 19 Fig.3. 2 Density Meter Apparatus. ...................................................................... 21 Fig.3. 3Reid Vapor Pressure Tester .................................................................... 23 Fig.3. 4Varian Detailed Hydrocarbon Analysis apparatus. ................................ 26 Fig.3. 5Octane Meter Apparatus ......................................................................... 27 Fig.3. 6 Cooperative Fuel Research (CFR)) Engine. .......................................... 30 Fig.3. 7 Experimental Blended Samples. ............................................................ 32 Fig.3. 8 Schematic Diagram for the Experimental Work. .................................. 33
Fig. 4. 1 ASTM Distillation Curves for Different Gasoline ± Blend Samples. .. 40 Fig. 4. 2 Comparison among Selected Refinery Gasoline ± Blend Samples. ..... 41 Fig. 4. 3The Composition Analysis of Selected Refinery Gasoline -Blend Samples by Gas Chromatography. .......................................................... 42 Fig. 4. 4The Volume Percent of Major Aromatic Components (BTEX) in Selected Refinery Gasoline- Blend Samples. ......................................... 42 Fig. 4. 5 Relationship between Octane Numbers and Gasoline ±Ethanol blends ............................................................................................................................. 47 Fig. 4. 6 Density and Reid Vapor Pressure curve versus ethanol percent in gasoline blend. ...................................................................................... 47 Fig. 4. 7 ASTM Distillation Curve for Gasoline - Ethanol Blend Samples. ...... 49 Fig. 4. 8 Composition Analysis for Gasoline -Ethanol Blend Samples by Gas Chromatography.................................................................................... 51 Fig. 4. 9 The Volume Percent of Major Aromatic Components (BTEX) in Selected Refinery Gasoline ±Ethanol Blend Samples. ......................... 52
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Fig. 4. 10 Relationship between Octane Numbers and Gasoline A80 -Ethanol blends. ................................................................................................. 57 Fig. 4. 11 Density and Reid Vapor Pressure Curves versus Ethanol Percent in Gasoline A80 Blend............................................................................ 57 Fig. 4. 12 ASTM Distillation Curve for Gasoline 80 -Ethanol Blend Samples. 58 Fig. 4. 13 The Composition of Gasoline A80- ethanol Blend Sample by Gas Chromatography.................................................................................. 59 Fig. 414 The Volume Percentages of Major Aromatic Components (BTEX) in Gasoline A80 -Ethanol Blend Samples. ............................................. 60 Fig. 4. 15 Relationship between Octane Numbers and Gasoline A80-Coker Naphtha blends.................................................................................... 62 Fig. 4. 16 Density and Reid Vapor Pressure Curves versus Coker Naphtha Percent in Gasoline A80 Blend........................................................... 62 Fig. 4. 17 ASTM Distillation Curves for Gasoline A80-Coker Naphtha Blend Samples. .............................................................................................. 63 Fig. 4. 18 The Composition of Gasoline A80- Coker Naphtha Blend Sample by Gas Chromatography. ......................................................................... 64 Fig. 4. 19 The Volume Percentages of Major Aromatic Components (BTEX) in Gasoline A80 -Coker Naphtha Blend Samples. ................................. 65 Fig. 4. 20 Relation ship among octane numbers and gassoline A80Hydrocracked Naphtha blends............................................................ 66 Fig. 4. 21 Density and Reid Vapor Pressure Curves versus Hydrocracked Naphtha Percent in Gasoline A80 Blend. ........................................... 68 Fig. 4. 22 ASTM Distillation Curves for Gasoline A80-Hydrocracked Naphtha Blend Samples..................................................................................... 69 Fig. 4. 23 The Composition of Gasoline A80-Hydrocracked Naphtha blend Samples by Gas Chromatography....................................................... 69 Fig. 4. 24 The Volume Percentages of Major Aromatic Components (BTEX) in Hydrocracked Naphtha-GasolineA80 Blend Samples........................ 71 džŝ
Fig. 425 Relationship between Octane Numbers and Gasoline A80-Reformate blends. ................................................................................................. 72 Fig. 4. 26 Density and Reid Vapor Pressure Curves versus Reformate Percent in gasoline A80 Blend............................................................................. 74 Fig. 4. 27 ASTM Distillation Curves for Gasoline A80-Reformate Blend Samples. .............................................................................................. 74 Fig. 4. 28 The Composition of Gasoline A80-Reformate blend samples by Gas ............................................................................................................................. 76 Fig. 4. 29 The Volume Percent of Major Aromatic Components (BTEX) in Reformate-Gasoline A80 Blend Samples. .......................................... 76 Fig. 4. 30 Relationship between Octane Numbers and Gasoline A80-Isomerate blends .................................................................................................. 77 Fig. 4. 31 Density and Reid Vapor Pressure Curves versus Isomerate Percent in Gasoline A80 Blend. ........................................................................... 77 Fig. 4. 32 ASTM Distillation Curves for Gasoline A80-Isomerate Blend Samples. .............................................................................................. 79 Fig. 4. 33 The Composition of Gasoline A80-Isomerate blend Samples by Gas Chromatography.................................................................................. 80 Fig. 4. 34 The Volume Percent of Major Aromatic Components ( BTEX) in Isomerate- Gasoline A80 Blend Samples. .......................................... 81 Fig. 4. 35 ASTM Distillation curve of Optimum Sample relative to gasoline A80...................................................................................................... 83
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List of Tables Table 3. 1The Raw Materials used to produce an environmental gasoline. ....... 16 Table 32 ASTM Standard Methods of Analyses. ............................................. 17 Table 3. 3ASTM Distillation ID. ....................................................................... 18 Table 3. 4The Properties of Density Meter......................................................... 20 Table 3. 5 The Properties of Reid Vapor Pressure Tester................................... 22 Table 3. 6 The Properties of Gas chromatography. ............................................ 25 Table 3. 7: octane meter specifications. .............................................................. 27 Table 3. 8 Detailed specifications of CFR engine. ............................................. 29 Table 3. 9 Typical Volume Shares and Properties of Standard Gasoline Blend stocks[46] .......................................................................................... 31
Table 4. 1 Refinery Gasoline - Blend Samples................................................... 37 Table 4. 2 Gas Chromatography Analysis of Refinery Gasoline -Blend Samples. ............................................................................................................................. 38 Table 4. 3 Physico-chemical Characteristics of Selected Samples according to Euro-6.................................................................................................. 39 Table 4. 4 Compositions of Gasoline-Ethanol Blend Samples........................... 44 Table 4. 5 Physico-chemical Characteristics of Gasoline -Ethanol Blend Samples. .............................................................................................. 45 Table 4. 6 The Composition of Gasoline A80-blend Samples. .......................... 54 Table 4. 7 Physico-chemical Characteristics of Gasoline A80-Ethanol Blends. 56 Table 4. 8 Physico-chemical Characteristics of Gasoline A80-Coker Naphtha Blend Samples..................................................................................... 61 Table 4. 9 Physico-chemical Characteristics of Gasoline A80-Hydrocracked Naphtha Blend Samples...................................................................... 67 Table 4. 10 Physico-chemical Characteristics of Gasoline A80-Reformate Blend Samples. ............................................................................................ 73 džŝŝŝ
Table 4. 11Physico-chemical Characteristics of Gasoline A80-Isomerate Blend Samples. ............................................................................................ 78 Table 4. 12 The Optimum Sample relative to gasoline A80.............................. 81 Table 4. 13 Physico-chemical Characteristics of the Optimum Sample relative to gasoline A80. .................................................................................... 82
Table A. 1 Euro-6 Gasoline Requirements[47, 48]. ........................................... 92 Table A. 2 Euro Emission Parameters[47].......................................................... 93 Table A. 3 Euro-3 Gaoline Requirements[49]. .................................................. 93
džŝǀ
Chapter One
Introduction CHAPTER ONE INTRODUCTION
Straight run naphtha, isomerate, reformate, Coker naphtha and hydrocracked naphtha produced from crude distillation unit, isomerization process, catalytic reforming and conversion processes respectively are blended with an oxygenated compound such as ethanol to produce environmental gasolines A98 and A95 satisfied to all specifications of Euro-6 regulations. Ethanol has many advantages such as friendly environmental, highly octane number and easily obtained by different methods. When gasoline-ethanol blends combust, the pollutants are reduced. Moreover, environmental gasoline has a low percent of benzene and aromatic content which have a negative effect on our environment. Also, ethanol is blended with gasoline A80 and the previously mentioned cuts to upgrade it to environmental gasoline approach to A92. Gasoline A80 has high percentages of benzene and aromatic content which are carcinogenic materials. Upgrading gasoline A80 has a positive effect on our environment because it produces an environmental gasoline which has less percentages of benzene and aromatic content. 1.1 Gasoline Gasoline or petrol is a transparent, petroleum-derived liquid that is used primarily as a fuel in internal combustion engines. Gasolines are complex mixtures of hydrocarbons having typical boiling ranges from 100 to 400 F ( 38 to 205 C ) as determined by the ASTM method and it consists mostly of organic compounds obtained by the fractional distillation of petroleum, enhanced with a variety of additives. Some gasoline also contains ethanol as an alternative fuel. It is a volatile, flammable liquid obtained from the refinement of petroleum, or crude oil. Gasoline is a complete mixture of over 500 hydrocarbons. Those ϭ
Chapter One
Introduction
hydrocarbons range from 5 to 12 carbons[1]. Figure 1.1shows the typical carbon chain lengths.
