Motor Fuels Technology

Table of Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i 1 Gasoline and Driving Performance . . . . . . . . . . . . . 1 Introduction Volatility Vapor Pressure Distillation Prole Vapor-Liquid Ratio Vapor Lock Index Driveability Index Volatility Specications Antiknock Performance Octane Number Requirement Power Fuel Economy Factors Affecting Fuel Economy Fuel Economy Road Test Other Performance Factors 2 Gasoline and Air Quality . . . . . . . . . . . . . . . . . . . . 13 Introduction Progress in the U.S. Legislation Administration/Regulation Air Quality Standards Air Polluants Origin of Vehicle Emissions European Union Japan 3 Gasoline Rening and Testing . . . . . . . . . . . . . . . . 27 Introduction Composition About Hydrocarbons Rening Raw Material Processes The Modern Renery Process Changes Required by Air Pollution Regulations Blending Contamination and Adulteration Gasoline Additives Specications Vehicle Emissions: Limits Inspection and Maintenance Vehicle Emissions: Gasoline Effects Reformulated Gasolines (RFGs) Test Methods Use
4 Oxygenated Gasoline . . . . . . . . . . . . . . . . . . . . . . 45 Introduction Chemistry Sources Specications Performance Issues 5 Gasoline Engines and Selected Systems . . . . . . . . . 53 Introduction Conventional Engine Technology Combustion Cycle Engine Structure Air System Intake Air Pressurizing Positive Crankcase Ventilation Fuel System Carburetors Injectors Storage Exhaust System Catalytic Converter Exhaust Gas Recirculation Control Systems Fuel Control Spark Control On-board Diagnostics (OBD) Advanced Engine Technology Conventional Engine Modications Alternative Engine Technology Hybrid Gasoline-Electric Fuel Cell Electric 6 Gasoline Vehicles Deposit Control . . . . . . . . . . . . 67 Introduction Engine Deposits and Performance Historical Development of Deposit Control Additives No Harm and Compatibility Deposits Affect Emissions Required Additive Use Aftermarket Additives Handling Gasoline Safely . . . . . . . . . . . . . . . . . . . 73 Questions and Answers . . . . . . . . . . . . . . . . . . . . . 77 Sources of More Information . . . . . . . . . . . . . . . . . 83 Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
Introduction
In May 1876, Nicolaus Otto built the rst practical four-stroke cycle internal combustion engine powered by a liquid fuel. He continued to develop his engine after 1876 and considered his work nished after his invention of the rst magneto ignition system for low-voltage ignition in 1884. The liquid fuel became known as gasoline in the United States (U.S.) and as petrol throughout much of the world. Although the U.S. petroleum industry was almost 50 years old when the rst Model T rolled off Henry Fords production line in 1908, gasoline and the automobile grew up together. The industry was born in August 1859 near Titusville, Pennsylvania, when a drilling effort nanced by Edwin Drake hit crude oil at a depth of 21 meters (70 feet). The major product in the early years wasnt gasoline; it was lamp oil, called coal oil or kerosene.1 People were reading more and wanted better light than that provided by candles and whale oil lamps. The natural gasoline in crude oil was a surplus by-product. Being too volatile to use in lamps, it was burned at the reneries, dumped or converted to a gaseous fuel for gas lights. The development of the electric light and the astonishing growth of the automobile in the rst decades of the 20th century turned the industrys focus from kerosene to gasoline. In 1911 gasoline sales exceeded sales of kerosene for the rst time. The simple engines in the rst cars would run on almost any liquid that burned. But as the demand for power increased and the engines became more sophisticated, gasoline was recognized as the right fuel for the spark-ignition internal combustion engine.2 Drivers obtain the performance they expect only when the characteristics of the fuel match the fuel requirements of the engine. As a result, the gasoline engine and its fuel matured as mutually dependent partners. An engine was not designed without considering the gasolines available in the market place. And gasoline was not made without considering the requirements of the engines in which it would be burned. The partnership became a triumvirate in the last decades of the 20th century as environmental considerations began to change both engine design and gasoline characteristics. This review collects information about all three members of the triumvirate in one place. As bets ChevronTexacos sponsorship, the major focus is on gasoline its performance, characteristics, rening and testing, and safe use. But signicant space is devoted to the operation of modern engines and to the impact of environmental regulation on both engines and fuels. Numerous cross-references emphasize how interconnected these topics are. We hope readers will nd the review a source of valuable and accurate information, whether they read it from cover to cover or zero in on an area of interest.
1 Both the names coal oil and kerosene were holdovers from the previous decades when lamp oil was distilled from coal. Kerosene, a corruption of the Greek words for wax and oil, was one American companys brand name for coal oil. 2 Petroleum Panorama, The Oil and Gas Journal, 57 (5), January 28, 1959. i
1 Gasoline and Driving Performance
Introduction
When most drivers think about gasoline, it is to remember to ll up and maybe to check the price. Because gasoline almost always performs well, drivers forget what a sophisticated product it is. More thought would reveal a demanding set of performance expectations: An engine that starts easily when cold, warms up rapidly, and runs smoothly under all conditions. An engine that delivers adequate power without knocking. A vehicle that provides good fuel economy and generates low emissions. Gasoline that does not add to engine deposits or contaminate or corrode the fuel system. Although proper vehicle design and maintenance are necessary, gasoline plays an important role in meeting these expectations. This chapter discusses how gasolines characteristics affect driving performance.
Volatility
Driveability describes how an engine starts, warms up and runs. It is the assessment of a vehicles response to the accelerator, relative to what the driver expects. Driveability problems include: hard starting, backring, rough idle, poor throttle response and stalling (at idle, under load or when decelerating). The key gasoline characteristic for good driveability is volatility the gasolines tendency to vaporize. Volatility is important because liquids and solids dont burn; only vapors burn. When a liquid appears to be burning, actually it is the invisible vapor above the surface that is burning. This rule holds true in the combustion chamber of an engine; gasoline must be vaporized before it can burn. In cold weather, gasoline is blended to vaporize easily. This allows an engine to start quickly and run smoothly until it is warm. In warm weather, gasoline is blended to vaporize less easily in the vehicle to prevent vapor lock or other hot-fuel handling problems and minimize evaporation, which contributes to air pollution. It is important to note that there is no single best volatility for gasoline. Volatility must be adjusted for the altitude and seasonal temperature of the location where the gasoline will be used. Later, this chapter will explain how gasoline specications address this requirement. Three properties are used to measure gasoline volatility in the U.S.: vapor pressure, distillation prole, and vapor-liquid ratio. A fourth property, driveability index, is calculated from the distillation prole. Instead of a vapor-liquid ratio, a Vapor Lock Index (VLI) is used outside the U.S. to control hot-fuel-handling problems.
Vapor Pressure For those materials that can exist as a vapor, some vapor is present even when the material is in its liquid or solid state. A materials vapor pressure is the pressure exerted by the vapor when the vapor is in equilibrium with the liquid or solid. The vapor pressure of gasoline is measured at a temperature of 38.8C (100F) and a pressure of one atmosphere, and expressed as kilopascals (kPa) or pounds per square inch (psi).
Vapor Pressure
Vapor pressure is the single most important property for cold-start and warm-up driveability. (Cold-start means that the engine is at ambient temperature, not that the ambient temperature is cold.) When the gasolines vapor pressure is low, the engine may have to be cranked a long time before it starts. When it is extremely low, the engine may not start at all. Engines with port fuel injection (see page 57 ) appear to start more readily with low vapor pressure fuel than carbureted engines. The vapor pressure varies with the season; the normal range is 48.2 kPa to 103 kPa (7.0 psi to 15 psi). Higher values of vapor pressure generally result in better cold-start performance, but lower values are better to prevent vapor lock and other hot-fuel handling problems.
Distillation Prole
Gasoline is a mixture of hundreds of hydrocarbons, many of which have different boiling points (see page 29). Thus gasoline boils or distills over a range of temperatures, unlike a pure compound water, for instance, that boils at a single temperature. A gasolines distillation prole or distillation curve is the set of increasing temperatures at which it evaporates for a xed series of increasing volume percentages 5, 10, 20, 30 percent, etc. under specic conditions (see page 41 ). (Alternatively, it may be the set of increasing evaporation volume percentages for a xed series of increasing temperatures.) Figure 1-1 shows the distillation proles of average conventional summer and winter gasolines. A distillation prole also is shown for a summer reformulated gasoline containing ethanol. Various ranges of a distillation prole have been correlated with specic aspects of gasoline performance.
Temperature C
Figure 1-1 Typical Distillation Proles of Summer and Winter Gasolines (ASTM D 86)
Temperature F 450 400 350
Front-end volatility is adjusted to provide: easy cold starting easy hot starting freedom from vapor lock low evaporation and running-loss emissions
200
160 300 250 200 80 150 100 50 0 0 10 20 30 40 50 60 70 80 90 100 40 120
Midrange volatility is adjusted to provide: rapid warm-up and smooth running good short-trip fuel economy good power and acceleration
0
protection against carburetor icing and hot stalling Tail-end volatility is adjusted to provide: good fuel economy after engine warm-up freedom from engine deposits minimal fuel dilution of crankcase oil minimal volatile organic compound (VOC) exhaust emissions (see page 19)
Percent Evaporated Regular-Grade Unleaded: 2003 United States Average Summer Conventional Gasoline Vapor Pressure: 7.6 psi Summer Ethanol Reformulated Gasoline Vapor Pressure: 7.0 psi Winter Conventional Gasoline Vapor Pressure: 13.1 psi
Chapter 1
Gasoline and Driving Performance
Figure 1-2 graphically illustrates these correlations. The temperature range is approximate; the exact range depends on the conditions that exist in the location where the vehicle is driven.
Figure 1-2 Correlation of Distillation Prole Ranges (ASTM D 86) with Gasoline Performance
Temperature F 500
Front End Midrange
Vapor-Liquid Ratio
The vapor locking tendency of a gasoline is inuenced both by the temperatures at the front end of its distillation prole and by its vapor pressure. But the property that correlates best with vapor lock and other hot-fuel handling problems (hard starting and no starting after a hot soak and poor throttle response) is the temperature at which the gasoline forms a vapor-liquid ratio of 20 (V/L = 20) the temperature at which it exists as 20 volumes of vapor in equilibrium with one volume of liquid at atmospheric pressure. The temperature for a V/L = 20 varies with the season; the normal range is 35C (95F) to 60C (140F). Higher values provide greater protection against vapor lock and hot-fuel handling problems. This correlation was developed for vehicles with suction-type fuel pumps and carburetors. Tests in later-model fuel-injected cars with pressurized fuel systems have shown a good correlation for hydrocarbon-only gasoline. A downward adjustment to the measured value is needed to predict the performance of ethanol blends.
Temperature C
Tail End
250
400
Carburetor Icing Hot Driveability and Vapor Lock Carburetor Evap. Losses E200 T50
T90 E300
150
300
100 200
50 100
Easy Cold Starting
Warmup and Cool Weather Driveability Short Trip Economy
0 80 100
20
Vapor Lock Index

