THE COLLEGE OF PETROLEUM AND ENERGY STUDIES OXFORD Gasoline Technology and Economics — Specifications, Quality, Blending Components and Market Developments Course Code RF5 Held at St Catherine’s College, Oxford 27 —29 October 1993 Course Director: E L MarshallTHE COLLEGE OF PETROLEUM AND ENERGY STUDIES Administrative Offices Sun Alliance House New inn Hall Street ‘Oxford, OX1 20D England Telex: 838950 COLPET-G Fax: +44 865 791474 Telephone: +44 865 250521 A limited liability company registered in England Registration No. 1686405 © 1993 THE COLLEGE OF PETROLEUM AND ENERGY STUDIES. NOTICE ‘The Course Manual copyright is held jointly by The College of Petroleum and Energy Studies and the individual authors of the papers contained within it. No parts of this Manual may be reproduced, transmitted, transcribed, translated, or stored in a retrieval system in any form or by any means without the permission of The College of Petroleum and Energy Studies.THE COLLEGE OF PETROLEUM AND ENERGY STUDIES Mark du Cane Daestor Lone Ne na al St Oars O81 290 ghd PO COUPMTC Fo ats usy ste “eephans Onoda Saer es THE COLLEGE OF PETROLEUM AND ENERGY STUDIES Roger Smeeton Matapiog Dreser Son Alan Hause, New ln Hsin Ole OX1 200 yond Tel RO COLPET CE Fou xh e108 “Telephone Oo nes 25824 ‘THE COLLEGE OF PETROLEUM AND ENERGY STUDIES George B. Roberts Director, Ditee Leaning Progrannes wt wh Hal Sire. vo O31 20 gl Teen MOOG tc tued aay See “eat One aoa O% a a S ° DrGordon E Andrews Reader in Combustion Engineering Department of Fuclaad Energy’ Tex SSA72 casos Fas 0832 400872 one 3281781 Dianne C. Taylor, M.A. Project Officer Department of Fuel and Energy VERSTEY OF LEDS Hof Fuel and Energy. Lewd 0.193 97 ‘Breet ne fx3s) 342511 Srercary (sta) s4afou Genet Ottce (sha) 3500 ‘eles Suny umse. Foe (os) 30099 Paul Stilwell ‘Technical Training Officer Customer Training Centre ROUS-ROYCE ple PO Box31, Derby DEZ ‘Telephone: 0382 13021 Ext 372, Telex: 37645, Fax: 0352 521584 Lucas Hugh C. Grigg asc ancse sat Arsh ato gn ‘Ween FonertanSysems ‘© division of Lucas Rotemotive tid (avon as ern {ono 9 79° Tel 061 7433101 Telex. 27887-Fax 0B) 1494181 RICARDO. Colin R Mears Paneipet Engnoar Ricardo Consulting Engineers Ltd (age Woks Srovenor by Seo. West Gzer ENIDETG Eagione| Tor0o73 e561 felon 80988 For 298 4os98 Ministry of Defence (PE) lan Harris. mse CEng (i) 53 Aviation Fuels and Oils Room 246 St Giles Court 13St Giles igh Street ‘Tol- 071-632-6411 London, WC2H8LD axe 071-632-6256 ® STANHOPE-SETA Mike Sherratt DIRECTOR OF RESEARCHXAVIER MONTAGNE Luiz. Fornande Monteiro SoS, ‘Assitnt Caroorane ec a Sboce Saoet ‘Secrutarst Conor ® INSTITUT FRANGAIS OU PETROLE. RENAULT BFS Rei com Force Direction des Etudes gece, Pram ‘soqnaraeatia Cen Teenrig Renal ~ Alle Conuel = $1810 Lard: PES ycge0 hosts ne ‘Tat standard ‘931 69 7000 tel vee GAC G8 ET 1.84 er “Telex 896300 OSLKe = Tettcopeur 38 (1) 6927.70.42 ‘MICHEL DERRIEN SEES ee nwa, ake ——_—-—- z ‘Telephone: 7319) 48 193789 / elfantar france [f / Si acu Herr ‘snee vy pepe Bemard LERY enspm elf antar france ff Adjolnt au Directeur ‘Chargé des Rolaons femotionales FORMATION Lue CHATIN CChof du Dépertoment Brute ot Produits Dicecion du Ratinage cole Naorale Supriure tours {eldphono 39 (4740271 {Wien oi 16400 fan 3 (1)47 43546 elf antar france MARC VALLEUR Donkin Airitio Bernard Sauvage Directeur Qualaé et Organisation AND FORMATION SYST, “TOUR TECIAMIP- LA DEFENSE 6 CEDEX 25. #290 PARIS LA DEFENSE - FRANCE ‘SUITEHGOARD 4 2149 792191 CIRECT LINE 4 30) 782100, PH ree rch A cine) Fak 4 101 a) HD. a {etpnose soy af a0 8.68 eter ela 615 400 F tlecope 99 (1) 47 44 4818PRODUCT PERFORMANCE TEST CENTAE Potor P. Scott, B.Eng Protest Padarmeree Ten Cente Quan XI3 GA Egan @LUBRIZOL DR. ROBIN G. M. LANDELLS Technical Manager uot Products Group - Europe LUBAZOL ITTERNATIONAL LAGORATORES 'HAZELIOOD. PO BOX 88, BELPER DERBY OES 10N, UK TELEPHONE: 0932:662211, TELEX 37448 FAX 0932-862003 ARCO Chemical Europe, ine [ARCO Chemis! Houte rs rc ance cnt a RAT sa eer care terre Sem es ranean ae Ww ‘Subsidiary of ARCO Chemical Company PARAMINS Gerry |. Brown FORE novATON &AmUCAONS. EXXON CHEMICAL LIMITED. 0, Bos No Aaron Ooch O€19 600 Erg ‘Wn 238) 498703 we one 795 99729 ee O23) ALO? zis) sasonyoasao) tw 26963 Cato Penh aon SW [ETHYL ASIA PaciFiC COMPANY 1220 BERRY STAEET NORTH SYDNEY NSW 2060 ‘TEL 02) 925 1588 FAX-|02) 9593783 Private: (02) 387 951 WAYNE MORRIS ‘Account Manger ETHYL ESC TE ASSOCIATED ooTEL COMPANY LnTED BERKELEY SOUAmE:LONCON WIR BOT NIKOLAS WILDE ‘Area Manager Letin America and The Caribbean ‘rns ocast 2332 Tes 0867oot OBE Bujddous win 2127 wop8urgy| ‘*say0yes0qe] Y>1e9say 0853] autodmata Ansnpuy 2010) cost ‘OebI-O6E) Jose. HONMTose!