Fig.1. 1Typical Carbon Chain Lengths[2]. 1-2 Gasoline Grades Gasoline is categorized into three grades based on the octane number : 1-Regular Gasoline: Gasoline that has an octane rating that is greater than or equal to 85 but less than 88. 2-Mid-Grade Gasoline: Gasoline that has an octane rating greater than or equal to 88 but less than 90. 3- Premium Gasoline: Gasoline that has an octane rating greater than 90. API survey reported that 40 types of gasoline are made by refineries, about of the total gasoline produced in United States is used as fuel in automobiles [1]. 1.3 Gasoline Octane Number Certain
gasoline samples have a different octane numbers. That number
allows us to understand the quality of that gasoline. That is how the gasoline is Ϯ
Chapter One
Introduction
graded into the different grades mentioned above. The octane number measures the quality of gasoline (the antiknoking performance) that is equivalent to the performance of a mixture of iso-octane (that has an octane number of 100) and normal heptane (that has an octane number of 0) at the same conditions [3]. To be able to calculate the average octane number of a gasoline sample, two octane numbers have to be determined. Research octane number (RON) and Motor octane number (MON). An average of both those number is what determines the octanenumber of the fuel and thus its quality. RON is calculated first followed by the MONThe main difference between those two tests is the running conditions of the engine. ForRON, the engine is at a low rpm of 600. And correlates best with low speed, mild-knocking conditions. On the other hand, the MON is worked out at a much more severe conditions of around 900 rpm and MON correlates best with high-speed and high-temperature knocking conditions for that reason, RON would always give a higher octane number than the MON for the same gasoline sample. The uses of those two tests allow us to understand the sensitivity of the gasoline sample[4]. 1.4 Streams Used in Gasoline Blending The components used in blending motor gasoline can be limited to light straight-run (LSR) gasoline or isomerate,catalytic reformate, catalytically cracked gasoline, hydrocracked gasoline, polymer gasoline, alkylate, n-butane, and such additives as MTBE (methyl tertiary butyl ether), ETBE (ethyl tertiary butyl ether), TAME (tertiary amyl methyl ether) and ethanol. Other additives, for examples, antioxidants, a metal deactivator, and anti-stall agents, are not considered individually at this time, but are included with the cost of the antiknock chemicals added. The quantity of antiknock agents added, and their costs, must be determined by making octane blending calculations[1, 5]. Light straight-run (LSR) gasoline consists of the C5-190°F(C5-88°C) fraction of the naphtha cuts from the atmospheric crude still. (C5-190°F fraction means ϯ
Chapter One
Introduction
that pentanes are included in the cut but that C4 and lower boiling compounds are H[FOXGHGDQGWKH7%3HQGSRLQWLVDSSUR[LPDWHO\ ) 6RPHUH¿QHUVFXWDW 180 (83) or 200°F (93°C) instead of 190°F, but, in any case, this is the fraction WKDWFDQQRWEHVLJQL¿FDQWO\XSJUDGHGLQRFWDQHE\FDWDO\WLFUHIRUPLQJ$VDUHVXOW it is processed separately from the heavier straight-run gasoline fractions and requires only caustic washing, light hydrotreating, or, if higher octanes are needed, isomerization to produce a gasoline blending stock[1, 6, 7]. Catalytic reformate is the C5+ gasoline product of the catalytic reformer. Heavy straight-run (HSR) and coker gasoline are used as feed to the catalytic reformer. Its converts low octane naphtha or gasoline into high-octane naphtha or gasoline (Reformate) through conversion of feedstock constituents to products of varying octane numbers[6]. The FCC and HC gasoline are generally used directly as gasoline blending stocks, but in some cases are separated into light and heavy fractions with the heavy fractions upgraded by catalytic reforming before being blended into motor gasoline. This has been true since motor gasoline is unleaded and the clear gasoline pool octane is now several octane numbers higher than when lead was permitted. It is usual for the hydrocracked to be sent to the reformer for octane improvement[1]. The reformer increases the octane by converting low-RFWDQH SDUDI¿QV WR high-octane aromatics. Some aromatics have high rates of reaction with ozone to form visual pollutants in the air and some are claimed to be potentially carcinogenic by the EPA. Restrictions on aromatic contents of motor fuels will KDYH LQFUHDVLQJ LPSDFWV RQ UH¿QHU\ SURFHVVLQJ DV PRUH VHYHUH UHVWULFWLRQV DUH applied. This will restrict the severity of catalytic reforming and will require UH¿QHUV WR XVH RWKHU ZD\V WR LQcrease octane numbers of the gasoline pool by incorporating more oxygenates in the blend[6, 8].
ϰ
Chapter One
Introduction
3RO\PHUJDVROLQHLVPDQXIDFWXUHGE\SRO\PHUL]LQJROH¿QLFK\GURFDUERQV where olifinic hydrocarbons antiknock quality to produce higher molecular ZHLJKWROH¿QVLQWKHJDVROLQHERLOLQJUDQJH5H¿QHU\technology favors alkylation processes rather than polymerization for two reasons: one is that larger quantities RIKLJKHURFWDQH SURGXFWFDQ EH PDGH IURP WKH OLJKWROH¿QVDYDLODEOH DQG WKH RWKHULVWKDWWKHDON\ODWLRQSURGXFWLVSDUDI¿QLFUDWKHUWKDQROH¿QLFDQGROH¿QVDUH highly photoreactive and contribute to visual air pollution and ozone production. The polymerization process is no longer widely used to produce gasoline blend stream[1, 9]. Alkylate gasoline is the product of the reaction of isobutane with propylene, butylene, or pentylene to produce branched-chain hydrocarbons in the gasoline boiling range.$ON\ODWLRQRIDJLYHQTXDQWLW\RIROH¿QVSURGXFHVWZLFHWKHYROXPH of high-octane motor fuel as can be produced by polymerization.In addition, the blending octane (PON) of alkylate is higher and the sensitivity (RON ± MON) is VLJQL¿FDQWO\ORZHUWKDQWKDWRISRO\PHUJDVROLQH[1, 10]. 1-4 Problem statement Nowadays, the automotive industry is expanding, especially in car selling is rapidly, as well as the increasing of fuel's price in the market.To overcome this problem in the overseas development, the use of alternative fuels become broad but in Egypt this area is still limited. There are many examples of alternative fuels used in the car such as ETBE, MTBE, Ethanol and Methanol. This research focuses on gasoline-ethanol blends or commonly known as gasohol and thus this work would contribute to the reduction of air pollution. This is done through the reduction of greenhouse gas emissions such as carbon monoxide, Sulphur oxides (SOX), whether its sulphur dioxide (SO2) or sulphur trioxide (SO3). Moreover, nitrogen oxide concentrations would also decrease due to the cleaner and safer combustion of fuel.
ϱ
Chapter One
Introduction
By reducing nitrogen oxide as well as nitrogen dioxide, the environment would be cleaner resulting in better human health in the long run. Using environmental gasoline would also enable the greater use of gasoline sources as well as other processes that would contribute to a higher and greater efficient gasoline. As a result, the yield of commercial gasoline would increase, maxmize the production of envirnomental gasoline, to support the increasing demand of automotive gasoline. An example of how the yield would increase is by blending some light refinery products such as straight run gasoline, isomerate, reformate, Coker naphtha and hydrocracked naphtha with ethanol to produce a high octane number envirnomental gasoline. This would be carried out through an economical approach in the refinery which would be energy effective and thus cost efficient. 1-5 Aim of the Work There are two main targets in this present work, the first is the production of new blends of environmental gasolines with high octane numbers which have less amount of benzene and aromatic content while the second is upgrading the commercial gasoline A80 to obtain the environmental gasoline A92. At the same time, the Physico-chemical Characteristics of Refinery Gasoline-Blends, in the part 1, are studied to select the base blend for adding ethanol and thus the Physicochemical Characteristics of Gasoline-Ethanol Blends are investigated to obtain new blends in the range of standard European regulations (Euro-6). In other words, the following steps will explain the objectives of the present work: x Select the optimum refinery gasoline blend from the mixtures of SRN, hydrocracked naphtha, reformate, isomerate and Coker naphtha in order to obtain an environmental gasoline with a high octane number. x Investigate the optimum percentage of ethanol that will be added to refinery gasoline blend to produce a high octane environmental gasoline with high antiknock characteristics according to Euro-6 regulations. ϲ
Chapter One
Introduction
x Choose individually the optimum percentages of ethanol, reformate, isomerate, SRN, hydrocracked naphtha and Coker naphtha and make a blend with gasoline A80 to enhance its properties.