Outside the U.S., Vapor Lock Index (VLI) is used to control vapor lock and other hot-fuel handling problems. VLI is a calculated index using vapor pressure in kPa and distillation prole percent evaporated at 70C (158F) fuel inspection data as follows:
VLI 10(VP) 7(E70)
40 60 Percent Evaporated
Vapor Lock Hot Fuel Handling Problems Vapor lock and hot fuel handling problems occur when excessive gasoline vapor accumulates somewhere in the fuel system fuel pump, fuel line, carburetor, or fuel injector and reduces or interrupts the fuel supply to the engine. When the fuel supply is reduced, the air-fuel
VLI varies with the season. The normal range is 800 to 1250. Lower values provide greater protec-
tion against vapor lock and hot-fuel handling problems.
Driveability Index
Although each range of the distillation prole is important, the gasoline represented by the entire prole is what the engine must distribute, vaporize and burn. To predict cold-start and warm-up driveability, a driveability index (DI) has been developed using the temperatures for the evaporated percentages of 10 percent (T10), 50 percent (T50) and 90 percent (T 90):
DI 1.5(T10) 3.0 (T50) (T90)
ratio becomes too fuel lean (too much air for the amount of fuel), which may cause loss of power, surging or backring. When the fuel supply is interrupted, the engine stops and may be difcult to restart until the fuel system has cooled and the vapor recondensed. After a hot soak (engine shutdown), it may be difcult to start the engine if there is too much vapor formed in the fuel system. Overheated or too volatile fuel is the main cause of vapor lock. Fuel temperature depends on the air temperature, how hard the vehicle is working,
The DI varies with gasoline grade and season; the normal range in the U.S. is 375C to 625C derived (850F to 1300F derived). In other parts of the world, the range may be narrower for example, in the Asia Pacic it ranges from 460C to 580C derived (1000F to 1200F derived). Lower values of DI generally result in better cold-start and warm-up performance, but once good driveability is achieved, there is no benet to further lowering the DI. The equation was originally developed using data for conventional gasolines in carbureted vehicles. Subsequent testing has shown the equation to be applicable to later-model fuel-injected engines for conventional gasolines. However, for ethanol blends an upward adjustment is needed for the equation to correlate with actual vehicle driveability performance.
how well the fuel system is isolated from the heat of the engine and how effectively the fuel system is cooled.
Carburetor Icing Carburetor icing occurs when the intake air is chilled below the freezing point of water by evaporation of the gasoline in the carburetor. The ice forms on the throttle blade and in the venturi and can interrupt carburetion, causing the engine to stall. Icing can be acute when the air is moist (70 percent or higher relative humidity) and the ambient temperature is between 2C and 13C (35F and 55F). These weather conditions are common during the fall, winter, and spring in many parts of the country and they can last well into the summer in some coastal regions. Carburetor icing is not a problem when the intake air temperature is below freezing because then the air is too dry. The extent of carburetor icing does not depend on the weather alone. It also involves carburetor and vehicle design and the mechanical condition of the engine in particular, those components that affect warm-up time, like thermostats, automatic chokes, intake air heaters, and heat risers. And it also involves gasoline volatility. The 70 percent evaporated temperature in the distillation prole is a good index of the tendency of a gasoline to cause carburetor icing the lower this temperature, the more severe the icing. Carburetor icing is not as big a problem as it used to be. For emission control reasons, most carbureted engines built since the late-1960s have been equipped with intake air heating systems, which generally eliminate carburetor icing. Today the problem is not large because vehicles with carburetors mostly have been replaced by fuel-injected vehicles.
Volatility Specications
The gasoline specication, ASTM D 4814 (see page 38), controls the volatility of gasoline by setting limits for the vapor pressure, distillation prole (temperatures at three evaporated points and end point), Driveability Index, and vapor-liquid ratio properties. The specication employs six vapor pressure/distillation prole classes (Figure 1-3a) and six vapor-liquid ratio classes (Figure 1-3b). The specication, except during transition months, assigns one vapor pressure/distillation prole class and one vapor-liquid ratio class each month to each geographical area (state or portion of a state) in the U.S. based on altitude and the expected ambient temperature range. Gasoline volatility not only affects a vehicles driveability but also its VOC emissions both evaporative and exhaust emissions (see page 19). Because of this relationship, the federal government and some states limit gasoline volatility to control the aspect of air quality affected by hydrocarbon emissions. ASTM incorporates federal volatility (vapor pressure) regulations into the gasoline specication as they are promulgated.
Figure 1-3a ASTM D 4814 Vapor Pressure and Distillation Class Requirements
Vapor Pressure/ Distillation Vapor Pressure, Class kPa (psi) max. Distillation Temperature, C (F) 10% Evap., max. 50% Evap., max. 90% Evap., max. End Point, max. Driveability Index, max.
AA A B C D E
54 (7.8) 61 (9.0) 69 (10.0) 79 (11.5) 93 (13.5) 103 (15.0)
70 (158) 70 (158) 65 (149) 60 (140) 55 (131) 50 (122)
77 121 (170 250) 77 121 (170 250) 77 118 (170 245) 77 116 (170 240) 66 113 (150 235) 66 110 (150 230)
190 (374) 190 (374) 185 (365) 185 (365) 185 (365) 185 (365)
225 (437) 225 (437) 225 (437) 225 (437) 225 (437) 225 (437)
597 (1250) 597 (1250) 586 (1240) 586 (1230) 580 (1220) 569 (1200)
Figure 1-3b ASTM D 4814 Vapor Lock Protection Class Requirements Vapor Lock Protection Class 1 2 3 4 5 6 Vapor-Liquid Ratio (V/L) Test Temperature, C (F) V/L, max. 60 (140) 56 (133) 51 (124) 47 (116) 41 (105) 35 (95) 20 20 20 20 20 20
Chapter 1
Fluctuating volatility requirements make gasoline manufacture and distribution a complex process. A rener producing gasoline for a multistate area may have to make gasolines with several different volatilities and change the volatility from month to month. And each gasoline has to be kept separate while it is shipped to the appropriate location. The European Unions EN 228 gasoline specication controls gasoline volatility by setting limits for the vapor pressure, distillation prole (percent evaporated at three temperatures), end point, distillation residue, and VLI. The specication employs six volatility classes (Figure 1-4) that are assigned by country for winter, summer, and transition periods. Other areas of the world may use ASTM, EU, or their own volatility specications that range from a single volatility class year-round, to winter and summer classes, and to systems similar to ASTM or EU.
Knocking Knocking or pinging is the sound of abnormal combustion. It is also known as spark knock. Normal combustion in a spark-ignition internal combustion engine is initiated by a spark. The ame front fans out from the spark plug and travels across the combustion chamber rapidly and smoothly until almost all the fuel is consumed. When combustion is abnormal, the last part of the unburned mixture ignites spontaneously (autoignites) and burns very rapidly, causing the pressure in the cylinder to rise rapidly. This creates
Antiknock Performance
Knock-free engine performance is as important as good driveability. Octane number is a measure of a gasolines antiknock performance its ability to resist knocking as it burns in the combustion chamber. There are two laboratory test methods to measure the octane number of a gasoline (see page 40). One yields the Research octane number (RON); the other, the Motor octane number (MON).
RON correlates best with low speed, mild-knocking conditions; MON correlates best with high-
the characteristic knocking or pinging sound. Occasional light knocking doesnt hurt an engine. But heavy or prolonged knocking can result in: Objectionable noise Loss of power Overheating of engine parts Knock-induced surface ignition Engine damage Knock occurs because the gasolines antiknock rating (octane number) is below the antiknock requirement of the engine at that moment. Generally, the situation involves high-load conditions, like hard acceleration or climbing a grade.
speed and high-temperature knocking conditions and with part-throttle operation. For a given gasoline, RON is always greater than MON. The difference between the two is called the sensitivity of the gasoline. Because RON and MON are measured in a single-cylinder laboratory engine, they do not completely predict antiknock performance in multicylinder engines. There is a procedure to measure the antiknock performance of a gasoline in vehicles (see page 41). The resulting value is called Road octane
Figure 1-4 EN 228 Volatility Class Requirements Volatility Vapor pressure Units kPa psi % Evaporated at 70C (158F), E70 vol % Class A 45.0 60.0 6.5 8.7 20.0 48.0 46.0 71.0 75.0 210 410 2 Class B 45.0 70.0 6.5 10.2 20.0 48.0 46.0 71.0 75.0 210 410 2 Class C/C1 50.0 80.0 7.5 11.9 22.0 50.0 46.0 71.0 75.0 210 410 2 C () C1(1050) C () C1(1050) Class D/D1 60.0 90.0 9.0 13.4 22.0 50.0 46.0 71.0 75.0 210 410 2 D () D1(1150) D () D1(1150)
Class E/E1 65.0 95.0 9.7 14.2 22.0 50.0 46.0 71.0 75.0 210 410 2 E() E1(1200) E() E1(1200)
Class F/F1 70.0 100.0 10.5 14.9 22.0 50.0 46.0 71.0 75.0 210 410 2 F () F1(1250) F () F1(1250) 5
% Evaporated at 100C (212F), E100 vol % % Evaporated at 150C (302F), E150 vol %, min Final boiling boint C, max F, max Distillation residue VLI (10 VP + 7 E70) VLI (68.95 VPpsi + 7 E158F) vol %, max Index, max Index, max
Other Abnormal Combustion Phenomena Other abnormal combustion phenomena occur in addition to knocking. Surface ignition involves the ignition of the air-fuel mixture by a hot spot rather than by the spark. Potential ignition sources include: glowing combustion chamber deposits, sharp edges or burrs in the combustion chamber or an overheated spark plug electrode. Heavy, prolonged spark knock can generate hot spots, which produce surface ignition. The hot spot ignites a portion of the mixture before it would normally start to burn. This may occur either before or after spark ignition. Surface ignition before the spark is called preignition. Surface ignition after the spark is postignition. When preignition occurs, ignition timing is lost and the upward movement of the piston is opposed by the high pressure generated by the early combustion. This results in engine roughness, power loss, and severe localized heating of the piston crown. If it is prolonged, the localized heating can burn a hole in the piston. When preignition is caused by a hot spot generated by prolonged, heavy spark knock, it is known as knock-induced preignition. It has the same adverse effect on engine operation as preignition from other sources. Knock-induced preignition is the most damaging side effect of spark knock. Postignition reduces the combustion time, and the loss of combustion control can cause knock, engine roughness and reduced power output. The extent of its effect depends on its location in the combustion chamber and the time in the cycle that it occurs. (continued on next page)
number (RdON ). Since vehicle testing is more involved than laboratory testing, there have been a number of attempts to predict RdON from RON and MON. The equations take the form:
RdON = a(RON) + b (MON) + c
A good approximation for RdON sets a = b = 0.5 and c = 0, yielding (RON + MON)/2, commonly written (R + M)/2. This is called the Antiknock Index (AKI ). The U.S. Federal Trade Commission requires dispensing pumps to be labeled (posted) with the gasolines AKI.1 Owners manuals in the U.S. also must indicate the octane number recommendation for vehicles 2 by AKI. (R + M)/2 is voluntarily posted in Canada. Neither the AKI nor the several other single-value indices that have been developed work for all vehicles. The performance of some vehicles correlates better with RON or MON alone than with a combination of the two. And for a given vehicle, the correlation can vary with driving conditions.3 As the formula indicates, gasolines with the same AKI can have different RONs and MONs. This may explain why a vehicle knocks with some ll-ups of the same brand but not with others; or why it knocks with one brand of gasoline but not with another. Of course, for a comparison to be valid, the vehicle must be operated under identical conditions, which is not easy for the typical driver. Generally, three grades of unleaded gasoline with different AKIs are available in the U.S. regular, midgrade, and premium. At sea level, the posted AKI for regular grade is usually 87 and for midgrade, 89. The AKI of premium grade varies more, ranging from 91 to 94. The posted AKIs are lower in the Rocky Mountain states. These altitude gasolines historically provided the same antiknock performance as higher-AKI gasolines at sea level. The octane requirement of older-model engines decreases as air pressure (barometric pressure) decreases. Barometric pressure is lower at higher elevations. Since 1984, vehicles have been equipped with more sophisticated control systems, including sensors to measure, and engine management computers to adjust for changes in air temperature and barometric pressure (see page 60). These vehicles are designed to have the same AKI requirement at all elevations and the owners manuals specify the same AKI gasoline at all elevations. Outside the U.S. and Canada where an octane number is posted, RON is generally used. The owners manuals also specify the minimum octane grade recommended in terms of RON. It is difcult for a driver to know whether a gasoline has the antiknock performance the engine requires when the engine is equipped with a knock sensor system. These systems, which temporarily retard spark timing to eliminate knocking, are installed on many late-model engines (see page 62). Retarding the spark reduces power and acceleration. The knock sensor responds so quickly that the driver never notices the knock. Loss of power and acceleration will be the only clues that the antiknock quality of the gasoline does not meet the vehicles octane requirement.
1 The gasoline being dispensed must have an antiknock index equal to or greater than the posted value. Rounding the number upward is not permitted. 2 Older owners manuals of some foreign cars specify RON; some more recent ones specify both RON and AKI.
3 See page 8 for the variables that affect an engines octane requirement.
Chapter 1
Using gasoline with an antiknock rating higher than that required to prevent knock or to prevent spark retardation by the knock sensor will not improve a vehicles performance.
(continued from previous page) Run-on is the phenomenon in which the engine continues to run after the ignition switch is
Octane Number Requirement

The technical octane number requirement (ONR) of an engine is dened as the octane number of a reference fuel that will produce trace knock under the most severe speed and load conditions. Trace knock is the knock intensity that is just audible to a trained technician. Customers may or may not be able to detect trace knock, so the customer ONR is usually less than the technical
ONR. For the rest of this discussion, ONR will refer to the technical ONR. ONR can be reported
turned off. It also is referred to as after-running or dieseling. The engine runs noisily and the exhaust smells bad. Run-on usually is caused by compression ignition where the air-fuel mixture is autoignited by the general high temperature of the combustion chamber but it also can be caused by surface ignition. The incidence of run-on is decreased or eliminated as the octane quality, especially the RON, of a gasoline is increased. Another important run-on factor is idle speed. This is why many carbureted engines are equipped with an idle stop (anti-dieseling) solenoid. Run-on is not a problem with modern fuel-injected engines because fuel cannot be delivered to the combustion chamber when the ignition switch is turned off.
as an RON or AKI value. The ONR of an engine is usually determined for either maximum-throttle or part-throttle acceleration conditions, whichever is the most critical. The ONR of different engines varies considerably and as much as a 10-octane-number range in ONR can be obtained for vehicles with the same engine model. The ONR of an engine is inuenced by its operating conditions. The effects of some of the more signicant of these are listed in Figure 1-5. Mechanical problems, such as a malfunctioning exhaust gas recirculation (EGR) valve, and electrical problems, such as advanced spark timing, can increase ONR. With late-model vehicles that use ECM control systems and knock sensors, the traditional denition of ONR may no longer apply since the knock sensor systems are calibrated to either totally or nearly eliminate audible knock. Work is being done to redene the ONR for modern vehicles based on a measure of acceleration performance. When an engine is brand-new, its ONR is determined by its design and manufacture. Generally, it will not knock when operated on a gasoline with the AKI or RON recommended by the automobile manufacturer. However, an engines ONR can increase dramatically during the rst several thousand kilometers (miles). This effect, called octane requirement increase (ORI), is caused by the buildup of carbonaceous deposits in the engines combustion chambers (see page 68). If the engine is equipped with a knock sensor, a slight loss of acceleration may occur during heavy accelerations if the ORI results in an ONR that exceeds the AKI of the gasoline being used.
Power
The power an engine develops depends on its design. In general, the more air an engine can process, the more power it can produce. Major design considerations for power are the displacement of the engine, the compression ratio, and the presence of a supercharger or turbocharger. Other factors affecting power are the number of valves per cylinder, valve timing, and spark timing (see Chapter 5). Because different grades of gasoline have essentially the same heating value, they all provide the same power in a given engine as long as their antiknock performance meets the engines requirement.
Figure 1-5 Average Effect of Some Variables on Engine Octane Number Requirement (ONR) Variable Compression ratio Air-Fuel ratio Spark advance Ambient temperature Absolute humidity Altitude Combustion chamber deposits
a In range 8:1 to 11:1 b Fuel leaning c In range 160F to 180F d For newer engines the change is almost zero because the ECM leans the air-fuel mixture and advances the spark timing as altitude increases. e Change depends on engine design, fuel, lubricant, and operating conditions.
Fuel Economy
Fuel economy in the U.S. is usually expressed as the number of miles
AKI Number +3 to +5 +2 +0.5 to +0.8 +0.5 0.3 1.5
d e
Change in ONR, Change in Variable +1a +1b +1 +10F c +10 grains/lb +1000 ft
traveled on one gallon of gasoline miles per gallon (mpg). Many drivers calculate it by counting the miles driven between ll-ups. Outside the U.S., fuel economy is usually expressed as litres per 100 kilometer (L/100 km). Driving on the road is not a good way to determine how fuel economy is affected by gasoline composition because it is difcult to control the many other factors that can affect fuel economy (see below). A more accurate determination is possible under controlled laboratory conditions. Vehicles are mounted on a chassis dynamometer in a temperature controlled space and driven through a specied operating cycle (see page 21). The weight or volume of the gasoline consumed during the cycle may be measured or the fuel economy may be calculated from the weight fraction of carbon compounds in the vehicles exhaust. Figure 1-6 shows that the average fuel economies of two eets of vehicles are proportional to the heating values of the gasolines tested.4 This is the relationship predicted by combustion theory. The newer eet was composed of 1989 model-year cars; the older eet of 1984 1985 model-year cars. The test involved two different sets of gasolines (Matrix A and Matrix B) which varied in aromatics content, olens content, oxygen content, oxygenate type, and several other properties. This result shows that heating values can be used as surrogates for actual fuel economy measurements when considering the effect of gasoline composition on fuel economy. Conventional fuels always have varied in heating value. One cause is the
+1 to +13
Figure 1-6 Relationship Between Fleet Average Fuel Economy and Heating Value
Fleet Average Fuel Economy, Miles/Gallon 22
1989 Fleet
21
20
formulation differences among batches and among reners. A survey of