-08zt Ouieg dinba wel Stet-cezt HONNVOLOHa OFSt-06z1 HONNT SHOUDDFG G| oezt c JOObL "334300 00-0801 Fas4100 | ‘SHOPURT ¥ Lonssnquio pue Ansiw945 ng { 0001-0060] | seugeg Konig ose9 oo 0060-0880) 10060 60 Rid G08 WOES 27 CIM 3 and SENOW suouidojanog YEW scd5—weusHeW71a ODD puv syuauodwo> Suipusia “Autend) ‘suone>yoods -ssquiouoag pue AZojouypo} auyose) ant, si “DnuD, £661 J940P0 67- A/S POD SHICN.LS ADVAN GNV Wha IOULad JO HDATIOO AHL PoeTHE COLLEGE OF PETROLEUM AND ENERGY STUDIES OXFORD Course Director TED MARSHALL is an independent consultant on automotive fuel quality. He joined BP Research in 1959 after a number of years working as an engineer in the motor industry. He then spent 20 years in various positions within BP, working on all aspects of gasoline and diesel fuel quality. In 1979 he was elected to a Fellowship at Cambridge University where he spent the next two years carrying out fundamental research into lean burn gasoline engines. He returned to BP where he was responsible for initiating and setting up fundamental combustion research facilities for both gasoline and diesel engines. In recent years he has again specialised in all aspects of fuel quality serving on various CORC, BTC, CEC and CONCAWE committees and representing BP in areas as diverse as the UK Stirling Engine Consortium, Electric Vehicle Development Group and the Universities Internal Combustion Engine Group. He is author and co-author of a number of papers on both gasoline and diesel fuel quality. Course Lecturers W EDWARD BETTS, BSc, has over 30 years experience of the energy industry, the last 22 years being with Esso working on environmental, combustion and product quality issues. His activities in BTC, and internationally with CEC and CONCAWE, include Groups dealing with driveability, reference fuels, emissions, ORI and knock damage. He is currently involved with emissions and product quality research on automotive fuels. ALF CLUER, BSc, FRSC, FiChemE, FinstPet, is an independent consultant on refining. Previously he was Group Refineries Manager, Burmah-Castrol, and in charge of the Burmah-Castrol manufacturing division. He has many years experience in atmospheric and vacuum distillation, FCC, thermal cracking, catalytic reforming of naphtha, and isomerization of light fractions. He has lectured on refining for The College since its inception in 1983. ROGER HUTCHESON joined Shell in 1961. His BSc in engineering was later sponsored by Shell. He spent several years in lubricants marketing before specializing in automotive fuels in 1978. Since July 1990 he has been seconded to CONCAWE as technical coordinator with special responsibility for automotive emissions. ROBIN G M LANDELLS, BSc, PhD, is currently technical manager, Fuel Products Group, Europe within Lubrizol Ltd. After graduating in chemistry from Edinburgh University he gained his PhD in 1977. This was followed by five years petrochemical research at BP Chemicals. In 1982 he moved to Orobis Ltd where he became involved in the development of lubricant formulations. He subsequently became Product Manager, Fuel Additives within BP Chemicals (Additives) Ltd. In late 1986 he joined the Fuel Products Group of Lubrizol and is currently responsible for all fuel technical activities within Europe. Robin Landells is co- author of Precombustion Gasoline Additives, Chapter One of Gasoline and Diesel Fuel Additives published by John Wiley and Sons Ltd.COLIN MEARS is currently employed as Principal Engineer with Ricardo Consulting Engineers ltd. He acts as consultant to engine manufacturers, component suppliers and oil companies worldwide on all aspects of the design, development and performance of gasoline engines. Previous experience includes 20 years of engine design and development with passenger car manufacturers in the UK and overseas. KRISTINE OLAFSEN, MSc, graduated form the University of Twente in the Netherlands in 1991 with a degree in chemical engineering. She is currently employed as a Product Specialist in the Oxygenated Fuels Department of ARCO Chemical Europe, Inc ( ACEI), the European arm of ARCO Chemical, a subsidiary of Atlantic Richfield and the world’s largest producer of oxygenated gasoline components. KEITH OWEN, BSc, CChem, MRSC, studied chemistry at London University. He has spent some 40 years in industry, of which nearly 30 were with Esso where he worked in the UK, Germany and the USA on topics concerned with refining, the environment, research and product quality. In recent years he specialized in gasoline quality topics and has been active on many BTC, CEC and other industry committees concerned with fuel quality and performance. He is the author of the Motor Gasoline section of the Institute of Petroleum’s manual on Modern Petroleum Technology and is the editor of a multi-author book on Gasoline and Diesel Fuel Additives published in 1989. He is also co- author, together with Trevor Coley, of the Automotive Fuels Handbook which was commissioned by the SAE and published in 1990. KAILASH C SALOOJA, PhD, DIC, DSc is now an independent consultant on fuel quality, combustion and environmental issues. He worked for ten years, at Shell Research Centre, on the mechanism of combustion processes and of the action of fuel additives. He then worked at Esso Research Centre, for over twenty years, on fuel quality requirements for