ϳ
Chapter Two
Literature Review
CHAPTER TWO LITERATURE REVIEW
Many trials are made to enhance the properties of gasoline in order to produce environmental gasoline such as: Rodríguez-Anton et al.[11] evaluated WKH LQÀXHQFH RI WKH VLPXOWDQHRXV addition of ethanol and ETBE on some physical properties of engine gasoline. The main conclusion is that the simultaneous addition of ETBE and ethanol changes the RVP, ASTM distillation curve, and the density in a way that can affect engine operation and the mandatory EN 228 and ASTM D4814 standards. Some opposite properties of both oxygenates could help to increase the renewable energy content without preventing compliance with these regulations. Altun et al. [12] studied the effect of 10 vol. % of ethanol and 10 vol. % of methanol blending in unleaded gasoline on engine performance and exhaust emission. Results indicated that M10 and E10 blended fuels demonstrated the best result in the exhaust emission. The HC emission of M10 and E10 are reduced by 13% and 15% and the CO emissions by 10.6% and 9.8%, respectively. Increased CO2 emission for M10 and E10 compared with unleaded gasoline was observed. The ethanol and methanol addition to unleaded gasoline demonstrated an increase of BSFC (brake specific fuel consumption) and a decrease of brake thermal efficiency in comparison to unleaded gasoline. Gravalos et al.[13] integrated approximately 1.9 vol. % methanol, 3.5 vol. % propanol, 1.5 vol.% butanol, 1.1vol.% pentanol and variable concentrations of ethanol with a gasoline engine. A total of 30 vol. % alcohol was incorporated into the gasoline. The alcohol-gasoline blend emitted less CO, HC and NOX but more CO2 than pure gasoline. ϴ
Chapter Two
Literature Review
Foong T. et al. [14] reported the RONs and MONs of ethanol blended with production gasoline, four gasoline surrogates, n-heptane, isooctane, and toluene. The ethanol concentration was varied from zero to 100 vol. %, resulting in a clear picture of the variations of the RONs and MONs in all cases. Of initial interest was the almost linear variation of the RON and MON with an ethanol content of blends with an Australian production gasoline. Zemrochet et al. [15] determined what happens to the volatility of the gasoline-ethanol blend up to 25% v/v, specifically its E70, E100, and RVP, when ethanol is splash blended into a wide range of base gasoline. Kheiralla et al.[16] investigated the experimental determination of fuel properties of gasoline-ethanol blends as bio-fuel for SI engines. Using standard laboratory methods, fuel properties of selected blends such density, API gravity, kinematic viscosity, cloud point, flash and fire point, heat value, ASTM distillation and Octane number were studied and compared to gasoline fuel. These blends were namely E10, E15, E20, and E25, E30, and E35.Fuel properties test results showed that blends densities and kinematics viscosity were found to increase continuously and linearly with increasing percentage of ethanol, while API gravity and heat value decreased with decreasing percentage of ethanol increase. Furthermore, cloud point, flash and fire points for blends were found to be higher than gasoline fuel while distillation curves were lower. The tested blends Octane rating based on Research Octane Number (RON) was found to increase continuously and linearly with increasing percentage of ethanol. Soheil et al. [17] studied the effect of oxygenate additives into gasoline for the improvement of physico-chemicalproperties of blends. Methyl Tertiary Butyl Ether (MTBE), Methanol, Tertiary Butyl Alcohol (TBA), and Tertiary Amyl Alcohol (TAA) blend into unleaded gasoline with various blended rates of 2.5, 5, 7.5, 10, 15, and 20 vol. % respectively. Physico-chemical properties of blends are analyzed by the standard American Society of Testing and Materials (ASTM) methods. Methanol, TBA, and TAA increase the density of the mixtures, but ϵ
Chapter Two
Literature Review
MTBE decreases density. The addition of oxygenates lead to a distortion of the EDVHJDVROLQH¶Vdistillation curves. The Reid vapor pressure (RVP) of gasoline is found to increase with the addition of the oxygenated compounds. All oxygenates improve both motor and research octane numbers. Khamis and Palichev [18] investigated the production of stock gasoline with ultra-low sulphur content up to 10 ppm (Euro-5 Standard) by blending of different gasoline streams produced in the Lukoil Nentochim Bourgas (LNHB) refinery units as well as on the study on the efficiency of ferrocene antiknock additives.Some recipes for the production of stock gasoline A92, A95, and A98 commercial grade on the basis ofcomponent streams produced in LNHB refinery units and satisfying all specifications of the Europeanregulations were elaborated. Thus, the gasoline blending provides a great potential benefit to the refinery in view of minimizing operating costs and product quality improvement. Petre [19] used two classical gasolines with different compositions and properties, and with proportions ranging from 2 to 10 vol. % of ethanol and other alcohols, she presents experimental results regarding the effect of the blend with alcohol on the RVP, ASTM distillation curves and evaporated percent at 70 oC. In another paper [20] by the same author and using two classical gasolines with different compositions and properties, and with proportions ranging from 4 to 15 vol. % of ETBE and other ethers, she presents experimental results regarding the effect of the blend with alcohol on the RVP, ASTM distillation curves and vapor lock index. Christensen et al.[21] studied the chemical and physical properties (RVP, vapor lock protection, ASTM distillation, density, octane rating, viscosity and potential for extraction into water) for various alcohol±gasoline blends of up to 3.7% w/w of oxygen and has compared them with the requirements of the ASTM D4814 specification to determine their utility as gasoline extenders.
ϭϬ
Chapter Two
Literature Review
Balaji et al. [22] studied the using of ethanol as a fuel additive to unleaded gasoline causes an improvement in combustion characteristics and significant reduction in exhaust emissions by about 46.5%, 24.3 and 18.2% of the mean average values of CO, HC and NOx emission respectively. On the other hand blending of all ethanol fuels, the CO2 concentration increases. By adding the ethanol with pure gasoline with various percentages, the octane number of ethanol blends are increased. Andersen [23, 24] determined the RVP and ASTM distillation curves for various alcohols±gasoline binary blends containing up to (100 - 85) vol. % of ethanol. This author has reported a simple method to prepare two alcohols± gasoline blends with a RVP that is indistinguishable from that of the base gasoline and has also demonstrated that those blends have ASTM distillation curves closer to that of the base gasoline than single-alcohol blends. Muzíková et al [25] studied WKHLQÀXHQFHRIHWKDQROXSWR vol. %, ETBE up to 10 vol. % and hydrocarbon composition over volatility and ASTM distillation characteristics. Johnson and Schramm [26] studied the low-temperature miscibility of gasoline ethanol -water blends in flex fuel applications at -25 and -2°C. It was found that the blend can be successfully used without phase separations within the tested temperature range. Karonis [27] has examined the impact of simultaneous addition of ETBE up to 6 vol. % and ethanol up to 6 vol. % on the main properties of motor gasoline (RVP, E70, E100, E150, RON, MON, and sensitivity).
Bilgin and Sezer [28] investigated the influence of methanol addition to gasoline on the engine performance. They reported that the maximum brake mean effective pressure (BMEP) was obtained from M5 fuel blend.
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Chapter Two
Literature Review
Menezes et al [29] analyzed the effect of the addition of an azeotropic ETBE/ethanol mixture in two gasolines (0±17) vol. % on the RVP, ASTM distillation curve, the density and the octane number.
Yamin et al. [30] investigated the effect of ethanol addition to low Octane Number gasoline, in terms of calorific value, Octane Number, compression ratio at knocking and engine performance. They blended locally produced gasoline (Octane Number 87) with six different percentages of ethanol, namely 10, 15, 20, 25%, 30, and 35 vol. %. They found that the octane number of gasoline increased continuously with the ethanol percentages in gasoline. They reported that the ethanol was an effective compound for increasing the value of the Octane Number ofgasoline.
Abdel-Rahman and Osman [31] recently
tested 10, 20, 30 and
40 vol. % respectively ethanol of blended fuels in a variable-compression-ratio engine. They found that the increase of ethanol content increases the octane number but decreases the heating value. The 10 vol. % addition of ethanol the most obvious
effect on increasing
the octane number.
had Under
various compression ratios of the engine, the optimum blend rate was found to be 10 vol. % ethanol with 90 vol. % gasoline.