19901991 conventional gasolines found that the heating value of summer
198485 Fleet
gasolines varied over an 8 percent range.5 The heating value also varies by grade and by season. On average, the heating value of premium-grade gasoline is about 0.7 percent higher than regular-grade because premiumgrade, in general, contains more aromatic hydrocarbons the class of hydrocarbons with the highest densities. The heating value of winter gasoline is about 1.5 percent lower than summer gasoline because winter gasoMatrix A Gasolines Matrix B Gasolines
19
18
line contains more volatile, less dense hydrocarbons.
17 108 110 112 114 Heating Value, Thousands Btu/Gallon 116 118
Reprinted with permission from SAE Paper No. 9301381993 Society of Automotive Engineers, Inc.
4 Albert M. Hochhauser et al., Fuel Composition Effects on Automotive Fuel Economy Auto/Oil Air Quality Improvement Research Program, Paper No. 930138, Society of Automotive Engineers, March 1993. 5 California Air Resources Board, Survey of California Gasolines, Sacramento, Ca., 1991.
Chapter 1
Oxygenated gasolines, which are required in some areas of the U.S. (see page 45 ), have lower heating values because the heating values of the oxygenate components are lower than those of the hydrocarbons they displace. The percentage decrease in heating value is close to the mass percent oxygen in the gasoline. For example, gasoline in carbon monoxide nonattainment areas must be oxygenated to a minimum of 2.7 mass % oxygen during four or ve winter months.6 As a result, its heating value is about 2.7 percent lower than conventional gasoline. Federal reformulated gasoline and California Phase 3 reformulated gasoline in federal reformulated gasoline areas must be oxygenated year-round to an average oxygen content of about 2 mass %. As a result, their heating values are about 2 percent lower than that of conventional gasoline. In addition, California Phase 3 reformulated gasoline sets some limits on distillation temperatures and aromatics content, which have the secondary effect of lowering the density of the fuel compared to conventional gasoline. This reduces the heating value by about another 1 percent. The gasolines that produced the result displayed in Figure 1-6 were specially formulated to span a wide range of compositions. The compositional variations were much greater than those that separate conventional and reformulated commercial gasolines. Thus, the result provides solid evidence that reformulated gasoline does not exert some unusual effect on fuel economy. Individual drivers have reported decreases of 10, 15, and even 20 percent in fuel economy when they began using reformulated gasoline. Not surprisingly, many of the claims are anecdotal. Few drivers keep continuous fuel-economy records, so they dont have a good fuel-economy baseline for the gasoline they previously used. Even with a baseline, a fuel-economy value based on the consumption of a single tankful of gasoline can be misleading. Drivers interested in fuel economy should average the result over several tanks of gasoline or, better yet, over several months of driving.
Heating Value The heating value (also referred to as energy content) of gasoline is its heat of combustion the heat released when a known quantity of fuel is burned under specic conditions. In the United States, the heating value is usually expressed as British thermal units (Btu) per pound or per gallon at 60F. [The international metric (SI) units are kilojoules per kilogram or per cubic meter at 15C.] For gross heating value, the water produced by the combustion is assumed to be recondensed to a liquid. For the lower net heating value, the water is assumed to remain a gas. Because all engines exhaust water as a gas, the net heating value is the appropriate value for comparing different fuels. Because gasoline is sold by volume, it is customary to express gasoline heating values per unit volume, specically, Btu per gallon (MJ/m3). This is the value that correlates with fuel economy because fuel economy is expressed per unit volume (miles per gallon) in the U.S. or volume per distance (L/100 km) in much of the rest of
Factors Affecting Fuel Economy

Fuel economy is affected by a vehicles size, weight, aerodynamics, fuel delivery system, engine design and transmission type. These factors remain constant for a specic vehicle. There also are many variable factors. As mentioned, the heating value of the gasoline is one. In addition, fuel economy is affected by weather conditions, air conditioner use, road conditions, the route driven, trafc, driving speed, and driving style. And it is affected by the mechanical condition of the car engine tune, wheel alignment and tire pressure. Some of these non-gasoline factors have the potential to cause substantial changes in fuel economy. Figure 1-7 is a list of average and maximum effects published by the United States Environmental Protection Agency ( EPA). Winter-related factors can combine to lower fuel economy up to 20 percent compared to summer factors. Rain or snow on the road offers more resistance to the tires. The driver also may need to slow down for safety to a less fuel-efcient speed. In cold weather, a richer air-fuel mixture is required to start and warm up the engine. And much of the warm-up is done at idle because of the need to defog or defrost the windows. Also, in many vehicles, the air conditioner is operated
the world. The densities of the hydrocarbons in gasoline vary over a much wider range from their heating values per unit weight. Consequently, compositional changes that result in density changes are accompanied by changes in heating value per unit volume. If the density of a conventional gasoline decreases, its heating value per unit volume also decreases. Adding oxygenates to conventional gasoline also decreases the heating value. Oxygenates have lower heating values than hydrocarbons on either a unit-weight or unit-volume basis. The amount of decrease depends on the amounts and identities of the oxygenates.
6 Nonattainment area is an EPA designation for an area where an air pollutant, carbon monoxide in this case, exceeds the limit established by the National Ambient Air Quality Standards more often than allowed.
to assist defogging. More energy is required to overcome the resistance created by the higher viscosities of cold lubricants engine oil, transmission uid, and differential lubricant. Short trips are worse for fuel economy than long trips because a cold engine uses more fuel than a warm engine and because of the energy required to overcome the resistance of cold lubricants. Trafc jams and bumper-to-bumper driving exact a heavy toll on fuel economy.
Fuel Economy Road Test

The results of a Wisconsin on-road fuel economy test demonstrate that some of the above factors can have a much bigger effect on fuel economy than a small percentage change in gasoline heating value.7 The test was designed to minimize all factors affecting fuel economy except gasoline composition. Vehicles were driven over the same route of 100 miles of urban and suburban roads. The fuel economy of each vehicle on the route was measured four times for each gasoline: once in the
Figure 1-7 Estimates of Fuel Economy Reductions Caused by Various Factors Percent Reduction in Fuel Economy Factor Temperature Idling/warmup Defroster Head wind Uphill driving Poor road conditions Conditions 20F vs. 77F Winter vs. summer Extreme use 20 mph 7% grade Gravel, curves, slush, snow, etc. 20 mph vs. 27 mph average speed 70 mph vs. 55 mph Hard vs. easy 0.5 inch Non-radial 15 psi vs. 26 psi Extreme heat Open vs. closed Average 5.3 Variable with driver Maximum 13 20
Analogous to air conditioning on some vehicles 2.3 1.9 4.3 6 25 50
Congested trafc
10.6
15
Highway speed Acceleration rate Wheel alignment Tire type Tire pressure Air conditioning Windows
N/A 11.8 1 1 3.3 21
25 20 10 4 6 N/A
Unknown, but likely small
Ofce of Mobile Sources, United States Environmental Protection Agency, Fuel Economy Impact Analysis of RFG, August 1995 (Document EPA 420-F095-003).
10
7 On-Road Study of the Effects of Reformulated Gasoline on Motor Vehicle Fuel Economy in Southeastern Wisconson, Wisconsin Department of Natural Resources, March 1995.
Chapter 1
morning and afternoon of the same day, and again in the morning and afternoon of a day a week later. Some vehicles were driven by the same driver all four times. Other vehicles were driven at different times by different drivers. When the results for the two weeks were compared, most of the fuel economies in the second week were lower. The differences were greater than 10 percent for a quarter of the car-fuel combinations. Two factors that probably contributed to the week-toweek differences were the driver change and a weather change. Ambient temperatures were lower in the second week; in some cases, noontime temperatures were as much as 17C (30F) cooler. The gasolines used in the Wisconsin test were commercial gasolines a conventional gasoline and federal reformulated gasolines (federal RFGs) oxygenated with MTBE, ETBE or ethanol. When the results for all the road tests of all the vehicles were combined, the average fuel economy of the three oxygenated federal RFG gasolines was 2.8 percent lower than the average fuel economy of the conventional gasoline a value much less than the 10 percent week-to-week difference for some of the car-fuel combinations, but right in the range predicted by the differences in the gasolines heating values.
Other Performance Factors

Both federal and California regulations require that some gasolines be oxygenated. Using oxygenated gasoline leans the air-fuel mixture of carbureted engines and fuel-injected engines without a closed-loop feedback system. Fuel leaning can cause some degradation in driveability, depending on the engines calibration (see page 49). Without additives, deposits form throughout an engines intake system in the fuel injectors, carburetor, intake manifold, intake ports and on the intake valves. Deposits can be very deleterious to engine performance degrading driveability, decreasing power and fuel economy, and increasing emissions (see page 68 ).
11
2 Gasoline and Air Quality
Introduction
Today we commonly discuss gasoline or gasoline-powered vehicles and their impact on air quality. A number of metropolitan areas in the U.S. fail to meet one or more federal air quality standards. In some of these areas, on-road vehicles are responsible for more than half of the emisviolations. Other major metropolitan areas throughout the world also are experiencing serious air pollution problems. This chapter explains who regulates emissions, and how, and why. It also explains which emissions come from vehicles and how they are formed. Finally, it explains how emissions are affected by gasoline characteristics and how gasoline is being reformulated to reduce emissions. The explanations are complicated because they involve complex regulations and complex science. Sometimes complete accuracy is sacriced to is unavoidable; both government regulation and science use them heavily. keep this review as short and simple as possible. The number of acronyms sions that either primarily or secondarily cause air quality standard
Figure 2-1 Maximum Hourly Pollutant Levels in California 1973 2002

0.6 0.5 0.4 Ozone, ppm 0.3 0.2 0.1 0.0
1973 1975
1980
1985 1990 Calendar year
1995
2000 2002
50 45 Carbon Monoxide (CO), ppm 40 35 30 25 20 15 10 5 0 1973 1975 1980 1985 1990 Calendar year 1995 2000 2002
Progress in the U.S.

Are the efforts of adding pollution control systems to vehicles and reformulating gasoline paying off in better air quality? The answer is yes. Urban air quality has improved dramatically over the past 20 years. To illustrate, Figure 2-1 shows the declining trend lines for the maximum hourly concentrations of three air pollutants ozone, carbon monoxide, and nitrogen dioxide in California.
0.8
The fact that these decreases are not uniform from year to year is a
Nitrogen Dioxide (NO2), ppm
0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 1973 1975 1980 1985 1990 Calendar year
Maximum hour 3-year average
result of annual variation in the weather (meteorology) on ambient pollutant concentrations. The improvement in urban air quality is due to signicant reductions in emissions from the various emission source categories such as factories, power plants, consumer products, and automobiles. For example, today a new-model passenger car emits less than 1 percent of the volatile organic compounds, less than 5 percent of the carbon monoxide, and only about 7 percent of the oxides of nitrogen emitted by a vehicle built before emissions controls began to be used. Similarly impressive improvements have been achieved for other emissions source categories.
1995
2000 2002
Key:
Federal standard California standard
The introduction of reformulated gasolines also has helped improve air quality. Federal Phase I gasoline was introduced in January 1995, Phase II in January 2000. California Phase 2 reformulated gasoline was required
Reprinted with permission from CVS News, July 2003.
13
The Beginning Smog is the common term for the forms of air pollution involving haze and oxidants, such as ozone. Smog was identied as a serious problem in the Los Angeles basin in the 1950s. As university scientists and government health agencies investigated the problem, they found that vehicle emissions were a signicant source of smog precursors. Acting on this information, the California Legislature established emissions limits for 1966 model cars. Federal legislation to reduce vehicular emissions, as part of a greater air quality program, was initiated with the adoption of the Clean Air Act of 1963. The rst Federal limits for exhaust emissions from gasoline-powered cars were implemented starting with the 1968 model year.
in California mid- 1996 and Phase 3 introduced at the end of 2003. Federal Phase II and California Phases 2 and 3 reformulated gasolines are believed to reduce ozone-forming emissions from cars and light trucks by about 10 to 15 percent. It is difcult to discern this effect in Figure 2-1 because of the year-to-year variability caused by other factors, such as meteorology.
Legislation
The Clean Air Act of 1963 initiated the U.S. federal governments regulation of air pollution. It was amended in 1967, 1970, 1977, and, most recently, in 1990. The stated purpose of the act is ... to protect and enhance the quality of the nations air resources ... As the purpose suggests, the act addresses a wide range of air pollution issues, not just vehicle emissions. One purpose of the act was to ... encourage cooperative activities by the states and local governments for the prevention and control of air pollution ... However, the act forbids states from setting separate vehicle emissions standards. This restriction was included so that auto manufacturers would not have to produce cars with different emission control systems to meet different state standards. The restriction was waived for California. Because of its more severe smog levels and its long history of working to control vehicle emissions, California is allowed to establish its own regulations for controlling vehicle emissions, subject to federal approval. Under certain circumstances, other states are allowed to require the sale of new vehicles that meet the more stringent California standards.
Administration/Regulation
Laws are not administered by the body that adopts them. The Congress or state legislature assigns the administrative responsibility to a governmental agency. The 1970 amendments of the Clean Air Act created the U.S. Environmental Protection Agency (EPA) and made it responsible for implementing the requirements of the act and its amendments. Californias laws covering vehicle emissions are administered by the California Air Resources Board (California ARB), which was established by the legislature in 1969. While some laws contain a lot of detail, they cant address all the issues surrounding their application in our complex industrial society. The agency administering the law has the responsibility to write regulations that will make the legislative intent a reality. Title 40 of the Code of Federal Regulations contains the EPA regulations concerning the protection of the environment. The states, as Congress intended, do much of the work to carry out the provisions of the Clean Air Act and its amendments. State and local air pollution agencies hold hearings, write regulations (based on guidance from the EPA), issue permits, monitor pollution, issue notices of violations, and levy nes. It is appropriate for the states to take the lead because state and local agencies need to select and enforce pollution control strategies that make sense for their region. Geography, weather conditions, housing patterns, regional trafc patterns, and the nature of local industry all inuence pollution levels.1
1 The Plain English Guide to the Clean Air Act, U.S. Environmental Protection Agency, EPA 400-K-93-001, April 1993.
14
Chapter 2
Gasoline and Air Quality
The Clean Air Act and its amendments ... set deadlines for the EPA, states, local governments and businesses to reduce air pollution. Each state is required to develop a plan that explains the actions it will take to meet or maintain the air quality standards set by the EPA. A state implementation plan (SIP) is a collection of the regulations the state will use. The EPA must approve each states SIP. The EPA assists the states by providing scientic research, expert studies, engineering designs, and money to support clean-air programs.
Figure 2-2 U.S. Ambient Air Quality Standards Maximum Average Concentration Criteria Pollutant Ozone; ppm Carbon monoxide (CO), ppm Nitrogen dioxide (NO 2), ppm Sulfur dioxide (SO 2), ppm Averaging Time 1-hour 8-hour 1-hour 8-hour 1-hour Annual 1-hour 24-hour Annual 24-hour Annual 24-hour Annual 30-day Quarterly 24-hour 1-hour 24-hour Federal Standard 0.12 0.08 35 9 0.053 0.14 0.03 150 50 65 15 1.5 California Standard 0.09 20 9.0 0.25 0.25 0.04 50 20 12 1.5 25 0.03 0.01
Air Quality Standards