different applications, effect on quality of changes in refining /blending and/or use of additives, development of combustion catalysts, and design of combustion systems for abatement of pollutant emissions. For several years he was a member of the Chemistry panel of International Flame Research Foundation, and of a NATO committee dealing with energy issues. His work has led to numerous publications and patents. G R SEARLE, LRSC is Section Head, Petroleum in the Fuel Technology Group at the Associated Octel Engine Laboratory. He has worked for more than 25 years on Projects associated with the use and performance of Fuel Additives and the production of transport fuels. For the past five years he has been responsible for managing technical projects in support of Octel’s customers, providing advice and assistance on the efficient production of gasolines and diesel fuels. CHRIS D SPINK is currently with Shell Research Ltd, Thornton Research Centre, Chester. He is a Senior Scientist engaged in gasoline R & D and is active in additive development, studies of base fuel performance and development of test procedures. He has been employed by Shell for eighteen years, all of that time in Research, but has worked at laboratories in Holland and the USA as well as in England. Before entering the transportation fuels area, he researched varied topics in continuous combustion directed at the safe, environmentally acceptable and efficient combustion of industrial fuels.CONTENTS:THE COLLEGE OF PETROLEUM AND ENERGY STUDIES OXFORD Gasoline Technology and Economics — Specifications, Quality, Blending Components and Market Developments Course Code RF5 Table of Contents Title Section Fuel Chemistry and Combustion ¢ Salooja Matching the Octane Requirements of Vehicles with Fuel Octane Quality w £ Betts. Gasoline Volatility w £ Betts... Environmental Concems —F ¢ Hutcheson Introduction to Gasoline Specifications ££ Marshall...... Gasoline Manufacture 4 Ciuer.. Oxygenated Gasoline Components and Reformulated Gasoline Olatsen.... Meeting Octane Quality @ seare Gasoline Stability owen. Gasoline Blending _k Ower.... Modern Multifunctional Gasoline Additives — Ensuring Gasoline Consumer Satisfaction FR Landolls.... Gasoline Additives —Non-Surfactants _¢ Spink. Motor Industry View of Gasoline Quality ¢ Mears. Altemative Fuels £1 Marshall... Glossary Bibliography Gasoline Blending Study...SECTIONISection 1 Fuel Chemistry and CombustionFUEL CHEMISTRY AND COMBUSTION Dr K C Salooja, Consuttant A knowledge of the structural chemistry of fuels, and of the manner of their combustion, is essential for understanding the acute sensitivity of gasoline engines to fuel quality. Boilers and furnaces, in contrast to gasoline engines, are insensitive to fuel quality - they can satisfactorily operate on any refined or unrefined gaseous or liquid fuel, or even on coal and logs. The most important quality parameter for gasolines is their octane quality. Fuel volatility is also important. But even within the acceptable volatility range, a gasoline engine will satisfactorily run only ona limited selection of fuels ~on those alone which have adequate octane quality. Octane quality is highly dependent on molecular structure of hydrocarbons. Other characteristics, including volatility, are also dependent on molecular structure; but these not quite to the extent that octane quality is. 1 Principal Structural Categories of Hydrocarbons They are: * Straight-chain paraffins 9, n-heptane (CHo-CHe-CHe-CHe-CHe-CHs.CHa * Branched-chain paraffins 09, 2.24rimatyl pentane (¢o-oetane) 7 cr Sb bins Hs ¢ Naphthenes (Cycloparaffins) 9, cydehexaneFuel Chemistry and Combustion ‘¢ Olefins-Thesearehydrocarbons with one ormoreunsaturated links in the molecule. As far as their overall structure, they could belong to any of the above mentioned categories. (0, t-hoptane (CHeaCH-CHe-CHeCHe-CHeCHs 22.4-timathy!2-pentene He Hy orf Bub Sis Ho ‘ety oytohexene gs cu Heese weol_be Che ‘¢ Aromatics ~Theseare ring structures containing alternate singleand double bonds. 9, benzene cH He H cH ‘-mathy! bonzens (toluene)Fuel Chemistry and Combustion 14-imotylbenzono (payne) gh é He SCH Oe ¥ ot Of these principal types, straight-chain paraffins have the lowest octane quality, and aromatics the highest. The octane quality of branched-chain hydrocarbons is increased by an increase in branching. Among naphthenes five membered ring compounds have a higher octane quality than six membered compounds, Presence of unsaturation in the molecule (olefins) has a complex effect: it increases ‘Research’ octane number,as shownin thenext section, but reduces ‘Motor’ octanenumber determined under more severe conditions.Fuel Chemistry and Combustion 2 Effect of Fuel Molecular Structure 2.1 Examples amongst hydrocarbons containing 6 carbon atoms Type ‘Sraight-chain on Engine Octane Quality Octane number fame Structure roxane: Cla-CHe-CHe-CHe-CHe CHa 248 Naphnene lotin (etraightehain paratin) ‘tet (branchedchain parattin) tia (naphineno} amabyipetan: CH