French et al. [32] illustrated the effect of the addition of ethanol to gasoline on the RVP, the ASTM distillation curves (0±10) vol. %, the Vapor/Liquid ratio (V/L), the Vapor Lock Index (VLI), the Drivability Index (DI), the phase separation and the material compatibility.
Hakan Bayraktar [33] investigated the effects of ethanol addition to gasoline on an SI engine performance and exhaust emissions experimentally and theoretically. Experimental applications have been carried out with the blends containing 1.5, 3, 4.5, 6, 7.5, 9, 10.5 and 12 vol. % ethanol. Experimental results ϭϮ
Chapter Two
Literature Review
have shown that among the various blends, the blend of 7.5 vol. % ethanol was the most suitable one from the engine performance and CO emissions. However, theoretical comparisons have shown that the blend containing 16.5 vol. % ethanol was the most suited blend for SI engine. Alexandrian and Schwalm[34] showed that Using gasoline-ethanol blended fuel instead of gasoline alone, especially under fuel-rich conditions, can lower CO and NOx emissions. increases
However,
the emission
using gasoline-ethanol
blended
fuels
of formaldehyde, acetaldehyde and acetone 5.12±
13.8 times than those from gasoline. Although the emission of aldehyde will increase when they use ethanol as a fuel, the damage to the environment by the emitted aldehyde is far less than that by the poly-nuclear aromatics emitted from burning gasoline. Therefore, using higher percentage of alcohol in blended fuel can make the air quality better in comparison with gasoline.
Bata et al. [35] studied different blend rates of gasoline-ethanol fuels in engines, and found that the ethanol could reduce the CO and UHC emissions to some degree. The reduction of CO emission is apparently caused by the wide flammability and oxygenated characteristic of ethanol. 3LNnjQDV HW DO.[36] investigated the engine performance and pollutant emission of a SI engine by using gasoline-ethanol blended fuel E10 and pure gasoline. Experimental results indicated that when gasoline- ethanol blend is used, the engine power and fuel consumption of the engine slightly increase; CO emission decreases dramatically as a result of the leaning effect caused
by
the ethanol
addition; HC
emission decreases
only in some
engine working conditions; and CO2 emission increases because of the improved combustion. In their study, they found that using gasoline-ethanol blend, CO emission may be reduced by 10±30%, while CO2
emission increases by
5±10% depending on engine conditions. The engine power and specific ϭϯ
Chapter Two
Literature Review
fuel consumption
increase approximately
by 5% and 2±3%, respectively,
in all working conditions.
Al-Hasan [37] investigated the eƲect of using unleaded gasoline±ethanol blends on SI engine performance and exhaust emission. Performance tests were conducted for equivalence air±fuel ratio, fuel consumption, volumetric eƳciency, brake thermal eƳciency, brake power, engine torque and brake speci¿c fuel consumption, while exhaust emissions were analyzed for carbon monoxide (CO), carbon dioxide (CO2) and unburned hydrocarbons(UHC).The 20 vol. % ethanol fuel blend gave the best results of the engine performance and exhaust emissions. Ethanol addition results in an increase in brake power, brake thermal eƳciency, volumetric ef¿ciency and fuel consumption by about 8.3%, 9.0%, 7% and 5.7% PHDQ DYHUDJH YDOXHV UHVSHFWLYHO\ ,Q DGGLWLRQ WKH EUDNH VSHFL¿F IXHO consumption and equivalence air±fuel ratio decrease by about 2.4% and 3.7% mean average value, respectively. Using an ethanol±unleaded gasoline blend OHDGVWRDVLJQL¿FDQWUHGXFWLRQLQH[KDXVWHPLVVLRQVE\DERXWDQG of the mean average values of CO and HC emission, respectivelyfor all engine speeds. On the other hand, CO2 emissions increase by about 7.5%. Palmer[38] used various blend rates of gasoline- ethanol fuels in engine tests. Results indicated that 10 vol. % ethanol addition increases the engine power output by 5 %, and the octane number can be increased by 5 % for each 10 vol. % ethanol added͘ Pumphrey et al.[39] offered a simple method to successfully predict vapor pressures of gasoline±alcohol mixtures and validate them with blends of gasoline with different oxygenates (0±100% v/v). There are two main targets in this research, the first is the production of new blends of environmental gasolines with high octane numbers which have less
ϭϰ
Chapter Two
Literature Review
amount of benzene and aromatic content while the second is upgrading the commercial gasoline A80 to obtain the environmental gasoline A92.
ϭϱ
Chapter Three
Experimental Work
CHAPTER THREE EXPERIMENTAL WORK
This chapter includes the experimental work such as; the chemical and materials and the experimental set-up that are followed during the course of this work performed to accomplish the objectives of the study. 3.1 Chemicals and raw materials Table 3.1 shows the chemicals and raw materials which present in Egypt that would allow us to produce an environmental gasoline. In addition, a source could be purchased to improve the quality of the gasoline produced. That source would include oxygenated compounds such as ethanol. Table 3. 1The Raw Materials used to produce an environmental gasoline.
Source
Blend stock
Crude Distillation
Straight Run Naphtha Isomerate
Upgrading Units
Reformate Coker Naphtha
Conversion Units
Hydrocracked Naphtha Ethanol
Purchases
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Chapter Three
Experimental Work
3.2 Apparatus and equipment
Table 32 ASTM Standard Methods of Analyses.
ASTM TestNumber
Test Name Density
ASTM4052
ASTM Distillation
ASTMD86-04
GasChromatography
ASTMD6839
ResearchOctaneNumber
ASTMD2699
MotorOctaneNumber
ASTMD2700
ReidVaporPressure
ASTMD5191
The samples produced are run through various tests. Each test would give us certain information about the sample. Combining that information, it would give an indication to determine which sample would represent our optimum sample in order to further improve it through the oxygenated compound ethanol whilst keeping environmental friendly. The Six tests shown in Table 3.2 help to determine the optimum standardized gasoline blend. This mean that all samples run those tests. By gathering information from the results of those tests, the optimum blend is determined to continue our experimental work on. 3.2.1 ASTM Distillation The distillation characteristic refers to the volatility of the hydrocarbon. How volatile a fuel or solvent is important to understand when it comes to the safety of storage and transportation? Furthermore, through distillation, the boiling range is acquired which gives us information on the compositions as well as the properties
ϭϳ
Chapter Three
Experimental Work
of the fuel. In any fuel or solvent, as the volatility of any fuel increases, the higher the chance of explosive vapors being produced. Distillation requires 100 ml of the sample. Other characteristics are equally important for their use of gasoline in todays applications. Gasoline characteristics could affect start-up, warm-up and the probability of vapor lock. It is because of those important information that is obtained through distillation, petroleum products often include specifications in order process refineries and other control applications to get an initial understanding of the characteristics of the product. In addition, it is required to determine the volume percentages at 100 oC and 150 oC, and estimate the final boiling point temperature. Furthermore, it is required to calculate the volume percentage of distillation residue. All of these measurements must have the specifications of standard European regulations (Euro-6) for the optimum samples. Today there are
various equipment that meet the ASTM D86-04
[40]standards and thus could be used to measure the distillation of petroleum products at atmospheric distillation. Table 3.3 shows the ASTM Distillation ID. Table 3. 3ASTM Distillation ID. Type
Name
Equipment Test Apparatus
Automatic Distillation
Testing Method
ASTM D 86
Equipment serial No.
2025
Equipment No.
2/5
Equipment Model
AD 86 5G
Equipment Name
LSL
Plant Item No.
57BD05/LM3550-20A
ϭϴ
Chapter Three
Experimental Work
The Figure 3.1 illustrates the apparatus of automatic atmospheric distillation .
Fig.3. 1 Atmospheric Distillation Apparatus. This distillation unit uses the boiling ranges to quantitatively determine the characteristics of various products. This test does not work for products that contain high amount of residues.
ϭϵ
Chapter Three
Experimental Work
3.2.2 Density It is the digital density analyzer[41]. This is made of a U-Shaped oscillating tube. In addition, a thermometer is needed to monitor the temperature. A small-scale pipette is required to transfer the small volume required into the testing tube. Table 3.4 shows the properties of density meter and Figure 3.2 shows the density meter apparatus. All results must have the specifications of standard European regulations (Euro-6) for the optimum samples. 3.2.3 Reid Vapor Pressure The pressure exerted by gasoline vapors in a confined space is called Reid vapor pressure. RVP is the most important indicator on both volatility and emissions because of the relation of the existing volatile organic compounds in fuels. Also, RVP is very important driveability of the fuels in year around. RVP of gasoline is different in summers than in winters. Both those seasons cause the RVP of gasoline to change. In summer, the temperature is higher causing the gasoline being volatile as its evaporation at a much faster rate than it does in the winter [42].