Air pollutants are natural and articial airborne substances introduced into the environment in a sufcient concentration to have a measurable effect on humans, animals, vegetation, or building materials. From a regulatory standpoint, substances become air pollutants when the EPA determines them to be. As part of the process, the Clean Air Act requires the EPA to
Suspended particulate matter (PM10), g/m3 Suspended particulate matter (PM2.5), g/m3 Lead, g/m3 Sulfates, g/m3 Hydrogen sulde, ppm Vinyl chloride, ppm
issue a criteria document for each pollutant that documents its adverse effects. Regulated pollutants therefore are referred to as criteria pollutants. The EPA uses the information in the criteria documents to set National Ambient Air Quality Standards (NAAQS) at levels that protect the public health and welfare. Figure 2-2 lists the criteria pollutants and their federal limits. California standards, which in most cases are more stringent, also are listed. Some of the criteria pollutants, like carbon monoxide, are primary pollutants, which are emitted directly by identiable sources. Others, like ozone, are secondary pollutants, which are formed by reactions in the atmosphere. And others, like particulates, are of mixed origin. Figure 2-3 shows the ambient air quality standards for the European Union.
Air Pollutants 2
Ozone Ground-level 3 ozone is a colorless gas that is the chief component of urban smog. It is
formed by the interaction of reactive organic gases, oxides of nitrogen (NO X), and sunlight. These reactions take time, which means that peak ozone concentrations can occur far downwind of the sources of the reactants. And weather plays an important role. High temperatures, stagnant air, and sunny skies are optimum for creating ozone. This is why ozone concentrations tend to be
2 Paul Degobert, Automobiles and Pollution, Society of Automotive Engineers, Warrendale, Pa., 1995. 3 In the stratosphere, a layer of ozone partially shields the earth from solar ultraviolet radiation. Stratospheric ozone is formed by a different mechanism from ground-level ozone.
15
Figure 2-3 European Union Ambient Air Quality Standards (Directive 1999/30/EC, 2000/69/ED, 2002/3/EC) Criteria Pollutant Ozone, g/m3** g/m3** Carbon monoxide (CO), mg/m3 Benzene, g/m3 Nitrogen dioxide (NO2), g/m3 Nitrogen oxides (NOX), g/m3 Sulfur dioxide (SO2), g/m3 Suspended particulate Matter (PM10 ), g/m3 Lead, g/m3 Averaging Time AOT40, calc. from 1h values from May to July Maximum daily 8-hour mean Maximum daily 8-hour mean Annual 1-hour Annual Annual 1-hour 24-hour Annual and winter** 24-hour 24-hour Annual Annual Annual Not to be exceeded more than 24 times per calendar year Not to be exceeded more than 3 times per calendar year Not to be exceeded more than 35 times per calendar year Not to be exceeded more than 7 times per calendar year Not to be exceeded more than 18 times per calendar year Averaged over 5 years Not to be exceeded more than 25 days per calendar year averaged over 3 years Maximum Average Concentration 18000 120 10 5 200 40 30 350 125 20 50 50 40 20 0.5 Jan 1, 2005 Jan 1, 2010 Jan 1, 2010 Jan 1, 2010 July 19, 2001 Jan 1, 2005 Jan 1, 2005 July 19, 2001 Jan 1, 2005 Jan 1, 2010 Jan 1, 2005 Jan 1, 2010 Jan 1, 2005 Date by Which Limit is to be Met
*Indicative, not mandatory **Winter = 1 October 31 March
highest in the summer months, and why higher concentrations occur in the afternoon and lower concentrations at night. There are both federal and California one-hour standards for ground-level ozone (Figure 2-2), which have been used to identify nonattainment areas. In 1997, however, EPA promulgated a new eight-hour standard believed to be more protective of human health. This new standard will eventually supersede the old. [Ozone] damages lung tissue, reduces lung function, and sensitizes the lungs to other irritants. [It is] responsible each year for agricultural crop yield loss in the U.S. of several billion dollars and causes noticeable [leaf] damage in many crops and species of trees. 4
Volatile Organic Compounds (VOC)5 VOC is not a criteria pollutant, although some specic VOCs are classied as toxics (see below). Their importance stems from their role in forming
ozone. Most hydrocarbon emissions are VOCs, which explains why so much effort is directed toward reducing hydrocarbon emissions from vehicles and other source categories.
4 National Air Quality and Emission Trends Report, 1992. Ofce of Air Quality Planning and Standards, U.S. Environmental Protection Agency, EPA 454/R-93-031, October 1993. 5 VOC is the preferred term when discussing emissions. When the focus is on ozone formation, the term Reactive Organic Gases (ROGs) is more common. The main difference is that VOC emissions include methane and ethane, which do not participate in ozone formation and thus, are not ROGs. Another term sometimes used is non-methane organic gases (NMOGs). For simplicity, this review will use the term VOC throughout.
16
Chapter 2
The EPA estimated that, nationwide, about equal quantities of VOC emissions come from man-made and natural sources. On-road gasoline vehicles accounted for about 28 percent of man-made VOC emissions in 1998 (Figure 2-4), the last year for which EPA data are available. Not all hydrocarbons contribute equally to ozone formation. Some are more reactive than others depending on their chemical structure and the atmospheric conditions to which they are subjected. Under most conditions, olens and aromatics are more reactive than parafns.
Carbon Monoxide (CO) CO is a colorless, odorless gas generated primarily by combustion processes.
Figure 2-4 Emission Sources: 1998 National Man-Made VOC Emissions

17,917,000 Short tons
Stationary fuel combustion 5.0% Miscellaneous 6.8% Off-road diesel and jet engines 3.2% On-road diesel vehicles 1.2% Off-road gasoline vehicles 10.0% On-road gasoline vehicles 28.4% Industrial processes 45.5% U.S. EPA National Air Pollution Emissions Trends
It is toxic to humans and animals, and at high enough levels causes headaches, nausea, and even death. COs toxicity stems from its ability to reduce the oxygen-carrying capacity of the blood by preferentially bonding to hemoglobin.
CO is formed when carbon in fuel is not burned completely. The highest ambient levels generally
occur during the colder months, when atmospheric temperature inversions are more common, trapping CO emissions near the surface under a layer of warmer air. EPA estimated that on-road gasoline vehicles were responsible for about 55 percent of man-made CO emissions nationwide in 1998 (Figure 2-5). But in major cities, 85 to 95 percent of all CO emissions come from motor vehicle exhaust. Over the last decade, however, the auto industry has made remarkable advances in controlling air-fuel ratio tightly, which reduces CO emissions. This, combined with continuing renements in catalyst technology, which clean up pollutants in the exhaust from the engine, has drastically reduced CO emissions from todays cars.
Nitrogen Oxides (NO X) NO X is the generic term for several reactive gases containing nitrogen
Figure 2-5 Emission Sources: 1998 National Man-Made CO Emissions
Industrial processes 4.1% Stationary fuel combustion 6.0% Miscellaneous 11.3% Off-road diesel and jet engines 2.5% On-road diesel vehicles 1.7% Off-road gasoline vehicles 19.7% On-road gasoline vehicles 54.6% U.S. EPA National Air Pollution Emissions Trends
and oxygen in various ratios. They form when fuel is burned at high temperatures. The air quality standard applies only to nitrogen dioxide (NO2), but where emissions are concerned, NO and NO 2 are usually analyzed simultaneously and expressed as NO X. The reason for this is that NO oxidizes in the atmosphere to form NO2, which is the compound of concern. Most (90 percent) NO X emissions are man-made. The main sources are motor vehicles and industrial/commercial sources that burn fuels. EPA estimated that on-road gasoline vehicles generated about 21 percent of man-made NOX emissions in 1998 (Figure 2-6).
NO is nontoxic by itself but contributes to ozone formation. However, the resulting atmospheric
Figure 2-6 Emission Sources: 1998 National Man-Made NOX Emissions

Stationary fuel combustion 42.0% Miscellaneous 1.8% Off-road diesel and jet engines 20.3% On-road diesel vehicles 11.0% Off-road gasoline vehicles 0.7% On-road gasoline vehicles 21.0% Industrial processes 3.3% U.S. EPA National Air Pollution Emissions Trends
product, NO2, irritates the lungs and lowers resistance to respiratory infection. In some Western areas, NOX is an important precursor to particulate concentrations.6
Sulfur Dioxide (SO2) SO2 is produced primarily from the combustion of fuels containing sulfur.
Facilities that burn fuel oil and coal are the major sources. On-road and off-road engine fuels are estimated to be the source of less than 3 percent of total SO2 emissions. SO2 is a moderate lung irritant. It and NOX are major precursors to acidic deposition (acid rain).
Particulate Matter (PM10 and PM2.5) PM10 is composed of airborne particles less than 10 microns
(0.0004 inch) in diameter. (For comparison, the diameter of a human hair is about 50 to 100 microns).
6 National Air Pollutant Emission Trends 19001998, Ofce of Air Quality Planning and Standards, U.S. Environmental Protection Agency, EPA 454/R-00-002, March 2000.
17
EPA estimates that fugitive dust from roads accounts for about two-thirds of total PM10 emissions. Less
than 2 percent is attributed to on-road and off-road engines, but the percentage is higher in urban areas.
PM10 attributable to vehicle exhaust includes both primary carbon particles (mainly from diesel) and
secondary sulfate and nitrate aerosols formed by reactions of SO2 and NOX in the atmosphere. Both EPA and California have established PM10 standards.
PM2.5 is a subset of PM10 composed of particles less than 2.5 microns in diameter. These are small
enough to deposit deep in the lung, and may contain substances particularly harmful to human health. EPA promulgated national 24-hour and annual PM2.5 standards in 1997. In 1999, EPA and its state, tribal and local air pollution control partners deployed a monitoring network to measure PM2.5 concentrations nationwide, and has now accumulated several years of data. EPA intends to use this information to designate geographical areas as attaining or not attaining the standards December 15, 2004, which will start the clock on State Implementation Plans for nonattainment areas.
Lead Gasoline-fueled vehicles were the primary source of airborne lead when gasoline contained the
antiknock additive tetra-alkyl lead. But total national lead emissions decreased sharply between 1970 and
1994 as the lead content in leaded gasoline was phased down, and as sale of unleaded gasoline increased.
The sale of gasoline containing lead additives was nally prohibited for on-road use in January 1996. On-road gasoline-fueled vehicles in the U.S. today are responsible for none of the atmospheric lead concentrations. Excessive exposure to lead may cause neurological impairments such as seizures, mental retardation and/or behavioral disorders. Fetuses, infants and children are especially susceptible to low doses of lead. The hazardous threshold for blood lead poisoning still is being disputed.
Toxic Organics The toxicity of organic compounds depends on their structure. Most hydrocar-
bons are nontoxic at low concentrations, with benzene a notable exception. Some low-molecularweight aldehydes are carcinogens and some monocyclic and polycyclic aromatic hydrocarbons (PAH)7 are suspected or known carcinogens. The Clean Air Act Amendments of 1990 classied the following as toxic air pollutants related to gasoline and gasoline vehicles: benzene, polycyclic organic matter (POM), acetaldehyde, formaldehyde, and 1,3-butadiene. EPA calculates that these ve toxic compounds comprise 3.8 percent of total VOC emissions; about 70 percent of that amount is benzene. 1,3-Butadiene, formaldehyde, and acetaldehyde are not present in gasoline; they are formed during combustion. Benzene is a known human carcinogen. Some POMs are also carcinogens, but the POM content of gasoline and gasoline exhaust is so low as to be difcult to measure. The two aldehydes are eye and throat irritants, and formaldehyde is a suspected human carcinogen.
Origin of Vehicle Emissions 8