EHCHCHchy 734 o smebyiponane: CHcheSicrechs 745 sseumy ome otro caammprnne orBtBon ww 918 ce hep erdobonae =) 0 Ha oh g ¥ meyeytponiane: we ona on benzene: we >>100.0 " % tonane: CHesCH-CKe-CHecHeoy 784 r ‘2-methyl-pentene: cre Bhe oreo 942 cH arcctonoes wo (Research) Bolling point °C 69 an R 63Fuel Chemistry and Combustion 2.2 Examples amongst hydrocarbons containing 7 carbon atoms Octane number Bolling Type Name ‘Structure (Research) point ‘C srptidn nomi Oeciecnececnesteo oo ma cate a Ear ante: cirftorowcton ese sonia ts Se eyieam: oesieBtomcicoe so sons a ceamtriomam owPbeoeos ek — " SSE csamtrowans ow BtBtoieat 81 siete Cou SEE amonrome: Stor Blon ern einin " SE casio oof met we f sen — aoe ug Soy Hee! He wep taiees anaes wep Spe ww He! He be g ‘Naphthene ethyl cyclopentane: He or? 103 Hee! He ‘Aromatic methyioenzene iovene); HC 7 1200 m % oat Sinan some: hateomoeoeon Hs oat os Sescan somntninme cones faa ow Ps ‘Olefin ‘-methyicyciohos 7 e981 110° tye Hee, +H a “eR SeFuel Chemistry and Combustion 23 Examples amongst hydrocarbons containing 8 carbon atoms Tyre ‘Staight-chain paratin Branches-chain paratin Naphthane Naphthene ‘aromatic Aromatic Olefin (eraight chain paratfin) (branched-chain paratfin) peat vee ou mana rom Ob-esteorcecresteot 7 szemamremne fede on (iso-octane) Ha ‘Hs fe g permis ee He He wep ‘seepnitene — 46 ws wel oe CHe i : nen tam aoe % CHs g Hs te 1.2-dimethylbenzene He na oe 1 i ee Saas EEL b ‘ootene: CHzeCH-CH2-CHe-CHe-CHe-CHeCHs = 28.7, fs 2.2.4-trimethyl-2-pentene: CI a Ha 105 Bolling point’ 130 "9 196 146 139 198 122 102Fuel Chemistry and Combustion 3 ‘The Nature of Combustion Process and Why Systems Differ in Their Sensitivity to Fuel Quality ‘The overall combustion process is the same whatever the combustion system. It involves a reaction between fuel molecules and oxygen to convert fuel hydrogen into water and carbon into carbon dioxide. This reaction is accompanied by release of heat, which constitutes the primary power source. The overall process isindeed simpleand fast whenitiscarried out within the flame environment, that is in a continuously burning flame. Fresh fuel and air, fed to the flame in the requisite proportion and at the requisite rate, are rapidly converted to water and carbon dioxide. When the combustion process is not continuous, as in internal combustion engines - gasoline engines or diesel engines~complications do arise. Taking the case of a gasoline engine, as every fresh fuel-air charge is ignited by the discharge of a spark, the flame initiated by the spark advances into the combustible mixture /Ahead of the flame front, the yet unconsumed mixtureis subjected to ever increasing temperature and pressure from the energy already generated, and this causes preflame reactions to occur. These reactions are neither identical to, nor as fastas, those in flames. However, when intense enough, they docause ignition and start up another flame kernel. This additional combustion, occurring simultaneous with that initiated by the spark, causes an excessive rate of energy release - and results in engine knock. While different hydrocarbons have very similar burning characteristics in a flame, they do differ widely in their propensity to undergo preflame reactions. The ease with which a fuel molecule can withstand an attack by oxygen differs from hydrocarbon to hydrocarbon. The ease of breakdown of the attacked molecule into fragments, and the nature of the fragments, also differ. The fragments, in turn, can widely differ in their pattern of oxidative degradation. This makes the preflame process highly dependent on molecular structure,and hence renders the internal combustion engine so sensitive to fuel quality. For gasoline engines the most desirable fuels are indeed those with a low propensity for preflame reaction, s0 that the combustible mixture ahead of the flame front does not self-ignite, but gets consumed by the advancing flame front. A diesel engine, like a gasoline engine, is also highly sensitive to fuel quality. However, since here there is no spark discharge to initiate combustion, and the onset of ignition is entirely dependent on self-ignition of the fuel, fuels with a high propensity for preflame reaction are the ones most desirable. Thus it is that the fuel constituents whichare least desirable for gasoline engines are the ones most desirable for diesel engines, and vice versa.Fuel Chemistry and Combustion 4 Octane Quality — Test Engine, Test Conditions and Their Relevance to Vehicle Performance Octane quality is assessed in a specially designed single cylinder unit — the CFR (Cooperative Fuel Research) engine. This engine was produced asa result of the joint efforts of the Society of Automotive Engineers and the American Petroleum Institute. Compression ratio of the engine can be changed at will, and the critical value for a fuel for the onset of knock, constitutes the primary arbiter of its octane quality. The auxiliary equipment of the engine includes a pickup unit to detect pressure