Table 3. 4The Properties of Density Meter. Model
KEM DA 500
Serial Number
10268
Applied test method
ASTM D 4052 0- 3 g/cm3
Range
± 0.0001 g/cm3
Accuracy
4-90 o C
Temperature
5-35 o C, less than 85 % RH
Ambient Condition
ϮϬ
Chapter Three
Experimental Work
Fig.3. 2 Density Meter Apparatus͘
Ϯϭ
Chapter Three
Experimental Work
This test is applicable to light petroleum products such as gasoline and volatile crude. This test is very important for gasoline because it gives direct information on the quality of gasoline as well as effect on the environment. Table 3.5 shows the properties of Reid vapor pressure tester and Figure 3.3shows the Reid vapor pressure tester. All results must have the specifications of standard European regulations (Euro-6) for the optimum samples. 3.2.4 Gas chromatography The compositions known through this test not only tell us the chemical composition but give us information needed for the research on an environmental gasoline. Compositions of paraffins, iso-paraffins, olefins, naphthenes and aromatics are known when producing this test. As stated earlier, some of those components are favored to produce a high-octane gasoline. Examples of those are iso-paraffins and aromatics. However, aromatic content is also has to be limited according to certain standard Euro-6 regulations. So this test could help us as a monitor to know how this fuel could be harmful when combusted. The main harm here as mentioned earlier is the amount of benzene present in the aromatic content which could also be known through this GC test[43]. The properties of the device shows in Table 3.6.
Table 3. 5 The Properties of Reid Vapor Pressure Tester.
Model
Herzog-HVP972
Serial Number
69720045
Tag number
A09-0355-05
Applied test method
ASTM D 5191
Pressure Range
0-1000 k Pa
Temperature Range
0-100 o C
ϮϮ
Chapter Three
Experimental Work
Fig.3. 3Reid Vapor Pressure Tester
Ϯϯ
Chapter Three
Experimental Work
3.2.5 Octane Number As stated, this test in a crucial way can help to determine the quality of gasoline fuels. Engine manufacturers as well as refiners aim to design products at high octane number gasoline to improve vehicle performance. On the other hand, refineries also strive to achieve a high octane number to increase profits as well as help to preserve environments. In addition, some refineries are regulated to produce a high octane number envirnomental gasoline. This test measures the knocking rating of liquid fuels for sparkignition engines. Octane number is measured as the research octane number and motor octane numbers by using ASTM tests D 2699[44] and D 2700 [45]respectively.Table 3.7 shows octane meter specifications and Figure 3.5 demonstrates the octane meter appartus which measures the Research octane Number and Motor Octane number . Figure 3.4 shows Varian Detailed Hydrocarbon Analysis apparatus. There is another apparatuse used in the research to measure the research octane number and motor octane number. Also, The blends Octane rating is determined by a Cooperative Fuels Research (CFR) Engine (D2699). The test engine is a standardized single cylinder, four-stroke cycle, variable compression ratio and carbureted for the determination of Octane Number. It is manufactured as a complete unit by Waukesha Engine Division, Model CFR F-1 Research Method Octane Rating Unit (see Fig. 3.6). Table 3. 8 lists detailed specifications of CFR engine.
3.3 Blendstock volumes Refinery gasoline blend samples is made according to Table 3.9 which lists the most common gasoline blendstocks and indicates typical ranges for the more important blending properties of each blendstock. The uesd blendstocks in this research from Refineries in Egypt are straight run naphtha, isomerate, reformate, Coker naphtha and hydrocracked naphtha blended with ethanol while alkylate and FCC naphtha are not found in Egypt. Furthermore, Our refinery gasoline blend
Ϯϰ
Chapter Three
Experimental Work
Table 3. 6 The Properties of Gas chromatography.
Analysis Conditions
GC
Varian 3600 GC
Carrier Gas
Helium, linear velocity =30 to 30.2 cm/sec @35 o C FID, Temperature: 250 to 300 o C, Range :32*10-12 , Fuel: Hydrogen
Detector
@29-31 cc/min, Air@ 300 cc/min, Makeup gas: Helium @ 24 cc/min 1075 split injector, Temperature: 250300 o C, glass insert
Injector
200:1, Vent flow :285-415 cc/min Split Ratio 100 m*0.25 mm fused silica coated with 0.5 micron bonded methyl
Column
silicon. o
35 C held for 15 min, 1degree/ min to 60 o C, held for 20 min, 2
Temperature Program
degree/min to 200 o C Sample Size
0.34 ul PIANO mix+ 0.3 ul methane+ 0.3 ul n- butane
Ϯϱ
Chapter Three
Experimental Work
Fig.3. 4Varian Detailed Hydrocarbon Analysis apparatus.
Ϯϲ
Chapter Three
Experimental Work
Fig.3. 5Octane Meter Apparatus
Table 3. 7: octane meter specifications. Item
Specifications
Operation Temperature Range
(-10)- (+4) o C
Range of measured Octane Number
67-120
Accuracy of measured Octane
± 0.2
Number Digital Data Display 90 mm Minimum Depth of Sensor Immersion 80 h Time of Continuous Operation
Ϯϳ
Chapter Three
Experimental Work
Samples are based on the typical share volume percent ranges for different blendstocks. Individual refineries produce one to four gasoline grades (distinguished by their octane, sulfur content, and other physical properties). Typically, each grade is a blend of six to ten blend stocks (refinery-produced or purchased). All of the grades are blended from the same set of blend stocks but with different recipes. Finally, the suggested percentages of each blend are carried out to study the physicochemical characteristics of blends and thus observe the performance improvement of them. The Figure 3.7 shows the samples blended in order to conduct the experimental work. From those blendstocks, samples with different compositions are made in order to conduct different tests. As shown, all samples are kept refrigerated because all those samples are volatile which mean every samples at room temperature they could slowly evaporate. Special sealing is conducted to each blendstock as sample and keep refrigerated to prevent evaporation of samples. 3.4 Plan of experimental work The following schematic layout summarizes the main steps of this research (Fig. 3.8 ). Different sources of blendstocks are brought in order to produce different blends. From the various blends produced, a three samples are selected to study their physicochemical characteristics to choose the optimum gasoline blend that satisfied Euro-6 specifications. This is chosen due to its less in aromatics and benzene content and thus this sample will be as a base sample for adding the oxygenated compound (Ethanol) to improve the octane number. From these different blends, an optimum sample is chosen and tested with various vol. % Ethanol from 0-20%. An optimum samples with E2.5 and E5, gasoline A95 and A98, are chosen to represent the environmental gasoline which regulations.
Ϯϴ
satisfied Euro-6
Chapter Three
Experimental Work
Table 3. 8 Detailed specifications of CFR engine.
Item
Specifications CFR F-1 Research Method Octane Rating Unit with cast iron, box type crankcase with
Test Engine
flywheel connected by V-belts to power absorption electrical motor for constant speed operation. Cast iron with flat combustion surface and integral coolant jacket Compression ratio
Cylinder type
Adjustable 4:1 to 18:1 by cranked worm shaft and worm wheel drive assembly in cylinder clamping sleeve.
Cylinder bore
82.25 standard (mm)
Stroke
114.3 mm
Displacement
24083.8 mm2 Forced lubrication, motor driven pump,
Lubrication
plate type oil filter, relief pressure gauge on control panel. Evaporative cooling system with water cooled condenser, Water shall be used in the
Cooling
cylinder jacket for laboratory locations where the resultant boiling temperature shall be 100 ± 1.5°C Water with commercial glycol-based antifreeze added in sufficient quantity to meet the boiling temperature requirement shall be used when laboratory altitude dictates
Ϯϵ
Chapter Three
Experimental Work
Fig.4.5: Reid Vapor Pressure Tester
Fig.3. 6 Cooperative Fuel Research (CFR)) Engine.
ϯϬ
Chapter Three
Experimental Work
Table 3. 9 Typical Volume Shares and Properties of Standard Gasoline Blend stocks[46]
On the other hand , gasoline A80 is enhanced by adding ethanol, coker naphtha, hydrocracked naphtha, reformate and isomerate to obtain Gassoline A92.
ϯϭ
Chapter Three
Experimental Work
Fig.3. 7 Experimental Blended Samples.