When fuel is burned with the correct amount of air in a gasoline-powered engine, the gases which are left are predominantly water vapor, carbon dioxide, and nitrogen all of which are benign,
7 Also called polycyclic organic matter (POM ), or polynuclear aromatics (PNA). 8 A signicant amount of emissions-related information may be obtained from the EPAs World Wide Web site at http://www.epa.gov/OMSWWW/.
18
Chapter 2
although carbon dioxide is a greenhouse gas. Deviations from this ideal combustion lead to the production of some VOCs, CO, NOX and PM10.9 As discussed above, gasoline-powered vehicles tend to be the main source of CO emissions, and contribute substantially to urban VOC and NOX, emissions. But due to substantial improvements in emission control of new cars, their contribution of these pollutants is diminishing. They emit only modest amounts of PM10 and PM2.5, but ill-maintained or tampered-with vehicles can emit much more. Diesel-powered vehicles, on the other hand, are substantial emitters of PM10, PM 2.5, and NOX, but only small emitters of CO and VOCs. (See Figures 2-4, 2-5, and 2-6.)
Exhaust VOC The vast majority of gasoline is burned before combustion gases exit the engine in
any properly operating vehicle, but a small fraction typically 1 to 5 percent manages, for a variety of reasons, to escape the combustion chamber unburned. These VOC emissions consist primarily of unburned hydrocarbons, but partially burned oxygen-containing compounds such as aldehydes are also present in small amounts. Most are removed by the vehicles catalytic converter. The quantity of exhaust VOC emission is inuenced by many factors, including engine design, operating temperature, air-fuel ratio (A/F), presence of fuel system deposits, the condition of the engine and its controls, and the performance of the catalytic converter. If the vehicle has some signicant malfunction that inhibits proper ignition or combustion, like a bad spark plug, VOC emissions can be many times higher than normal.
Evaporative VOC Exhaust gases are not the only source of VOC emissions from gasoline-fueled
vehicles. In fact, EPA estimated that in 1990, more than half the VOC emitted from gasoline vehicles resulted from evaporative-type processes. These are emissions of gasoline vapors that are generated due to heating of the fuel as a result of daily temperature variations and operation of the vehicle as well as leakage from the fuel system. Evaporative VOC emissions are different from exhaust VOC emissions. They contain no combustion products and their composition is weighted heavily toward the lowest boiling components of gasoline, because gasoline vapor is the main source. Gasoline vapor escapes from the typical vehicle from various locations on the vehicle, including the fuel tank, carburetor (on vehicles that use them), and intake manifold. In addition, liquid gasoline can permeate through plastic fuel tanks and elastomeric fuel hoses. It also can leak or seep from fuel system components or connections.10 Factors that inuence the amount of evaporative emissions include fuel system design (see page 56 ), component integrity, ambient temperature, and gasoline vapor pressure (see page 2). And, of course, there is the amount lost during refueling, which may be collected by service station vapor recovery systems.
Carbon Monoxide CO results from the incomplete combustion of fuel, and the main factor inu-
encing its production is the ratio of air to fuel (A/F) in the combustion chamber. If the mixture is fuel-rich, i.e., has insufcient air (O2) to convert all fuel carbon to carbon dioxide (CO2), the exhaust will contain a high level of CO. Fuel-rich operation can result either by design or by accident.
9 For a detailed discussion of pollutant formation and control in gasoline engines, see J.B. Heywood, Internal Combustion Engine Fundamentals, McGraw-Hill, 1988. 10 In these cases the composition of the evaporative VOCs will be characteristic of the whole gasoline. 19
Fuel Economy and Emissions Intuition suggests that an engine burning more fuel per kilometer (mile) would produce more emissions per distance, but that is not true. Vehicle emissions standards for new vehicles are set in terms of the mass of pollutant emitted per distance traveled. So, for example, a heavy, large-engine passenger vehicle can burn twice as much fuel per distance as a lighter, smallengine vehicle. But both must meet the same emissions standards and both will produce equivalent emissions per distance traveled. The large-engine vehicle in this example will, however, produce twice as much CO2 per distance as the small-engine vehicle. CO2 results from the complete oxidation of the carbon atoms in gasoline, and the amount produced is directly proportional to fuel economy. EPA does not classify CO2 as a pollutant, and therefore there are no CO2 vehicle emissions standards. CO2 is, however, a greenhouse gas. So there is much debate about CO2 emissions and fuel economy. In Europe, the auto industry has a target of 140g CO2 /km for the new-car eet by 2008. Europe uses g CO2 /km as a more appropriate fuel economy measure, as the eet contains both gasoline- and diesel-fueled passenger cars.
Prior to the introduction of vehicle emissions standards, most gasoline vehicles ran slightly fuel-rich most of the time, and produced a lot of CO. Later, vehicles were designed to minimize fuel enrichment, but manufacturers still used short periods of enrichment to aid vehicle starting and to increase power output under high-power conditions. Todays cleanest vehicles use minimal or no cold-start enrichment. And power enrichment is being greatly reduced as a result of EPA adding an additional high-speed and high-power conditions test (the Supplemental Federal Test Procedure [SFTP] to its vehicle certication requirements [discussed later]). A vehicle also can operate fuel-rich by accident, due to a malfunction of the fuel supply or control system. The causes are many but include: (1) deterioration or failure of components like a carburetor or oxygen sensor, (2) deposits formed over time in fuel injectors or carburetors by poor-quality gasoline, or (3) maintenance deciencies such as maladjustment or neglect.
Oxides of Nitrogen NOX is produced by a different mechanism than that for CO and exhaust VOCs.
Whereas the latter are products of incomplete combustion, NOX is produced when combustion is robust. It is generated by reactions of nitrogen and oxygen, which occur at high temperatures. Nitrogen is always present in the combustion chamber because air is 80 percent nitrogen. The production of NOX occurs whenever there is any residual oxygen during combustion and is particularly prevalent with higher combustion temperatures. Thus, NOX is affected by the A/F and by engine design factors that inuence temperature, such as compression ratio, spark timing, and cooling system performance. Combustion chamber deposits generally are believed to have a modest insulating effect, thus raising combustion temperatures and increasing NOX emissions slightly.
Vehicle Emissions: Limits

The Clean Air Act required the EPA to set standards or limits for exhaust emissions from gasoline powered cars starting with the 1968 model year. These rst limits applied to CO and hydrocarbons (HC), with limits for NOX added starting in the 1973 model year. Figure 2-7 shows how the federal limits for passenger cars, expressed as grams per mile (g/mile), have been tightened over the years. Since 1994, vehicles are certied for 10 years/100,000 miles, but for ve years /50,000 miles the limits are more stringent, as shown in Figure 2-7. The new federal Tier 2 120,000 mile tailpipe standards with eight permanent and two temporary certication bins are set at an average standard of 0.07 g/per mile for nitrogen oxides for all classes of passenger vehicles beginning 2004. The associated, somewhat variable, NMOG, CO, and PM standards for 0.07 g/mile NOX are 0.090 g/mile or lower, 4.2 g/mile or lower, and 0.01 g/mile (more or less), respectively. This includes all light-duty trucks, as well as the largest SUVs. Vehicles weighing less than 6,000 pounds will be phased in to this standard between 2004 and 2007. California has a separate set of passenger car limits that were applied initially to the 1966 model year passenger cars and typically have preceded the federal limits by a couple of years. There are other federal and California limits for other gasoline vehicles: light-duty trucks, heavy-duty trucks, and buses. Chapter 5 describes the variety of emission control devices and strategies employed to reduce the emissions from gasoline-powered vehicles.
20
Chapter 2
Figure 2-8 shows the current and future European Union vehicle emissions standards. The Japanese vehicle emissions standards for passenger cars and light-duty trucks are presented in Figure 2-9. Exhaust emissions are very dependent on how a vehicle is operated. So a standard set of test conditions is needed to certify that new vehicles meet their prescribed emissions limits. EPA requires that exhaust emissions be measured while the vehicle is driven according to a specied speed-time cycle on a dynamometer. The cycle used is called the Federal Test Procedure (FTP 75), which simulates a 7.5-mile urban driving route with a cold start, frequent stops, and an average speed of 19.6 mph. Currently,
EPA is phasing in an additional certication
Figure 2-7 U.S. Federal Passenger Car Exhaust Emission Standards Maximum Emissions g/mile (FTP-75 Cycle) Useful Life, Carbon Hydrocarbons Oxides of Particulates Years/1000 Miles Monoxide (CO) ( PM10 ) (HC) Nitrogen (NOX ) 5/50 5/50 5/50 5/50 5/50 5/50 5/50 5/50 5/50 5/50 10/100 5/50 10/100 84 51 34 28 28 15 15 7.0 3.4a 3.4 3.4 4.2 3.4 4.2 10.6 6.3 4.1 3.0 3.0 1.5 1.5 0.41 0.41 0.41 0.25b 0.31b 0.075
c
Model Year Pre-control (estimated) 1968 69 197071 1972 197374 197576 197779 1980 19811990 199193 199498 199498 1999 2003 NLEV 1999 2003 NLEV
4.1 3.1 3.1 2.0 2.0 1.0 1.0 0.4 0.6 0.2 0.3
0.20 0.08 0.10 0.08 0.08
requirement called the SFTP, or Supplemental Federal Test Procedure. This test cycle has a higher average speed, and incorporates some robust vehicle accelerations, to ensure that new vehicles have acceptably low exhaust emissions under these conditions.
0.090c
a 1981 82 model years allowed 7.0 g/mile with waiver. b NMHC c NMOG
Figure 2-8 2000, 2005 European Union Emission Limits: Passenger Cars and LCVs Gasoline Vehicles (Directive 98/69/EC) Passenger Cars and LCVs Class I 2.30 0.20 0.15 1.00 0.10 0.08 LCVs Class II 4.17 0.25 0.18 1.81 0.13 0.10 LCVs Class III 5.22 0.29 0.21 2.27 0.16 0.11
Inspection and Maintenance

In addition to establishing emission limits for new vehicles, the EPA has long recognized the importance of making sure that vehicles in use continue to function as they were designed. The emission control systems of a modern gasoline powered vehicle are complex (see Chapter 5). To deliver the intended emissions performance, all of the systems must function properly. A single defect can hurt the effectiveness of several subsystems, thus greatly increasing emissions. For example, a fault that causes the engine to operate fuel-rich not only will increase production of CO and HC in the engine, but will drastically reduce the ability of the catalyst to eliminate these pollutants, thus increasing their emissions by a factor of
2005 Year 2000 g/km CO HC NOX CO HC NOX
Straight comparison with the U.S. is impossible since test cycles are different.
21
Figure 2-9 Japanese Vehicle Emission Specications Implementation Year 2000 2000 2000 2005 2007 2005 2005 Vehicle Type PC 4-cycle LDT 1,700 kg LDT 1,700 2,500 kg PC 1,250 kg LDT mini-sized LDT 1,700 kg LDT 1,700 kg 2,500 kg NOX 0.17 (0.08) 0.17 (0.08) 0.25 (0.13) 0.17 (0.08) 0.17 (0.08) 0.17 (0.08) 0.17 (0.08) Limit (Average) THC 0.17 (0.08) 0.17 (0.08) 0.17 (0.08) 0.17 (0.08) 0.17 (0.08) 0.17 (0.08) 0.17 (0.08) CO 0.217 (0.67) 0.27 (0.67) 3.36 (2.10) 0.17 (0.08) 0.17 (0.08) 0.17 (0.08) 0.17 (0.08) Unit g/km g/km g/km g/km g/km g/km g/km Test Method 10.15 mode 10.15 mode 10.15 mode Revised Revised Revised Revised
Straight comparison with the U.S. is impossible since test cycles are different. For 2000, 0.17 (0.08) indicates 0.17 as the meaximum permissible value for the vehicle and 0.08 indicates the average value for the vehicle type.
perhaps 10 or more. When this happens, one broken vehicle can pollute as much as 10 properly functioning vehicles! Thus, regular inspection of the engine and its emissions controls, plus prompt and effective repair of any defects, is as important to clean air as requiring the controls initially. In 1983, the EPA oversaw the introduction of Inspection and Maintenance (I/M) programs in a number of states with air quality problems. These mandatory programs, often referred to as smog inspections, subject a vehicle to a set of inspections to detect if the emissions control systems are defective or have been tampered with. The inspections may be conducted at state-run facilities or at privately owned shops. Most involve a visual check of the vehicle for obviously broken, damaged or missing emissions control components and some type of measurement of emissions from the vehicles tailpipe. If the vehicle fails any of the tests, the owner usually is required to have the affected items repaired, subject to certain cost limits. The 1990 Clean Air Act Amendments require a number of regions in the U.S. to implement more stringent I/M programs.11 Todays new vehicles have mandatory systems called on-board diagnostics (OBD), which can identify many of the problems that lead to signicant increases in emissions, e.g., problems with the catalytic converter, or with the exhaust oxygen sensors that are part of the closed-loop A/F control system. Eventually, OBD may obviate the need for I/M programs.
Vehicle Emissions: Gasoline Effects

Changes in gasoline properties and composition can help reduce vehicle emissions. Certain gasoline modications are very effective in enabling vehicle emissions control systems to perform at their optimum levels. But other gasoline modications are not nearly as effective at reducing emissions compared to the use of the vehicle emission control systems described in Chapter 5. The explanations here apply chiey to vehicles built since 1985.
11 Detailed information regarding inspection and maintenance programs can be obtained from the U.S. Environmental Protection Agency, Ofce of Mobile Sources, National Vehicle and Fuel Emission Laboratory, 2565 Plymouth Road, Ann Arbor, Michigan 48105. Regulations regarding I/M programs can be found in Code of Federal Regulations, Volume 40, Part 51 (40 CFR 51), Subpart S.
22
Chapter 2
Sulfur Sulfur in the fuel becomes sulfur oxides in the exhaust, which temporarily poison the
three-way catalyst. Reducing gasolines sulfur content increases converter efciency and decreases
VOC, CO, NOX, and toxics emissions.
Reducing the sulfur content also reduces the direct emission of sulfur dioxide a criteria pollutant, but gasoline engines are not a major source of this pollutant.
Vapor Pressure Decreasing the vapor pressure of gasoline reduces evaporative VOC emissions and
to a lesser extent can reduce exhaust VOC and CO.