impulses, an electronic amplifier, and a meter to record knock intensity. Inpractice the CFR engineis operated with the test fuel undera standai set of conditions, and the compression ratiois adjusted to givea standard level of knock intensity. This knock intensity is then bracketed by two blends of reference fuels made up from n-heptane (octane quality 0) and iso-octane (octane quality 100). The blends chosen are such that one of them knocks a little more than the test fuel, and the other a little less. Octane quality of the test fuel is then determined by interpolation between the reference fuel readings to a composition whose performance would just match that of the test sample. The test conditions adopted at first were those that represented the best judgment as to what was required to make the laboratory results match those in vehicles on the road. However, as technological developments produced engines and vehicles capable of more severe operation — higher speeds and heavier loading - road results showed lower octane values than those registered by the CFR engine. A new set of test conditions, far more severe than before, were then adopted. Both methods have continued in use ever since, because together they predict a gasoline’s road performance better than either alone. ‘The less severe method has become known as the ‘Research’ method, and the more severe the ‘Motor’ method. Test Conditions for CFR Octane Rating ‘Research’ ‘Motor’ Ratings Ratings Engine speed, rpm 600 900 intake air temperature Specified, but 100°F (38°C) depends on barometric pressure Intake mixture temperature — Not specified ‘300°F (149°C) ‘Coolant temperature 100 100°F (38°C) Spark advance, bide 13 automatic’ “Changes automatically with compression ratio; basic setting is 26 before top dead centre (bide) at 5 : 1 compression ratio.Fuel Chemistry and Combustion The primary reference fuels for both ratings, up to 100, are n-heptane and iso-octane. For ratings above 100, up to 120, mixtures of iso-octane and tetraethy! lead (TEL) are used. The relationship between octane values above 100 and the amounts of TEL in iso-octane are shown in Figure 1 ‘The Research ratings correlate best with low-speed, relatively mild driving conditions, whereas the Motor ratings relate to high-speed, high severity conditions. Obviously, vehicles on the toad operate, most of the time, at a severity somewhere between the two levels. Indeed in some countries, notably North America, gasolines are specified by an AntiknockIndex whichis theaverageof RONand MON ofthe fuel ‘That is: Antiknock index = ¥ (RON + MON) InEurope RON and MON are usually specified Separately although for marketing and identification purposes only RON is qu: wmpore je Most gasolines have a higher RON than MON, and the difference Por apkas between the two ratingsis referred toas the’sensitivity’ of the fuel. Large cae differences in sensitivity are not uncommon. Examples of such ae blencling- differencesareshown in Figure2. Between fuels of similar RON, a higher sensitivity signifies a greater proneness to knocking as engine operating SENSI BILIDADE conditions become more severe. I the diffe sf hydrocarbor ole eae t is interesting to note that among different categories of hydrocarbons ri ead: olefins have the highest sensitivity, and branched-chain paraffins the POVORMaS Tar fea lowest. Fae 5 Air-to-Fuel Ratio — Significance and Effect on Engine Power, Thermal Effici and Exhaust Emissions 5.1 Significance of Air-to-Fuel Ratio ‘Theoretically, a fuel should be burned with a chemically correct amount of air ~ no more, no less ~ to completely convert fuel carbon to carbon dioxide and fuel hydrogen to water. Insufficient air would prevent complete combustion of the fuel. Products of incomplete combustion will be formed and some of the fuel may remain totally unburnt. The full energy content of the fuel will not be released and utilized. Too much air, on the other hand (if not far too excessive even to support a flame), will reduce the intensity of combustion and soak up some of the heat. ‘This would prevent the attainment of optimum temperature necessary for maximum thermal efficiency.Fuel Chemistry and Combustion The chemically correct air-to-fuel ratio, called the stoichiometric ratio, is not the same for all components of a gasoline. It depends on the number of carbon and hydrogen atoms in the molecule. For instance, for iso-octane it is 15.12. This is calculated as follows: CoH + 12%02 + 8CO, + 9H,O 114 400 352 162 (1724, air) * aittuel = 1724444 = 15.12 For cyclohexane, calculations below show it to be 14.78. CoHi2 + 9O2 + 6CO, + 6HO 84 288 264 108 (1241.28, air) caitftuel = 122% = 14.78 And for benzene, calculations show the stoichiometric ratio to be 13.26 CcHe + 7%O2 ~» 6CO, + 3H0 78 240 264 54 (1034.4, air) + aitftuel = '9444g = 13.26 Gasolines are composed of all manner of hydrocarbons, and their stoichiometric ratio is usually around 14.5, 5.2 Effect of Air-to-Fuel Ratlo on Engine Power and Thermat Efficiency Although one