ϯϮ
6- RVP
5-GC
4-MON
3-RON
2-Distillation
1-Density
Physicochemical characteristics:
ϯϯ
1-Hydrocracked Naphtha 2-Coker Naphtha
Oxygenated compound (Ethanol)
Euro-6
Gasoline Blends
2- Isomerate
1-Reformate
Fig.3. 8 Schematic Diagram for the Experimental Work. Optimum Sample
Additives (Ethanol)
4. Coker Naphtha
3. Hydrocracked Naphtha, or
2. Isomerate, or
1. Reformate, or
Gasoline A80 (feed)
Crude oil
Optimum Environmental High Octane Gasoline Blend According to Euro-6
Straight Run Naphtha
Upgrading Samples (Part 2)
6- RVP
5-GC
4-MON
3-RON
2-Distillation
1-Density
Physicochemical characteristics:
Experimental Work
The Production of New Blends (Part 1)
Chapter Three
Chapter Four
Results and Discussion
CHAPTER FOUR RESULTS AND DISCUSSION The purpose of this chapter is to discuss the experimental results obtained throughout the present work. In this study, different factors are studied such as octane numbers, Reid vapor pressure, density, ASTM distillations, PIONA and benzene content for gasoline-ethanol blends and gasoline A80.
Part 1: The Production of Environmental, Clean and High 2FWDQH 1XPEHU *DVROLQH %OHQGV ,W¶V WKH EHVW VROXWLRQ LQ the Long Run) Part one represents physico-chemical characteristics of refinery gasolineblend samples, physico-chemical characteristics of gasoline-ethanol blend samples, ASTM distillation curves of selected samples and gasoline- ethanol blend, the relationship among octane numbers and gasoline-ethanol blends, the composition analysis of selected refinery gasoline -blend samples and gasoline-ethanol blend samples by gas chromatography and density and Reid vapor pressure curve versus ethanol percentages in gasoline blends[47]. 4.1 Physico-chemical Characteristics of Refinery Gasoline-Blend Samples Acquiring different sources of blend stocks are completely blended in order to produce different refinery gasoline - blend samples which have different composition of Straight Run Naphtha, Reformate, Isomerate, Coker Naphtha and Hydrocracked Naphtha. Those blends are tabulated in Table 4.1. The Gas Chromatography Device uses to know the percentages of n-paraffins, isoparaffins, olefins, naphthenes, aromatics (PIONA) and benzene content of each blend stock sample, as shown in Table 4.2. Three samples are chosen according to European Regulations Euro-6 and directly complete physico-chemical characteristics are achieved to select an optimum gasoline blend sample for experimental works as a blend with ethanol. ϯϰ
Chapter Four
Results and Discussion
The Selected samples ; sample 4, sample 9 and sample 19; are chosen based on the percentages of aromatics, isoparaffins, olefins and benzene content in each of three samples. These samples contain the smallest percent of aromatics which represent a content approach to Euro- 6 Regulations and the percentages of aromatics content of them are 34.1, 31.9 and 34.8 vol. % respectively. In addition, the benzene content of these samples is less than 1 vol. %. Moreover, the standard percentage of aromatic content is 35 by vol. % including 1 vol. % benzene as a maximum percent; Euro-6. 4.2 Physico-chemical Characteristics of three Samples Prepared for Euro-6 Table 4.3 illustrates physico-chemical characteristics of the selected three samples prepared for Euro-6. It shows density, RVP, RON, MON, PON, ASTM distillation and PIONA for them. The optimum selected sample contains the maximum percent of isoparrafins (29.4 vol. %) and the minimum percent of aromatics (31.9 vol. %). Moreover, the benzene content in this sample is a minimum percent (0.61 vol. %). In the same sample, volumes at 100 oC and 150 o
C are 49 and 89 vol. % respectively and the FBP is 190.4 oC. In addition, the
sample has a good start octane number for all blends. 4.2.1 ASTM Distillation Curves of Selected Samples ASTM distillation curve shows the percentage of hydrocarbons that boil and distill at various temperatures andhelps us to determine the volatility of each sample and thus gives us information on how to handle those samples and even store them. The main factor to understand here is what the sample is composed off. For example, if the sample contains heavier contents, then a greater temperature would be required to evaporate it. This would then mean that different volume percent would be achieved at higher temperatures. On the other hand, lighter components in samples would require less heat in order for them to evaporate and thus would for example have a lower IBP. ϯϱ
Chapter Four
Results and Discussion
Figure 4.1 represents ASTM distillation curves for selected refinery gasoline - blend samples. There are three points are taken on the distillation curve to compare the distillation among the three different samples. These points are the volume percent at 100 oC and 150 oC and the FBP temperature of the optimum sample. Therefore, volumes at 100 oC and 150 oC are 49 and 89 vol. % respectively and the FBP is 190.4 oC. In addition, the distillation residue is 1.2 vol. %. From Figure 4.1, Sample (19) has components lighter than sample (9) and (4) because it has a high content of isomerate. In other words, isomerate is lighter than any components. The percentages of isomerates in samples19, 9 and 4 are 24,19and18 vol. % respectively, as shown in Figure 4.2.
4.2.2 Gas chromatography (PIONA &BTEX) It is a device which used for determining the amount of Parrafins, Olefins, Aromatics, isoparaffins, Naphthenes and benzene content. The comparison among the three samples is based on the aromatics, Iso-paraffin and benzene content. The highest percentage of aromatic content in the sample will increase the octane number but it affects on our environment negatively. The aromatics in sample (4), sample (9) and sample (19) are 34.10, 31.9 and 34.8 vol. % respectively. The optimum percent of aromatics is chosen according to the least percent in the three samples; sample (9). The isoparaffins in sample (4), sample (9) and sample (19) are 27.7, 29.4 and 29.10 vol. % respectively. The optimum percent of isoparaffins is selected based on the highest percentage in the three samples; sample (9).
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Chapter Four
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Fig. 4. 3The Composition Analysis of Selected Refinery Gasoline -Blend Samples by Gas Chromatography.
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Fig. 4. 4The Volume Percent of Major Aromatic Components (BTEX) in Selected Refinery Gasoline- Blend Samples.
ϰϮ
Chapter Four
Results and Discussion
From the previous Tables and Figures, the Sample (9) represents the optimum sample because it contains benzene content 0.61 vol. %, aromatics content 31.9 vol. % and isoparaffins 29.4 vol. %. It is used to produce environmental gasoline according to Euro-6 regulations by adding different percentages of oxygenated compounds. An oxygenated compound (ethanol) is added to gasoline pool (sample (9)) to produce environmental gasoline with high octane number. The different percentages of ethanol added to sample (9) are E0, E2.5, E5, E10, E15 and E20 respectively. Table 4.4 shows the composition of gasoline-ethanol blend samples. 4.3 Physico-chemical Characteristics of Gasoline-Ethanol Blend Samples
Table 4.5 demonstrates physico-chemical characteristics of gasoline-ethanol blend samples. It shows density, RVP, RON, MON, PON, ASTM distillation and PIONA for them. The optimum selected samples are samples (23) and (24) for gasolines A 95 and A98 respectively. In the sample (23) , the density at 15 oC, RVP, RON, MON, PON, aromatics and benzene contents are 740.2 kg/m3, 57 kPa, 95, 86.1, 90.55, 31.3 vol. % and 0.6 vol. % respectively. In sample(24), the density at 15 oC, RVP, RON, MON, PON, aromatics and benzene contents are 742.6 kg/m3, 58 kPa, 98, 96, 97, 30.9 vol. % and 0.6 vol. % respectively. Additions of E2.5 and E5 by volume to gasoline pool are the main target to produce environmental gasolines A95 and A98 according to Euro-6 regulations. Some recipes for the production of stock gasolines A95 and A98 commercial grades on the basis of component streams produced in refinery units and satisfying all specifications of the European regulation are elaborated. Thus, the gasoline blending provides a great potential benefit to the refinery in view of minimizing operating costs and product quality improvement.