Oxygenates As explained earlier, CO is the result of incomplete combustion and its formation is very
dependent on the A/F. In older cars, adding oxygenates to gasoline has the same effect as increasing the amount of combustion air. It adds more oxygen to the combustion chamber, makes combustion more complete, and reduces formation of carbon monoxide. Oxygenates also tend to reduce exhaust VOC emissions somewhat, but they increase aldehyde emissions and tend to increase NOX emissions in many vehicles. As explained previously, NOX formation is increased by excess oxygen and higher combustion temperatures. This potential relationship between oxygen and increased NOX caused California to limit the oxygen content of Phase 2 reformulated gasoline to 2.2 mass %. Initially, the EPA also limited the oxygen content of federal RFG but removed the limit in 1996. The emissions benet of oxygenates was greatest in pre-1990 vehicles with less effective A/F control systems. The closed-loop A/F control systems in newer vehicles have become progressively better and better over time (see Chapter 5). By adjusting intake A/F based on the oxygen content of the exhaust, these systems decrease intake air to compensate for oxygen in the fuel, negating most of the emissions benet associated with having oxygenate in the gasoline. The addition of adaptive learning systems has improved A/F control even more. Consequently, oxygenates seem to have little effect on exhaust emissions from these newer vehicles, so long as they are operating in closed-loop mode.
Olens Increasing the olen content of gasoline tends to reduce exhaust VOC emissions, because
olens burn more easily and more completely than the other classes of hydrocarbons in gasoline. However, increasing olen content also tends to increase NOX formation. And it increases the olen content of evaporative emissions, which is undesirable because olens are among the most reactive hydrocarbons for ozone formation. For reformulated gasolines, the choice is to decrease olens.
Aromatics Decreasing the total aromatics content of gasoline may reduce CO and exhaust VOC emis-
sions, but the effects are variable and complex, probably because the aromatic compounds in gasoline are so diverse. Decreasing aromatics content reduces benzene in vehicle exhaust emissions because larger aromatic molecules are partly converted to benzene during combustion or in the catalytic converter.
Benzene Decreasing the benzene content of gasoline reduces the amount of benzene in both
evaporative and exhaust VOC emissions.
23
Figure 2-10 Chronology of United States Gasoline Regulations
Distillation Prole Temperatures Gasoline containing signicant
amounts of high boiling components tends to give high VOC exhaust emissions. High boiling components are more difcult to vaporize, especially in a cold engine, making complete combustion more difcult. Thus, placing limits on the distillation prole can lower
VOC emissions.
Federal
California
1960 Bromine Number Control/reduce the formation of ozone Summer Vapor Pressure Reduce evaporative hydrocarbon emissions from vehicles and fuel distribution system, and reduce ozone
1971 1974 Unleaded Gasoline Reduce health risks from airborne lead oxides and enable use of catalytic converters on vehicles to reduce emissions 1976 1978 1980 1989 Summer Vapor Pressure Reduce evaporative hydrocarbon emissions from vehicles and fuel distribution system and reduce ozone Summer Vapor Pressure Further reduce evaporative hydrocarbon emissions and ozone Winter Oxygen Reduce carbon monoxide emissions from vehicles in nonattainment areas 1992 1992
Reformulated Gasolines (RFGs)

Acting on the above relationships, the EPA and the California Air Resources Board have established a number of regulations that control gasoline properties to reduce emissions from gasoline-fueled vehicles. The chronology is shown in Figure 2-10. In 1992, for example, EPA required the maximum vapor pressure of summertime gasoline be decreased to reduce evaporative VOC emissions. The EPA capped (placed an upper limit on) vapor pressure at 7.8 psi (54 kPa) in ozone nonattainment areas in the southern and western states, where average summer temperatures are highest, and at 9.0 psi (62 kPa) elsewhere. That same year, California Phase 1 RFG was required throughout California. These regulations capped summertime vapor pressure at 7.8 psi (54 kPa) for the entire state, not just for ozone nonattainment areas, and forbade the use of lead-containing additives. They also made the use of deposit control additives mandatory, on the basis that engine intake system deposits increase emissions (see page 68).
EPA mandated that all U.S. motor gasoline contain a deposit control
Sulfur Content Reduce sulfur oxide emissions and particulates
Phase 1 Reformulated (Summer Vapor Pressure) Further reduce evaporative hydrocarbon emissions and ozone more restrictive than federal requirements Winter Oxygen Reduce carbon monoxide emissions from vehicles Leaded Fuels Banned Protect public health Deposit Control Additives Reduce carbon monoxide emissions
Phase I Reformulated Reduce ozone and toxics in nonattainment areas Deposit Control Additives Reduce vehicle emissions caused by fuel system deposits
1995
additive beginning in 1995.

1992 also saw implementation of the EPAs Winter Oxygenate program,
which required the addition of oxygenates to gasoline sold in the 39 areas of the country that had not attained the National Ambient Air Quality Standard for CO. Gasoline in these areas must contain 2.7 mass % oxygen
Leaded Fuels Banned Protect public health
1996
1996
Phase 2 Reformulated Achieve maximum costeffective reductions in vehicle emissions, including toxics
minimum, during the high-CO winter months. The four or ve applicable winter months varied from area to area. Most of the original
39 areas now have attained the National Ambient Air Quality Standard
Phase II Reformulated Further reduce ozone and toxics in nonattainment areas Tier 2 Sulfur Regulation Ensure effectiveness of advanced emission control technologies
2000
for CO, and most no longer are required to participate in the Winter Oxygenate program.
2004
2004
Phase 3 Reformulated Bans MTBE and provides more refinery blending flexibility
EPA introduced federal Phase I RFG in 1995. It had to be used in the
nine extreme or severe ozone nonattainment areas across the country.12 Less severe nonattainment areas were allowed to participate in (opt in) to the RFG program.
24
Chapter 2
EPA xed two characteristics of federal Phase I RFG. The average benzene content had to be less
than 1 vol % and the average year-round oxygen content had to be greater than 2.1 mass %. Summertime vapor pressure also was limited. Otherwise, the general approach was to set vehicle emission reduction targets, rather than place property or composition limits on the gasoline. To make this work, EPA provided reners with a Simple Model, which expired in 1998, and a more detailed mathematical model which relates gasoline composition with vehicle emissions, the so-called Complex Model. Inputs to the Complex Model are essentially those gasoline properties listed in the previous section. The model outputs are predicted levels of VOC , NO X, and toxics emissions from a standard in-use vehicle eet. The Complex Model gives reners exibility to meet the prescribed vehicle emissions reductions in the most cost-effective way for each particular renery. California introduced its Phase 2 RFG in mid-1996. It was required throughout the state. In its initial form, the regulation created a recipe for gasoline by specifying eight parameters of gasoline volatility and composition. It placed limits on summertime vapor pressure, benzene, total aromatics, olens and sulfur content, as well as the temperatures for the 50 percent and 90 percent evaporated points from the distillation prole. It also required a minimum oxygen content year-round. California subsequently modied the Phase 2 RFG regulation, allowing reners to certify alternative compositions through the California Predictive Model. This model was similar to EPAs Complex Model in concept but different in some particulars. Californias intent was to reduce the cost of producing Phase 2 RFG by allowing reners to show that an alternative gasoline (presumably less expensive to produce) would reduce vehicle emissions at least as much as the original recipe. Even when the Predictive Model is used, however, the eight gasoline parameters are still subject to limits. Some of these limits are less stringent than the equivalent limits in the original recipe but are still quite restrictive. Oxygen addition is not mandatory when using the California Predictive Model. But, in practice, roughly 70 to 80 percent of California gasoline is sold in areas designated as severe or extreme ozone nonattainment, and are subject to the federal RFG rule that requires oxygenate addition. The California Air Resources Board believes its Phase 2 RFG when rst introduced reduced vehicle VOC emissions by 17 percent, CO and NOX emissions by 11 percent, and air toxics by 44 percent, relative to California Phase 1 RFG. This was equivalent to removing 3.5 million cars from Californias roads!
EPA introduced Federal Phase II RFG in 2000. This rule continues the Phase I
Phase I Simple Model Complex Model Phase II Complex Model Figure 2-11 Reductions in Vehicle Emissions for Federal Phase I and Phase II Reformulated Gasoline Programs
Effective Date
Reduction in Emissions, % (Averaged Standard, Compared to 1990 Baseline Renery Gasoline)
VOC
Toxics
NOx
1995 1998a
Vapor pressure limits 17.1b 36.6c 27.4b 29.0c
16.5 16.5 21.5
No increase 1.5 6.8
limits on benzene and oxygen content, and the use of the Complex Model. But it requires larger reductions in VOCs, toxics, and NOX. (Figure 2-11 summarizes the emissions reductions that must be achieved for gasolines formulated under the federal Phase I and Phase II programs). Most reners have decreased vapor pressure, benzene content, and sulfur content as their primary strategies to meet the Phase I and Phase II emission limits.
2000
a Optional 19951997; mandatory starting in 1998. b Northern states c Southern states
12 The number of areas increased to 10 in 1996 with the addition of Sacramento, California and then to 11 in 2002 with the addition of the San Joaquin Valley in California.
25
When put on the same basis, California Phase 2 gasoline and federal Phase II gasoline give roughly comparable reductions in VOC and air toxics. But the California fuel is believed to reduce NOX emissions by about 11 percent compared to 4 percent for the federal fuel. This difference is due largely to the lower sulfur content of the California fuel, a difference that will diminish by 2006 when EPA implements lower 30 ppm maximum average sulfur limits for gasoline (EPA phase-in program begins in 2004). California changed from Phase 2 to Phase 3 RFG beginning January 1, 2004 (regulation effective December 31, 2003), although several reners began producing the new fuel earlier than that. Phase 3 RFG prohibits the intentional blending of MTBE into California gasoline, and disallows its presence and other oxygenates, except for ethanol, above a very small de minimus level. California took this step because MTBE had been found in various fresh-water resources throughout the state, and because tiny amounts of MTBE affect the taste and odor of drinking water. Ethanol is the only other oxygenate that reners can use to satisfy the federal oxygen mandate that applies to most gasoline sold in California. In addition to the prohibition of MTBE, Phase 3 sets lower limits for sulfur and benzene. The maximum average sulfur will be reduced from 30 to 20 ppm and the maximum level of benzene will be reduced to 0.8 volume %. Most other requirements for the new fuel are similar to Phase 2, and the California Air Resources Board believes the new fuel will further reduce vehicle emissions.
European Union
Through the Committee for Standardization gasoline specication CEN EN 228, the European Union beginning in 2005 is reducing sulfur to 50 ppm and 10 ppm on a balanced geographical basis (determined by each country) and limiting aromatics to a maximum content of 35.0 volume %. All gasoline will be at 10 ppm maximum sulfur by 2009.
Japan
Beginning in 2005, the Japanese Industrial Standard gasoline specication JIS K 2202 will limit sulfur content to 50 ppm maximum and summertime vapor pressure to 65 kPa (9.4 psi) maximum.
26
3 Gasoline Rening and Testing
Introduction
Technology exists to make gasoline from coal, shale oil, tar sands and exotic sources like recycled plastics and rubber tires. But these processes are complicated and expensive. Petroleum crude, also called crude oil or crude, is still the most economical source of gasoline. The rst step of gasoline rening isolates the gasoline naturally present in crude, much as the rst reners did. Then, in more complex steps, non-gasoline components of crude are converted into gasoline and gasoline molecules are rearranged to improve their characteristics. Understanding the various conversion steps requires knowing something about the hydrocarbon building blocks that make up gasoline and crude. So, this chapter rst discusses the composition of gasoline and the nature of hydrocarbons. Then it explains the various rening steps and how the resulting products are blended to create a nished gasoline. Finally it describes the gasoline specication properties and the tests used to measure them.
Figure 3-1 Gasoline Carbon Number Distribution

30
25
Volume Percent
20
15
10
10
12
14
Composition
There are two ways to describe a material by its chemical composition or by its properties. Both viewpoints can be instructive. Gasoline is a complex mixture of hundreds of hydrocarbons. The hydrocarbons vary by class parafns, olens, naphthenes, and aromatics and, within each class, by size. The mixture of hydrocarbons (and oxygenates) in a gasoline determines its physical property and engine performance characteristics. Gasoline is manufactured to meet the property limits of the specications and regulations, not to achieve a specic distribution of hydrocarbons by class and size. But, to varying degrees, the property limits dene chemical composition. Consider, for example, gasoline volatility. Chapter 1 explains that gasoline boils over a range of temperatures its distillation prole and that the gasoline specication limits this range. Each individual hydrocarbon boils at a specic temperature called its boiling point and, in general, the boiling point increases with molecular size. Consequently, requiring a distillation prole is equivalent to requiring a population of hydrocarbons with a range of sizes. The temperature limits of the distillation prole exclude smaller hydrocarbons with lower boiling points and larger hydrocarbons with higher boiling points. The most common way to characterize the size of a molecule is molecular weight. For a hydrocarbon, an alternate way is carbon number the number of carbons in its molecular structure. Butane, for example, has a molecular weight of 58 grams per gram-mole (g/g-mole) and a carbon number of 4 (C4); benzene has a molecular weight of 78 g/g-mole and a carbon number of 6 (C6). Figure 3-1 shows the carbon number distributions for typical regular and premium unleaded gasolines. Note that the range of sizes runs from C4 to C12 with the most prevalent size, C5 for regular and C8 for premium and the average size, C6.9 for regular and C7.1 for premium. The average molecular weight of gasoline ranges from 92 to 95. Figure 3-2 shows, as expected, that the cumulative carbon number distribution parallels the distillation prole.
Carbon Number
Regular unleaded Premium unleaded
Figure 3-2 Distillation Prole vs. Cummulative Carbon Number Distribution