might expect the stoichiometric fuel-air mixture to be the ideal one for optimum engine performance, tests have established that maximum power is obtained with roughly 10 per cent fuel rich mixture, and maximum fuel economy with roughly 10 per cent fuel lean mixture igure 4). ‘That maximum power is achieved not ‘by thestoichiometric mixture, but fone somewhat richer in fuel, is due to several factors. The more significant of these are maldistribution of the charge to individual cylinders, and quenching of a part of the flame by cooled metal surfaces of the combustion chamber (head and cylinders cooled by water, and pistons by oil). There is also some energy loss through high temperature dissociation of some of the products. Itis to make up for such losses that mixtures somewhat fuel rich are needed for maximum power. Maximum fuel economy, on the other hand, is achieved with mixtures containing some excess air to ensure complete combustion of the fuel.Fuel Chemistry and Combustion Engines, of course, are designed to change air-to-fuel ratio according to operational requirements, and for excess power requirement, especially when the engine is particularly cold, chokes are provided to restrict air and hence increase the proportion of fuel in the mixture. 5.3 Effect of Alr-to-Fuel Ratio on Exhaust Emissions ‘The major components of exhaust gas, as expected, are nitrogen, carbon dioxide and water vapour. Whenever engineis operating fuel-rich italso juces carbon monoxide, some unburnt hydrocarbons and hydrocarbon related products of partial combustion, such as low molecular weight olefins, aldehydes and ketones. Another product that is formed, and this even when combustion is carried out under stoichiometric conditions, is a mixture of oxides of nitrogen (nitric oxide and nitrogen dioxide). These nitrogen oxides can form by the combustion of nitrogenous compounds which may be present in trace amounts in the fuel, but quite apart from this, some are formed by direct reaction between atmospheric nitrogen and oxygen. This reaction is favoured by high flame temperature and indeed they are encountered in their highest concentration when the combustion temperature in engines is at its highest. Typical results on the effect of air-to-fuel ratio on carbon monoxide, unburned hydrocarbons and oxides of nitrogen in the exhaust gas are shown in Figure 5. ‘The emission of these products from the engine is undesirable. Carbon monoxide and unburned hydrocarbons constitute wasted fuel. Moreover, products of partial combustion can be highly malodorous, and they along with the rest of unburned fuel, in conjunction with nitrogen oxides, can lead to the formation of unpleasant smog, especially under the influence of bright sunshine under static atmospheric conditions. Much effort has been expended over the past 20-30 years, notably in the USA, to prevent the discharge of these products into the atmosphere. Formation of nitrogen oxides has been curbed through reduction of peak flame temperature -not without considerablesacrifice in combustion efficiency - by recirculating a part of the exhaust gas through the engine, and in some cases by even running engines slightly fuel-rich. The unburned and partially burned hydrocarbons are destroyed by passing the exhaust gas througha catalyticconverter. since none of the catalysts developed has been found immune from the poisonous effect of lead compounds formed from antiknock lead additives, the use of such additives has had to be abandoned. More recently theuse oflead antiknocks has been greatly curtailed,even where thereis hardly any risk of photochemical smog and carshave no catalytic converters, on the realization of some health hazards associated with the discharged products. "Fuel Chemistry and Combustion 6 Combustion Chamber Deposits, Octane Requirement Increase, Preignition Deposits are invariably formed in combustion chambers. They arise, in part, from the fuel, whenever the cylinders operate on fuel-rich mixtures. Some smoke (solid carbonaceous matter) is formed besides the volatile products of incomplete combustion. Whilst most of the solid product is exhausted, a part is deposited on the chamber surfaces. In part deposits arise from the thermal oxidative degradation of the lubricating oil that creeps past the piston rings. Deposits contain metallic compounds besides carbonaceous material. ‘The metallic part is derived from organo-metallic additives present in lubricating oils. It can also arise, partly, from fuel if it contains lead antiknock additives. Deposit formation isaffected by driving conditions. More are formed by city type driving, ie low speed, stop-start operation, than during extended high-speed operation. Their mass does not go on increasing indefinitely, but reaches an equilibrium level as some of the deposit continually breaks up and is exhausted following flaking due to thermal and physical stresses. Deposits can lead to adverse effects as discussed below. 