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ϰϰ
2.5
31 18 27.5
32 19 28
Reformate Isomerate Hydrocracking Naphtha Coker Naphtha
Upgrading Units Conversion Units
17
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Results and Discussion
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17
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Fig. 4. 23 The Composition of Gasoline A80-Hydrocracked Naphtha blend Samples by Gas Chromatography. ϲϵ
Chapter Four
Results and Discussion
Figure 4.24 illustrates the volume Percentages of major Aromatic components (BTEX) in gasoline A80-Hydrocracked naphtha blend samples. It shows the percentages of benzene, toluene, ethyl benzene and xylenes (BTEX). The percentage of benzene content is 1 vol. % and thus it is satisfactory according to the European regulations of the environmental gasoline which has less amount of emissions. 4.7 Physico-chemical Characteristics of Gasoline A80 -Reformate Blend Samples. Different percentages of Reformate are added to gasoline A80 and observe the effect of each percent on gasoline A80. The percentages of reformate are 22.5, 25, and 27.5 vol. % respectively. Some measurements are made such as Reid Vapor Pressure, density, research octane number, motor octane number, ASTM distillation, PIONA, and benzene content according to ASTM methods. Table 4.10 shows physico-chemical characteristics of gasoline A80-reformate blends. It represents the values of density, RVP, RON, MON, PON, ASTM distillation and PIONA for them. After analyses, the optimum selected sample contains the minimum percent of aromatics (34.6 vol. %). Moreover, the benzene content in this sample is (1.4 vol. %). At the same time, volumes at 100 oC and 150 oC are 38.6 and 84.6 vol. % respectively. The FBP and distillation residue is 205 oC and 0.6 vol. % respectively. 4.7.1 Octane Number Measurement Research octane number, Motor octane number, and Posted octane number are measured when reformate is added to gasoline A80. Figure 4.25 shows relationship between octane numbers and gasoline A80-reformate blends. The octane numbers (RON, MON and PON) increase continuously and linearly with increasing percentages of Reformate. The Research octane number for R22.5, R25 and R27.5 is 91.6, 92 and 92.2respectively.Finally, the optimum sample is H14 which has RON, MON and PON is 92.2, 83 and 87.6 respectively. ϳϬ
Chapter Four
Results and Discussion ƉͲyLJůĞŶĞ
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Fig. 4. 24 The Volume Percentages of Major Aromatic Components (BTEX) in Hydrocracked Naphtha-GasolineA80 Blend Samples. 4.7.2 Density and Reid Vapor Pressure Figure 4.26 illustrates the density and Reid vapor pressure curves versus Reformate percent in gasoline A80. It shows that the density values increase and Reid vapor pressure values decrease with increasing reformate percentage. The density values of R22.5, R25 and R27.5 are 759.3, 762.0 and 765.8 Kg/m3 and its Reid vapor pressure percentages are 39, 37 and 35 kPa. The density and Reid vapor pressure values of the optimum sample are 765.8 kg/m3 and 35 kPa respectively. 4.7.3 ASTM Distillation Figure 4.27 shows ASTM Distillation curves for gasoline A80-Reformate blend samples. The optimum selected sample is R 27.5 and volumes of it at 100 o
C and 150 oC are 38.6 and 84.6 vol. % respectively. In addition, the FBP of it is ϳϭ
Chapter Four
Results and Discussion
205.0oC and its distillation residue is 0.6 vol. %. These results approach to the standard European regulations (Euro-6).
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Fig. 425 Relationship between Octane Numbers and Gasoline A80-Reformate blends. 4.7.4 Gas Chromatography (PIONA &BTEX) Figure 4.28 shows the composition of gasoline A80-reformate blend samples by Gas Chromatography. It illustrates the percentages of parrafins, isoparrafins, aromatics, naphthenes and olefins. Clearly, the aromatic percentages in R22.5, R25 and R27.5 are 41.1, 40.7 and 40.4 vol. % respectively. Finally, the optimum sample is selected according to less one in the aromatic content (R27.5). Figure 4.29 shows the volume Percentages of major Aromatic components (BTEX) in gasoline A80-Reformate blend samples. It shows the percentages of benzene, toluene, ethyl benzene and xylenes (BTEX). ϳϮ
Density at 15 oC Reid Vapor Pressure RON MON PON Distillation at 100 oC at 150 oC at FBP Distillation Residue composition Paraffins Iso- Paraffins Olefins Naphthenes Aromatics oxygenates Benzene dŽůƵĞŶĞ ƚŚLJůďĞŶnjĞŶĞ ŵͲyLJůĞŶĞ ƉͲyLJůĞŶĞ ŽͲyLJůĞŶĞ
composition
Test
ASTM D6729
ASTM D4052 ASTM D5191 ASTM D2699 ASTM D2700 (R+M)/2 ASTM D86
Method
Vol. % Vol. % Vol. % Vol. % Vol. % Vol. % Vol. % sŽů͘й sŽů͘й sŽů͘й sŽů͘й sŽů͘й
Vol. % Vol. % 0 C Vol. %
Kg/m3 kPa
Units
ϳϯ
0.0
0.0
0.0
ͷǤͺ ͵ͷ 92.2 83 87.6 38.6 84.6 ʹͲͷǤͲ ͲǤ
Sample 39 R 27.5G72.5
ʹǤͲ ͵ 92 82.6 87.3 39.1 84.8 ʹͲͶǤͷ ͲǤͻ
Sample No. Sample 38 R 25G 75
ͷͻǤ͵ ͵ͻ 91.6 81.7 86.65 41 85 ʹͲͷǤ͵ ͳ
Sample 37 R 22.5G77.5
Results and Discussion
Table 4. 10 Physico-chemical Characteristics of Gasoline A80-Reformate Blend Samples.
Chapter Four
Chapter Four
Results and Discussion
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Results and Discussion
Fig. 4. 28 The Composition of Gasoline A80-Reformate blend samples by Gas Chromatography. 4.8.1 Octane Number Measurement Research octane number, Motor octane number, and Posted octane number are measured when isomerate is added to gasoline A80. Figure 4.30 represents the relationship between octane numbers and gasoline A80-reformate blends. The octane numbers (RON, MON and PON) increase up to 2.5 vol. % and decrease continuously with increasing percentages of isomerate. The Research octane number for I2.5, I5 and I7.5 is 86.2, 85.7 and 84.2 respectively. At the end, the optimum sample is I2.5 which has RON, MON and PON is 86.2, 78.9 and 82.55 respectively.
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Fig. 4. 29 The Volume Percent of Major Aromatic Components (BTEX) in Reformate-Gasoline A80 Blend Samples. 4.8.2 Density and Reid Vapor Pressure Figure 4.31 illustrates the density and Reid vapor pressure curves versus Isomerate percent in gasoline A80. It shows that the density values increase up to 2.5 vol. % and thus Reid vapor pressure values decrease until 2.5 vol. %. On the other hand, the density values after 2.5 vol. % decrease while Reid vapor pressure ϳϲ
Chapter Four
Results and Discussion
values increase. The density percentages of I2.5, I5 and I7.5 are 738.9, 737.3 and 735.5 Kg/m3 and its Reid vapor pressure values are 45, 47 and 47 kPa respectively. The density and Reid vapor pressure of the optimum sample are 738.9 kg/m3 and 45 kPa respectively. ZKE
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Fig. 4. 30 Relationship between Octane Numbers and Gasoline A80-Isomerate blends
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Fig. 4. 31 Density and Reid Vapor Pressure Curves versus Isomerate Percent in Gasoline A80 Blend. ϳϳ
Density at 15 oC Reid Vapor Pressure RON MON PON Distillation at 100 oC at 150 oC at FBP Distillation Residue composition Paraffins Iso- Paraffins Olefins Naphthenes Aromatics oxygenates Benzene dŽůƵĞŶĞ ƚŚLJůďĞŶnjĞŶĞ ŵͲyLJůĞŶĞ ƉͲyLJůĞŶĞ ŽͲyLJůĞŶĞ
composition
Test
ASTM D6729
ASTM D4052 ASTM D5191 ASTM D2699 ASTM D2700 (R+M)/2 ASTM D86
Method
Vol. % Vol. % Vol. % Vol. % Vol. % Vol. % Vol. % sŽů͘й sŽů͘й sŽů͘й sŽů͘й sŽů͘й
Vol. % Vol. % 0 C Vol. %
Kg/m3 kPa
Units
0.0
0.0
͵Ǥ͵ Ͷ 85.7 78.6 82.15 51.6 90.1 ϭϵϰ͘ϴ ϭ͘Ϭ
ϳϴ
Sample No.
Sample 41 I5G 95
͵ͺǤͻ Ͷͷ 86.2 78.9 82.55 51 89.6 ϭϵϱ͘ϭ ϭ͘Ϭ
Sample 40 I 2.5G97.5
0.0
͵ͷǤͷ Ͷ 84.2 78.8 81.5 52 90.3 ϭϵϴ͘ϰ Ϭ͘ϲ
Results and Discussion
Sample 42 I 7.5G92.5
Table 4. 11Physico-chemical Characteristics of Gasoline A80-Isomerate Blend Samples.