Temperature F C 450 225 400 350 300 250 200 150 100 50 0 0 200 175 150 125 100 75 4 25 0 20 40 60 Volume Percent 80 100 2 8 6 12 10 Carbon Number 14
Distillation Profile Cumulative Carbon Number Distribution
27
Octane number is another example of how property limits dene chemical limits. Figure 3-3 illustrates how Research octane number (RON) varies with class for hydrocarbons of the same carbon number. So, an octane number limit requires greater representation of some classes and less of others. But octane number differentiation goes beyond class. Different isomers of the same hydrocarbon can have different octane numbers. The RON of isooctane (2,2,4-trimethylpentane) is 100 by denition, while the RON of normal octane is less than zero. Other properties, such as volatility, also are inuenced by isomer structure. With the advent of air pollution regulations, property specications have been supplemented by some composition specications. As noted in Chapter 2, the rst gasoline-related air pollution regulation limited the amount of olens in gasoline sold in Southern California by establishing a Bromine Number maximum specication. More recent regulations limit the amounts of both olens and aromatics in reformulated gasolines. Gasolines contain small amounts less than 0.1 volume % of compounds with sulfur, nitrogen and oxygen atoms in their structures (excluding added oxygenates). Even though these compounds also are composed primarily of carbon and hydrogen atoms, they are not classied as hydrocarbons because of the presence of the other atoms. The compounds either originate in the crude or are formed by the rening processes. Rening destroys many nitrogen- and, particularly, sulfurcontaining compounds (see below), but some survive. Reducing the sulfur content of gasoline is required by California Phase 3 RFG regulations, is a major tool in complying with federal Phase II
RFG, and will be the key factor in meeting future Tier 2 regulations.
Figure 3-3 Research Octane Number (RON) Varies with Hydrocarbon Structure
Compound n-Hexane 1-Hexene Cyclohexane Benzene
Formula
C6H14
C6H12
C6H12
C6H6
Structure
CH3(CH2 )4 CH3
CH2qCH (CH2 )3CH3
RON
25
76
83
123 (est.)
Compound Formula
2,2,4 -Trimethylpentane (Isooctane) C8H18 CH3 CH3
2,4,4-Trimethyl1-pentene (Isooctene) C8H16 CH3 CH3 CH2q C CH2 C CH3 CH3 106
Cis 1,3-dimethylcyclohexane C8H16 CH3
1,3-Dimethylbenzene C8H10 CH3
Structure
CH3CCH2 CH CH3 CH3
CH3 72 118
CH3
RON
100
28
Chapter 3
Gasoline Rening and Testing
About Hydrocarbons
Butane C4H10
Hydrocarbons are organic compounds composed entirely of carbon and
H H C H
H C H
H C H
H C H H CH3CH2CH2CH3
Shorthand
hydrogen atoms. Each of the four major classes of hydrocarbons parafns, olens, naphthenes and aromatics represents a family of individual hydrocarbons that share some structural feature. The classes differ in the ratio of hydrogen to carbon atoms and how the atoms are arranged. Parafns Parafns have the general formula CnH2n+2, where n is the number of carbon atoms. The carbon atoms in parafns are joined by single bonds and are arranged in a zigzag pattern, but the molecules usually are represented
Structural Isomers C8H18

n-Octane
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH3 CH3 CH3 CH3 CCH2 CHCH3 CH3
by a shorthand linear structure. It is possible for parafns with four or more carbon atoms to exist as two or more distinct compounds, which have the same number of carbon and hydrogen atoms. These compounds, called structural isomers, differ in the arrangement of the carbon atoms. Normal octane (n-octane) and isooctane are two examples of eight-carbon structural isomers. Isooctane is the common name for 2,2,4-trimethylpentane, which species the branching pattern of
Isooctane (2,2,4-Trimethylpentane)
2-Butene C4H8 CH3CHqCHCH3
the three methyl groups on a pentane backbone. Olens Olens (CnH2n ) are similar to parafns but have two fewer hydrogen atoms and contain at least one double bond between carbon atoms. They rarely occur naturally in crude oil but are formed during rening. Like parafns, olens with four or more carbons can exist as structural isomers. Naphthenes In naphthenes, also called cycloparafns, some of the carbon atoms
Cylcohexane C6H12 H2C H2C CH2 CH2 CH2 CH2

Shorthand
are arranged in a ring. The naphthenes in gasoline have rings of ve and six carbon atoms. Naphthenes have the same general formula as olens, CnH2n. As with the normal parafns, the carbon atoms in cycloparafns naturally arrange themselves in a zigzag pattern, but the molecule usually is drawn as the planar structure, usually in a shorthand notation that indicates the bonds but omits the carbon and hydrogen atoms. Aromatics Like naphthenes, some of the carbon atoms in aromatics are arranged in a ring, but they are joined by aromatic bonds, not single bonds.
Benzene C6H6 CH HC HC CH CH CH HC HC CH CH CH CH
Shorthand
The structure can be envisioned as an average of two discrete cyclohexatriene molecules, as it was thought to be in the early days of organic chemistry. But the aromatic bond character is now known to be distributed evenly around the ring. The shorthand representation for a monocyclic aromatic ring is a hexagon with a circle representing the aromatic bonds. Aromatic rings always contain six carbons; in polycyclic aromatics, like naphthalene, some of the carbons are shared by two or more rings.
29
Continuous Processing The change from a batch to a continuous ow process was a major step in the evolution of petroleum rening. Today, almost all processes are continuous ow, because it would be impossible for a modern renery to process the volume of crude it does using batch processes.
Rening
Raw Material
As it comes out of the ground, petroleum crude can be as thin and light-colored as apple cider or as thick and black as melted tar. Thin crudes have high American Petroleum Institute (API) gravities and, therefore, are called high-gravity crudes; conversely, thick crudes are low-gravity crudes. High-gravity crudes contain more natural gasoline and their lower sulfur and nitrogen contents make them easier to rene. But modern rening processes are capable of turning low-gravity crudes into high-value products like gasoline. Rening low-gravity crudes requires more complex and expensive processing equipment, more processing steps, more energy and, therefore, costs more . The price difference between high-gravity and low-gravity crudes reects the rening cost difference. All crudes are composed primarily of hydrocarbons of the parafnic, naphthenic, and aromatic classes. Each class contains a very broad range of molecular weights.
Processes
Todays renery is a complex combination of interdependent processing units, the result of a fascinating intertwining of advances in chemistry, engineering and metallurgy. It all started with the simple physical separation process called distillation.
Distillation In the late 1800s, crude was separated into different products by boiling. Distillation
works because crudes are composed of hydrocarbons with a broad range of molecular weights and, therefore, a broad range of boiling points. Each product was assigned a temperature range and the product was obtained by condensing the vapor that boiled off in this range at atmospheric pressure (atmospheric distillation). The earliest crude stills were simple pot stills consisting of a container where crude was heated and a condenser to condense the vapor. Later, distillation became a continuous process with a pump to provide crude ow, a furnace to heat the crude, and a distillation column to separate the different boiling cuts. In a distillation column, the vapor of the lowest-boiling hydrocarbons propane and butane rises to the top. The straight-run gasoline (also called naphtha), kerosene, and diesel fuel cuts are drawn off at successively lower positions in the column (see Figure 3-4)1. Hydrocarbons with boiling points higher than diesel fuel arent vaporized; they remain in liquid form and fall to the bottom of the column (atmospheric bottoms). Initially, atmospheric bottoms were used for paving and sealing. Later it was found that they could yield higher-value products like lubricating oil and parafn wax when they were distilled in a vacuum. Vacuum distillation requires sturdier stills to withstand the pressure differential and more sophisticated control systems. The limits of distillation as the sole rening process were quickly recognized: Because the yield of each product is determined by the quantity of the hydrocarbons in its boiling range in the crude, distillation couldnt produce enough gasoline to meet the demand. And it was producing higher-boiling material for which there was no market.
30 1 Straight-run products are those isolated from crude by simple distillation.
Chapter 3
Figure 3-4 Gasoline Processing in a Modern Petroleum Renery

H2 From bottom of page
Coker Light Gasoline Coker Heavy Gasoline
Coker Light Gasoline Hydrotreater
H2
Isomerization and/or Benzene Saturation
Straight-Run Light Gasoline
Straight-Run Light Gasoline
H2
Straight-Run Heavy Gasoline
Atmospheric Distillation Heavy Gasoline Hydrotreater
H2
Reformate
Reformer
Straight-Run or Hydrocracked Light Gasoline or Isomerate
Crude Oil
H2
Straight-Run Jet (Kerosene) Straight-Run Diesel (Heating Fuel) To Distillate Fuel Blending
Hydrocracker
Hydrocracked Heavy Gasoline Hydrocracked Light Gasoline Hydrocracked Gasoil To Distillate Fuel Blending Propylene (C3) Isobutane (C4) Butylenes/Amylenes (C4 /C5 )
Alkylation
Polymerization
Polymerized Gasoline Alkylate
Motor Gasoline Blending
Blocked to FCC or Hydrocracker
Straight-Run Heavy Gasoil Atmospheric Vacuum Light Vacuum Distillation Bottoms Gasoil Heavy Vacuum Gasoil
FCC Heavy Cycle Oil
H2
FCC Feed Hydrotreater FCC
Butylenes/Amylenes (C4 /C5 ) MeOH/EtOH

FCC Gasoline Hydrotreater or Sweetener
Rejected (C4 /C5 )

Ether Plant MTBE/TAME/ETBE
FCC Light Gasoline FCC Heavy Gasoline
FCC Light Gasoil Heavy Gasoil
To Distillate Fuel Blending
Coker
Vacuum Resid
Coker
Light Gasoil Heavy Gasoline Light Gasoline Coke
To Distillate Fuel Blending
To top of page
Cracking The discovery that hydrocarbons with higher boiling points (the larger ones left in the
distillation bottoms) could be broken down (cracked) into lower-boiling hydrocarbons by subjecting them to very high temperatures offered a way to correct the mismatch between supply and demand. This process thermal cracking was used to increase gasoline production starting in 1913. It is the nature of thermal cracking to make a lot of olens, which have higher octane numbers but may cause engine deposits. By todays standards, the quality and performance of this early cracked gasoline was low, but it was sufcient for the engines of the day. Two common examples of thermal cracking still in use today are visbreaking and delayed coking. Visbreaking heats a heavy petroleum fraction just enough to break down large molecules but not enough to carbonize it. It is more prevalent in Europe than in the U.S. In delayed coking, petroleum residua are heated enough to cause carbonization. Both thermal processes produce highly
31
olenic, high-sulfur, high-nitrogen products in the gasoline range and must be further processed to be acceptable motor gasoline blend components. Eventually heat was supplemented by a catalyst, transforming thermal cracking into catalytic cracking. A catalyst is a material that speeds up or otherwise facilitates a chemical reaction without undergoing a permanent chemical change itself. Catalytic cracking produces gasoline of higher quality than thermal cracking. There are many variations on catalytic cracking, but uid catalytic cracking (FCC) is the heart of gasoline production in most modern reneries. The term comes from the practice of uidizing the solid catalyst so that it can be continuously cycled from the reaction section of the cracker to the catalyst regeneration section and back again. The FCC process also produces building blocks for other essential renery processes, like alkylation. Hydrocracking is similar to catalytic cracking in that it uses a catalyst, but the catalyst is in a hydrogen atmosphere. Hydrocracking can break down hydrocarbons that are resistant to catalytic cracking alone. It more commonly is used to produce diesel fuel than gasoline. The next group of processes increases a renerys octane number pool. Although these processes predate the regulation of antiknock additives, they became more important as lead was phased out of gasoline. Without antiknock additives, the only way to produce high-octane-number gasolines is to use inherently high-octane hydrocarbons or to use oxygenates, which also have high-octane-number values2 (see Figure 3-3).
Reforming The reforming process literally re-forms the feed molecules, converting straight-chain
parafns and naphthenes into aromatics. For example, reforming cyclizes normal heptane (RON = 0) and then abstracts hydrogen to produce toluene (RON = 120). The hydrogen by-product is almost as important as the octane number upgrade. Hydrogen is an essential ingredient for processes like hydrocracking and hydroning. Reneries often have a hydrogen decit, which has to be made up by making hydrogen from natural gas (methane) or other hydrogen-rich feeds.
Alkylation The alkylation process combines small, gaseous hydrocarbons with boiling points too
low for use in gasoline to form liquid hydrocarbons. The feed, which primarily comes from the
FCC unit, includes C 4 hydrocarbons like isobutane and butylenes and sometimes C 3 and C 5 paraf-
ns and olens. The principal products are high-octane-number isomers of trimethylpentane like isooctane (RON = 100). Alkylation is a key process for producing reformulated gasolines because the contents of the other classes of high-octane-number hydrocarbons olens and aromatics are limited by regulation. Polymerization Another combination process is the polymerization of olens, typically the C3 olen, propylene, into a series of larger olens differing in molecular weight by three carbon atoms C6, C9, C12, etc. Polymerization is a less-favored process than alkylation because the products are also olens, which may have to be converted to parafns before they are blended into gasoline.
2 A manganese-based antiknock additive is not widely used in the United States at this time (2003) (see page 37). 32
Chapter 3
Isomerization Isomerization increases a renerys octane number pool by converting straight-chain
(typically C 5 and C 6) parafns into their branched isomers. For a given carbon number, branched isomers have higher-octane-number values than the corresponding straight-chain isomer.
Hydrotreating Hydrotreating is a generic term for a range of processes that use hydrogen with
an appropriate catalyst to remove impurities from a renery stream. The processes run the gamut from mild, selective hydrotreating to remove highly reactive olens to heavy hydrotreating to convert aromatics to naphthenes.
Desulfurization Sulfur removal, or desulfurization, traditionally has been a specialized example
of a hydrotreating process. The lower sulfur limits for reformulated gasoline may require the desulfurization of a signicant proportion of FCC gasoline. There are also processing reasons to desulfurize renery streams. In reforming, excess sulfur in the feed deactivates the catalyst. In FCC, excess sulfur in the feed results in high levels of sulfur in the FCC gasoline and greater production of sulfur dioxide during catalyst regeneration. The lower sulfur limits for reformulated gasoline (and diesel) have prompted the commercialization of several non-hydrotreating processes for sulfur removal. One option is adsorption, where an appropriate adsorbent will remove selected sulfur species directly from the FCC gasoline. One variation requires chemically changing existing sulfur species to more easily adsorbed species. Another process reacts sulfur species with olens in the FCC gasoline, producing heavier sulfur species that may be removed by simple distillation. Another variation oxidizes many sulfur species so that they may be removed by water washing.
Etherication of olens High-octane oxygenates called ethers may be produced at the renery by
reacting suitable alcohols such as methanol and ethanol with branched olens from the FCC, such as isobutene and isopentene, under the inuence of acid catalysts. In the mid-1990s MTBE, made by etherication of isobutene with methanol, became the predominant oxygenate used to meet
EPA and CARB reformulation requirements for adding oxygen to mitigate emissions from gaso-
line-powered vehicles. By 2002, some 38 etherication plants were in place at reneries in the U.S. (See sections in Chapter 2 on Gasoline and Air Quality and in Chapter 4 on Oxygenated Gasolines for more detail pro and con.)
Isobutene Dimerization Very recently, environmental issues with MTBE have made it more desir-
able to dimerize isobutene from the FCC unit, rather than etherify it. Fortunately, isobutene dimerization may be done with minimal modications to existing MTBE plants and process conditions, using the same acidic catalysts. Where olen levels are not restricted, the extra blending octane boost of the di-isobutylene can be retained. Where olen levels are restricted, the di-isobutylene can be hydrotreated to produce a relatively pure isooctane stream that can supplement alkylate for reducing olens and aromatics in reformulated gasolines.
33
The Modern Renery