6.1 Octane Requirement increase Deposits, because of their poor thermal conductivity compared to clean metal, slow down the cooling of the combustion chamber surfaces. They also reduce, slightly though significantly, the volume of the combustion chamber, thereby effectively increasing the compression ratio of the engine. Both these factors raise combustion chamber temperature and promote knocking tendency. Asa result a fuel of higher octane rating is now required to give knock-free performance. The octane requirement increase can rise as high as 8 octane numbers! 62 — Preignition Higher temperature within cylinders, because of deposits, raise the surface temperature of the chamber. A further considerable increase in temperature of some parts of deposits can occur with the catalytically active metal derived constituents promoting the combustion of the carbonaceous material. Asa result bts of deposit can begin to glow,and ignite the charge even before spark discharge. This leads to even higher temperature and more persistent uncontrolled combustion. This phenomenon is called ‘preignition’, The root cause of preignition, as of octane requirement increase, is , § gi iO = 2: ’ e 3 2 ’ & a. ’ - 3 for 9 yewey, ~ 3 i uejoyjo jeuueyf ~ ~ _ _ <>< on AONA1DIdSAa IWAYAHL GNV YaMOd NO OllWY TaNS-OL-YlV AO JONANTANIpy ainbiy O1Nes [ONJ-OF-dIY es 24 oo oo cf @ Ww oOo 6 2 ‘uoiGas | eee! : T Tr H o ooz} eusiN ~~ ~ Q » OObFE oor 3. ooz{z 009 : o06+e oog oor dy ooo oosjs g Zz 8 ooz 009 49 3 8 " i oor gine 4g a 0091 | \ {8 8 s \ 2 = 008h 00%, 464 + 9002 * or XON GNV SNOSYVOOXGAH GANXNENN OS NO OllVY TaNS-OL-YIV 4O LOAAAA© Jequunu aueyO = Jaquinu auejeg 6h SANIDNA 14SAId NI SONVWHOAYAd GOOD HLIM GNOdSaYdyxOO G330NI S30 SANIDN3 ANIIOSV9S NI SONVIWNHOAYAd 14N4 HOOdSECTIONSection 2 Matching the Octane Requirements of Vehicles with Fuel Octane QualityMATCHING THE OCTANE REQUIREMENTS OF VEHICLES WITH FUEL OCTANE QUALITY WE Betts, Esso Itisnecessary that the octane quality of fuel marketed in a specificregion matches that of the car population in that area. The consequences of using a lower octane quality fuel than a vehicle requires can bea minor irritation because of the engine noise that occurs - or it can lead to catastrophic engine damage. There are a number of engine factors that are important in considering knock. Compression ratio has a very important effect, and an increase of one number will raise octane requirement by some 4 to 6 numbers. It is, desirable for vehicle manufacturers to use as high a compression ratio as possible since this improves engine efficiency and so can give fuel economy and power benefits. Ignition timing also affects octane requirement — the further it is advanced, the higher the octane requirement of the vehicle. Two degrees of crank angle will change the Tequirement of an engine by about one number, but power / economy are adversely affected by ignition retard. As engine speed increases, so octane requirement falls and as the load onan engine increases; this will, in tum, increase the octane requirement. Mixture charge temperature and air/fuel ratio also influence octane requirement. Most of the above factors relate to engine design but there are a number of additional influences which are important. Ambient conditions of temperature and humidity can have a significant effect and so can atmospheric pressure — which is related to altitude. On average octane requirements increase by 0.1 O.N. per degree celsius increase in temperature and decrease by about 0.25 ON. per g water / kg dry air increase. Altitude effects are very variable but an increase in altitude of 300m can reduce octane requirements by up to 1.5 numbers. These external influences mean that it is possible to market different octane qualities at different times of the year and in different geographical locations where the vehicle population is essentially the same. Ithasalready been stated that octane requirements depend upon engine speed and load and from this it is clear that driving mode is important. At low speed, Research Octane Number (RON) correlates best with octane requirement and as speed and load increase, so Motor Octane Number (MON) becomes more and more important. During full throttle acceleration a mixture of RON and MON correlate best and at high constant speed when cruising at full throttle; MON is by far the most important octane parameter. Low speed knock is most frequently heard during hard accelerationsand although it is of concer to customers, it does little harm since itis only transient in nature and although combustion chamber temperatures do increase, they donot stay ata high level for very long. On the other hand, knockat high constant speed can be very damaging indeed. Thisis partly because it cannot usually be heard over the wind, engine and road noise so that the driver may have no inkling of what is happening until it isMatching the Octane Requirements of Vehicles with Fuel Octane Quality too late. Continuous knock of this type will frequently damage the cylinder head gasket and will erode