Chapter Four
Chapter Four
Results and Discussion
5.8.3 ASTM Distillation Figure 4.32 shows ASTM Distillation curves for gasoline A80 - isomerate blend samples. The optimum selected sample is I2.5 and the Volumes of it at 100 o
C and 150 oC are 51 and 89.6 vol. % respectively. In addition, the FBP of it is
195.1oC and its distillation residue is 1 vol. %. These results approach to the standard European regulations (Euro-6). 4.8.4 Gas Chromatography (PIONA &BTEX) Figure 4.33 shows the composition of gasoline A80-Isomerate blend samples by Gas Chromatography. It illustrates the percentages of parrafins, isoparrafins, aromatics, naphthenes and olefins. Clearly, the aromatic percentages in I2.5, I5 and I7.5 are 43.1, 43.8 and44.6 vol. % respectively. Finally, the optimum sample is selected according to less one in the aromatic content (I2.5). ^ĂŵƉůĞϰϬ;/Ϯ͘ϱ'ϵϳ͘ϱͿ
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Fig. 4. 32 ASTM Distillation Curves for Gasoline A80-Isomerate Blend Samples͘
ϳϵ
Chapter Four
Results and Discussion
Figure 4.34 illustrates the volume Percent of major Aromatic components (BTEX) in gasoline A80-isomerate blend samples. It shows the percentages of benzene, toluene, ethyl benzene and xylenes (BTEX). The percentage of benzene content is 0.9 vol. % and thus the percentage of benzene is satisfactory according to the European regulations of the environmental gasoline which has less amount of emissions. 4.9 Optimum Sample relative to gasoline A80 The optimum sample which has a composition (E 7.5C 3.75H 14R 27.5I 2.5G44.75) is prepared to determine the density, Reid vapor pressure, RON, MON ,PON, ASTM Distillation and PIONA. The data is tabulated in Table 4.12 which demonstrates the optimum sample relative to gasoline A80. EĂƉŚƚŚĞŶĞƐ
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Fig. 4. 33 The Composition of Gasoline A80-Isomerate blend Samples by Gas Chromatography. 4.9.1 Physico-chemical Characteristics of the Optimum Sample relative to Gasoline A80 Table 4.13 illustrates the physico-chemical characteristics of the optimum sample relative to gasoline A80. It illustrates the values of density, RVP, RON, MON, PON, ASTM distillation and PIONA for them. The optimum selected
ϴϬ
Chapter Four
Results and Discussion
sample contains percentage of aromatics (39.5 vol. %). Moreover, the benzene content in this sample is (1.1 vol. %). Table 4. 12 The Optimum Sample relative to gasoline A80.
Ethanol
7.5
Coker
3.75
Hydrocracker Naphtha
14
Reformate
27.5
Isomerate
2.5
Gasoline 80
44.75
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Fig. 4. 34 The Volume Percent of Major Aromatic Components ( BTEX) in IsomerateGasoline A80 Blend Samples. In the same sample, volumes at 100 oC and 150 oC are 54.5and 84.5 vol. % respectively. In addition, the FBP is 199.6 oC and the distillation residue is 1.3 vol. %. Moreover, the density, RON, MON, PON and RVP values are 734.4
kg/m3,
91.3, 84.1, 87.7 and 44.9 kPa respectively. These results match with ϴϭ
Chapter Four
Results and Discussion
standard European regulations (Euro-6) except the percentages of aromatics is in the range of Euro-3. Therefore, the optimum sample in the overall case exactly meets the conditions of Euro-3 and approach to Euro-6 regulations. Finally, upgrading for gasoline A80 is achieved to obtain gasoline A92 as an environmental gasoline (It is the best solution in the short run). 4.9.2 ASTM Distillation Figure 4.35 illustrates ASTM distillation curve for selected refinery gasoline -blend samples. There are three points are taken on the distillation curve to compare with the standard European regulations (Euro-6). These points are the volume percent at 100 oC and 150 oC and the FBP temperature of the optimum sample. The volumes at 100 oC and 150 oC are 54.5 and 84.5 vol. % respectively and the FBP is 199.6 oC. Table 4. 13 Physico-chemical Characteristics of the Optimum Sample relative to gasoline A80. Test
Method
Units
Optimum Sample (43) E 7.5C 3.75H 14R 27.5I 2.5G44.75
Composition Density at 15 oC Reid Vapor Pressure RON MON PON Distillation at 100 oC at 150 oC at FBP Distillation Residue Composition Paraffins Iso- Paraffins Olefins Naphthenes Aromatics Oxygenates Benzene dŽůƵĞŶĞ ƚŚLJůďĞŶnjĞŶĞ ŵͲyLJůĞŶĞ ƉͲyLJůĞŶĞ ŽͲyLJůĞŶĞ
Kg/m3 kPa
ASTM D4052 ASTM D5191 ASTM D2699 ASTM D2700 (R+M)/2 ASTM D86
Vol. % Vol. % O C Vol. %
734.4 44.9 91.3 84.1 87.7 54.5 84.5 199.6 1.3
Vol. % Vol. % Vol. % Vol. % Vol. % Vol. % Vol. % sŽů͘й sŽů͘й sŽů͘й sŽů͘й sŽů͘й
17.5 28.9 1.7 12.4 39.5 7.5 1.1 ϴ͘Ϯ ϭ͘ϴ ϱ ϭ͘ϵ Ϯ͘ϱ
ASTM D6729
ϴϮ
Chapter Four
Results and Discussion
KƉƚŝŵƵŵ^ĂŵƉůĞ ϮϭϬ ϭϵϬ
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Fig. 4. 35 ASTM Distillation curve of Optimum Sample relative to gasoline A80. In addition, the distillation residue is 1.3 vol. %. These results approach to the standard European regulations (Euro-6). Gasoline A80 which has a lot of pollutants and high percentage of aromatic and benzene content. Therefore, it is upgraded to approach to gasoline A92 and thus a new blend is made for creating an environmental gasoline A 92 according to Euro-6 (EN 228). Finally, the composition of an environmental gasoline (a new blend) contains mainly 39.5 vol. % aromatic content, 28.9 vol. % isoparaffins and 1.1 vol. % benzene content[48].
ϴϯ
Chapter Five
Conclusion &Recommendations CHAPTER FIVE
CONCLUSIONS AND RECOMMENDATIONS Conclusions Based on the observations in the present work, the following conclusions can be drawn: 1. The composition of the optimum sample (sample 9) which prepared for Euro-6 is 17vol. % straight run naphtha, 32 vol. % reformate, 19 vol. % isomerate, 28 vol. % hydrocracked naphtha, and 4 vol. % Coker naphtha. 2. Ethanol-gasoline-blends can be used as an alternative fuel for variable speed spark ignition up to 5 vol. % blends without engine modification. 3. Gasoline A 98 and A 95 are produced by adding oxygenated compound (ethanol) to the optimum sample to achieve a satisfactory blends corresponding with all specification of Euro-6 regulations. The new blends are friendly environmental and contain the less amount of benzene content. 4. E2.5 (sample 23) and E5 (sample 24) are the optimum selected percentages which give the best results in comparisons with others according to standard European regulations (Euro-6). 5. Maximize the quality and quantity of environmental gasoline according to standard European regulations (Euro-6). 6. Gasoline A80 which has a lot of pollutants and high percentage of aromatic and benzene content. Therefore, it is upgraded to approach to gasoline A92 and thus a new blend is made for creating an environmental gasoline A 92 according to Euro-6 (EN 228). 7. The optimum sample contains ethanol, reformate, isomerate, Coker naphtha and hydrocracked naphtha with the percentages of 7.5, 27.5, 2.5, 3.75 and 14 Vol. % respectively. 8. The optimum sample in the overall case exactly meets the conditions of Euro-3 and approach to Euro-6 regulations. ϴϰ
Chapter Five
Conclusion &Recommendations
9. An Environmental gasoline provides a great potential benefit to the refinery in view of minimizing operating costs, product quality improvement, safe and healthy living environments.
Recommendations
The following recommendations could be put for the future work: 1- This thesis should be applied in the industry to prevent the hazards of air pollution. 2- The optimum composition of refinery gasoline blend should be applied for maximizing its quantity and quality with ethanol percentages. 3- Modelling and Simulation should be investigated for this type of work.
ϴϱ
References
REFERENCES [1]. J. H. Gary and G. E. Handwerk, "Petroleum Refining Technology and Economics" 4th edition. Marcel Dekker, NewYork, 2001. [2].
http://www.mfe.govt.nz/publications/hazards/contaminated-land-mgmt-
[3].
J. Bowden and L. Stavinoha,''Evaluation of Motor Gasoline Stability'',
guidelines-no5/4-laboratory-analysis
Belviors Fuel, 2005, 16. . [4].
U. R. Chaudhuri, ''Fundamentals of Petroleum and Petrochemical Engineering'', Calcutta: CRC Press, 2010.
[5].
6 3DUDNDVK µµ5HILQLQJ 3URFHVVHV +DQGERRN¶¶ (OVHYLHU $PVWHUGDP
[6].
M. Fahim, ''Fundamentals of Petroleum Refining'', 1st Edition, Elsevier
2003.
B.V, 2010. [7].
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[8].
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