the top of the piston crown on the side opposite the spark plug i.e, in the end gas area. In severe cases the top edge of the piston and the top piston ring will break up. Combustion chamber deposits increase octane requirement until the deposits stabilize, so that the octane requirement of a new car may well be some 4 to 6 numbers lower than the same vehicle after several thousand miles have been accumulated. This increase in octane requirement with miles is known as ORI. Stabilization of the octane requirement occurs more rapidly with leaded gasolines than with unleaded, presumably because thelead catalysesthe burning of carbon deposits and the scavenging of lead as the halide or oxyhalide also removes some of the other deposits at the same time. The deposits themselves consist of carbonaceous materials, lead compounds (when running on leaded gasoline), and metal compounds arising from lube oil components. They increase octane requirements by increasing combustion chamber temperature because of the thermal barrier they present as well as by increasing compression ratio. Severe high speed driving can reduce octane requirement because the carbonaceous deposits can be burt off and similarly low speed city driving can increase octane requirements. Thus ORI depends very muich on the type of driving that is carried out prior to its measurement. Measurement of the octane requirement of a vehicle is usually carried out ona chassis dynamometer since it is easier to get repeatable results, weather changes have less influence on the results and in general it is muuch cheaper. However, care must be taken that the stabilized engine temperatures are the same as those achieved on the road and that the loading characteristics of the chassis dynamometer are such that similar acceleration curves are obtained to those on the road. The tests themselves involve full throttle and part throttle acceleration from low and medium speeds (in Europe, 1500 rpm and 80 kph are often used). In addition constant speed full throttle tests are also carried out. A number of fuel series are used which are generally selected to be representative of the extremes of quality that can be found in the market. Primary reference fuels (PRFs — blends of iso-octane and n-heptane) are also frequently used in order to provide a constant basis and reference point. Each of the fuel series consists of a high RON anda low RON fuel which are blended together in one octane number increments, The highest octane number fuel in each series that gives trace knock is the requirement of the vehicle on that type of fuel under the specified test conditions used. The maximum octane number of the vehicle is usually sought — whether it occurs at high constant speed or under full or part throttle accelerating conditions. Test data of this type are usually obtained cooperatively by a group of oil companies using standard fuels and test conditions and the raw data are shared. The analysis of the data can be very complex but they are often presented in the form of satisfaction curves for a given car populationso that itis possible to read off the percentage of carssatisfied bya given octane number for different types of fuel.‘Matching the Octane Requirements of Vehicles with Fue! Octane Quality ‘The data obtained from the tests outlined above relate to octane levels that will satisfy cars rather than customers and in order to be able to predict customer satisfaction it is necessary to apply a correction. Many tests have been carried out to establish a relationship between customer and technical rater assessments of a vehicle’s octane requirement. One such test showed that customers are on average 5 octane numbers less severe than technical raters although some customers are very perceptive indeed and drive in such a way as to be more severe than the standard tests - while other customers never notice knock at all. A complication is the fitting of knock sensors to some vehicles ~ usually ones that have high performance engines. These knock sensors are usually attached to the cylinder head and when they detect frequencies inthe knock range, they activate a mechanism which reduces the octane requirement of the vehicle. This is usually done by retarding the ignition although other methods are available. The retard is gradually relaxed back to the normal ignition setting since power and fuel economy are sacrificed if the engine is not operating at the optimum timing. The customer may notice if he is using a low octane fuel by the loss in performance of his vehicle rather than by the noise of knock. In summary, it can be said that the fuel octane quality should match as far as possible the octane requirements of the vehicle population for which it is intended. It is impossible to satisfy every car because some vehicles are maladjusted or the manufacturing tolerances in terms of compression ratio etcall conspire to give a high requirement or for some other reason. 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