The schematic layout of a modern, fully integrated U.S. renery is shown in Figure 3-4. Crude oil is fed to the distillation column where straight-run light and heavy gasoline, jet and diesel are separated at atmospheric pressure. Whereas straight-run jet and diesel are usually acceptable as is, the straight-run gasolines typically require more processing to convert them into gasoline blending components. The straight-run light gasoline may be isomerized to increase octane number, or hydrotreated to convert benzene to cyclohexane so that the nal gasoline blend will meet a benzene specication limit, or both. The straight-run heavy gasoline is hydrotreated to remove sulfur and then reformed to improve octane number and generate hydrogen for the hydrotreaters. The bottoms from the atmospheric column are vacuum distilled to obtain gasoils for FCC or hydrocracker feed. The gasoils are hydrotreated to reduce sulfur and nitrogen to levels that will not interfere with the FCC process. Even though the feed was substantially desulfurized, the FCC product must be sweetened to convert reactive sulfur compounds (mercaptans) to more innocuous ones, otherwise the gasoline blend will be odorous and unstable. Alternatively, in California and other areas with tight restrictions on the sulfur content of nished gasoline, the FCC product must be further desulfurized. Previously, the vacuum resid might have been used as low-value, high-sulfur fuel oil for onshore power generation or marine fuel. Now, to remain competitive, reners wring as much high-value product as possible from every barrel of crude. As a result, the vacuum resid is sent to a resid conversion unit, such as a resid cracker, solvent extraction unit or coker. These units produce more transportation fuel or gasoil, leaving an irreducible minimum of resid or coke. The resid-derived streams require further processing and/or treating before they can be blended into light fuels like gasoline or diesel. The complex renery shown in Figure 3-4 contains processing units that are not in all reneries in the U.S. or in the world. Many simple reneries consist of only a distillation unit and a reformer. Others in addition have an FCC unit and an alkylation unit. There are many combinations of units in reneries throughout the world. Figure 3-4 shows an ether plant. In areas where ethers are banned, this plant may be shut down or converted into a plant that makes isooctene (a high octane olen). The isooctene can be hydrotreated to make isooctane. The selection of renery units depends on the product volumes for the marketplace it serves. If diesel fuel is a larger part of the market than gasoline, processing units will be selected to maximize diesel fuel.
Processing Changes Required by Air Pollution Regulations

The balance among the various processes in a renery is dynamic, responding both to external and internal developments. The impact of air pollution regulations (see Figure 2-10) on renery operations is a good example. The requirement for unleaded gasoline and the gradual increase of its sales roughly paralleled the gradual phase-down of lead in leaded gasoline. Both these trends increased the need for higher-octane-number components. In response, reners produced more reformate,
FCC gasoline, alkylate, and oxygenates, roughly in this order. Later, tighter and tighter vapor pres-
sure limits reduced the amount of butane that could be added to gasoline in the summer. This resulted in excess butane, and, because butane has good octane quality, further increased the need for higher-octane-number components. A solution that solved both problems was to use butane to
34
Chapter 3
make alkylate. The requirements for oxygenated gasoline helped the octane number shortfall, because oxygenates have high octane numbers. The need for oxygenates prompted some reners to add units to make MTBE and other ethers. Most recently, the advent of California Phase 2 reformulated gasoline placed new restrictions on olens, aromatics, heavy ends, and sulfur. This required more hydrotreating, alkylation and cracking capability. The investment to make all these changes through 1996 is in the tens of billions of dollars, nearly equaling the capitalization of the rening industry at the beginning of the reformulated gasoline era. Now, with Tier 2 sulfur reduction in the U.S. and other sulfur reduction regulations abroad in the near future, sulfur reduction units will have to be installed. Desulfurization of gasoline blending streams may be required in addition to severe hydrotreating of FCC feed to meet the very low sulfur content limits. Severe conventional hydrotreating can result in a loss in octane number because of saturation of high-octane-number olens and aromatics. New versions of hydrotreaters do not cause as much of an octane number loss. New renery processes for removing sulfur do not involve the use of hydrogen (see page 33).
Blending
Despite the diversity and ingenuity of the processes within a modern petroleum renery, no single stream meets all the requirements of gasoline. Thus, the nal step in gasoline manufacture is blending the various streams into a nished product. It is not uncommon for the nished gasoline to be made up of six or more streams (see Figure 3-4 ). Sometimes, to provide more exibility, a stream is distilled into several fractions and each fraction is used as a separate blending component, for example, FCC light and FCC heavy gasoline. Several factors make this exibility critical: The requirements of the gasoline specication (ASTM D 4814) and the regulatory requirements are complex. Different marketing locations served by the renery may have different performance and regulatory specications (see Chapters 1 and 2 ). A blend must satisfy multiple internal inventory and economic requirements. To obtain an on-test blend, on time, every time, reners use computerized blending programs to generate an optimized blend recipe. A computer program integrates all the performance, regulatory, economic, and inventory requirements.
Contamination and Adulteration

During the manufacturing and distribution of gasoline, it comes into contact with water and particulate matter. It can become contaminated with such materials. Water is allowed to settle from the fuel in storage tanks and the water is regularly withdrawn and disposed of properly. Particulate matter is removed by lters installed in the distribution system. Appendix X6 of
ASTM D 4814 recommends the installation of lters of 10 (micrometer) or less nominal pore
size on all dispensers delivering fuel to the customer.

35
Adulteration differs from contamination in that unacceptable materials deliberately are added to gasoline by unscrupulous people to enhance their income. It may be as simple as adding regulargrade gasoline to the premium-grade gasoline storage tank, which lowers the octane number of the premium. In areas where kerosene is less expensive than gasoline because of government subsidies and/or no road taxes, kerosene may be added to gasoline. This not only lowers the octane number but also adversely affects the volatility, which in turn affects driveability. Used toluene from manufacturing processes containing soluble silicon compounds, which was supposed to be used as a paint solvent, has found its way into gasoline. The silicon fouled oxygen sensors and plugged exhaust catalysts, causing severe performance problems and expense. In some countries, dyes and markers are used to detect adulteration. ASTM D 86 distillation testing and/or ASTM D 2699/ASTM D 2700 octane number testing may be required to detect adulteration.
Gasoline Additives
Additives are gasoline-soluble chemicals mixed with gasoline to enhance certain performance characteristics or to provide characteristics not inherent in the gasoline. Typically, they are derived from petroleum-based raw materials and their function and chemistry are highly specialized. They produce the desired effect at the parts-per-million (ppm) concentration range. (One ppm is 0.0001 mass percent or 1mg/kg.)
Oxidation inhibitors, also called antioxidants, are aromatic amines and hindered phenols. They
prevent gasoline components from reacting with oxygen in the air to form peroxides or gums. They are needed in virtually all gasolines, but especially those with a high olens content. Peroxides can degrade antiknock quality, cause fuel pump wear, and attack plastic or elastomeric fuel system parts, soluble gums can lead to engine deposits, and insoluble gums can plug fuel lters. Inhibiting oxidation is particularly important for fuels used in modern fuel-injected vehicles, as their fuel recirculation design may subject the fuel to more temperature and oxygen-exposure stress.
Corrosion inhibitors are carboxylic acids and carboxylates. The facilities tanks and pipelines
of the gasoline distribution and marketing system are constructed primarily of uncoated steel. Corrosion inhibitors prevent free water in the gasoline from rusting or corroding these facilities. Corrosion inhibitors are less important once the gasoline is in the vehicle. The metal parts in the fuel systems of todays vehicles are made of corrosion-resistant alloys or of steel coated with corrosion-resistant coatings. More plastic and elastomeric parts are replacing metals in the fuel systems. In addition, service station systems and operations are designed to prevent free water from being delivered to a vehicles fuel tank.
Metal deactivators are chelating agents chemical compounds that capture specic metal ions. The
more-active metals, like copper and zinc, effectively catalyze the oxidation of gasoline. These metals are not used in most gasoline distribution and vehicle fuel systems. But when they are present, metal deactivators inhibit their catalytic activity.
Demulsiers are polyglycol derivatives. An emulsion is a stable mixture of two mutually insoluble
materials. A gasoline-water emulsion can be formed when gasoline passes through the high-shear
36
Chapter 3
eld of a centrifugal pump if the gasoline is contaminated with free water. Demulsiers improve the water-separating characteristics of gasoline by preventing the formation of stable emulsions.
Antiknock compounds are lead alkyls tetraethyl lead (TEL) and tetramethyl lead (TML), manganese
compounds methylcyclopentadienyl manganese tricarbonyl (MMT), and iron compounds ferrocene. Antiknock compounds increase the antiknock quality of gasoline. Because the amount of additive needed is small, they are a lower cost method of increasing octane number than changing gasoline chemistry. Gasoline containing tetraethyl lead was rst marketed in 1923. The average concentration of lead in gasoline gradually was increased until it reached a maximum of about 2.5 grams per gallon (g/gal.) in the late 1960s. After that, a series of events resulted in the use of less lead: new rening processes that produced higher-octane gasoline components, steady growth in the population of vehicles requiring unleaded gasoline, and EPA regulations requiring the reduction of the lead content of gasoline in phased steps beginning in 1979. The EPA completely banned the addition of lead additives to on-road gasoline in 1996 and the amount of incidental lead may not exceed 0.05 g/gal.
MMT was commercialized in 1959 and was used in gasoline alone or in combination with the lead
alkyls. The Clean Air Act Amendments of 1977 banned the use of manganese antiknock additives in unleaded gasoline unless the EPA granted a waiver. MMT continued to be extensively used in unleaded gasoline in Canada at concentrations up to 0.068 g/gal. (18 mg/L). In 1996, after several waiver requests and court actions by the manufacturer, the courts ordered the EPA to grant a waiver for MMT. Its use is limited to a maximum of 0.031 g/gal. (8.2 mg/L). California regulations continue to ban the addition of manganese to gasoline.
MMTs future in the U.S. is clouded: Its use in gasoline is opposed by environmental groups and
the automobile manufacturers. Gasoline containing MMT leaves signicant red-orange deposits on spark plugs, catalytic converters, oxygen sensors and combustion chamber walls. The additive manufacturer has developed a large body of data to support its claim that MMT in gasoline does not reduce performance or increase emissions. The auto manufacturers have expressed concerns about shortened catalyst, oxygen sensor, and spark plug life and interference with the performance of the new on-board diagnostic system (OBD; see page 62). The auto industry conducted a large vehicle test of MMT that showed increased exhaust hydrocarbon emissions and increases in other emissions in some vehicles at high mileages in vehicles designed to meet low-emission limits. There have been reports of plugging in high-density honeycomb (brick) catalyst systems with MMT. The additive manufacturer takes exception to the autos test results and concerns over catalyst plugging. Some new vehicle owners manuals recommend against using gasoline containing MMT. Very little
MMT is being used in U.S. gasoline at this time (2003). The controversy over MMT continues.
In many parts of the world, lead antiknocks are being eliminated from gasoline used in vehicles that do not have catalytic exhaust emission controls. This gasoline frequently is referred to as lead replacement petrol. Because many of the reneries in the world do not have the processing capability in place to meet octane number needs without an antiknock additive, MMT is being using in lead replacement petrol. The use of MMT helps protect engines susceptible to exhaust valve recession. Alternatives to using MMT for octane enhancement are the use of oxygenates, alkylates, and aromatics until processing can be constructed. The auto industry also opposes the use of MMT in this gasoline
37
Density and Gravity Density ( ) is the mass of a unit volume of material at a selected temperature. For example, the density of water is 0.9990 grams per cubic centimeter (g/cm3) at 15.6C (60F). Relative density (RD) also called specic gravity is the ratio of the density of the material at a selected temperature to the density of a reference material at a selected temperature. For the relative density of petroleum crudes and products in the U.S., the reference material is water and both temperatures are 60F (15.6C). sample (60F) water (60F)
because of concern that this lead replacement petrol will nd its way into emission-controlled vehicles. Lead replacement petrol is usually dispensed through wide nozzles to prevent misfueling. Ferrocene (dicyclopentadienyl iron) has been around for nearly 50 years. It has not been widely marketed as an antiknock, although it has seen limited use in Europe. When combusted, it forms ferric oxides (also known as jewelers rouge), a ne abrasive. Early studies of ferrocene showed excessive piston ring, cylinder bore, and camshaft engine wear at the concentrations investigated. Recent studies by the auto industry at lower iron concentrations have shown premature spark plug failures at the current recommended concentration of 30 ppm (9 ppm Fe). Concern also has been expressed that the ferric oxide will act as a physical barrier on oxygen sensors and exhaust catalyst surfaces and possibly cause catalyst plugging in modern vehicles. In the U.S., ferrocene cannot be used in reformulated gasoline because of a ban on the use of heavy metals. Further, it cannot be used in conventional gasoline without rst obtaining a waiver from EPA, which requires extensive vehicle emission testing.
Deposit control additives See Chapter 6. Anti-icing additives are surfactants, alcohols, and glycols. They prevent ice formation in the
RD (6060F) =
carburetor and fuel system (see page 4). The need for this additive is disappearing as older-model
The U.S. petroleum industry often uses API gravity instead of relative density. The following equation relates API gravity, in degrees API (API), to relative density. 141.5 RD (6060F) While API gravity measurements may be made on liquids at temperatures other than 60F (15.6C), the result is always converted to the value at 60F (15.6C), the standard temperature. As the above formula indicates, API gravity is inversely proportional to relative density: API gravity increases as relative density decreases. Thus, a high-gravity crude has a lower density than a low-gravity crude. Many other parts of the world use Density (usually at 15C and expressed as kg/m 3) rather
vehicles with carburetors are replaced by vehicles with fuel injection systems.
Dyes are oil-soluble solids and liquids used to visually distinguish batches, grades, or applications of
gasoline products. For example, gasoline for general aviation, which is manufactured to different and more exacting requirements, is dyed blue to distinguish it from motor gasoline for safety reasons.
API =
131.5
Markers are a means of distinguishing specic batches of gasoline without providing an obvious
visual clue. A rener may add a marker to its gasoline so it can be identied as it moves through the distribution system.
Drag reducers are high-molecular-weight polymers that improve the uid ow characteristics of
low-viscosity petroleum products. As energy costs have increased, pipelines have sought more efcient ways to ship products. Drag reducers lower pumping costs by reducing friction between the owing gasoline and the walls of the pipe.
Specications
It has been critical to the successful development of gasoline and gasoline-powered vehicles to have consensus among reners, vehicle manufacturers, and other interested parties on the characteristics of gasoline necessary for satisfactory performance and reliable operation. This consensus is reached in the U.S. under the auspices of the ASTM International (formerly the American Society for Testing and Materials or ASTM). Many countries have gasoline specications that control similar properties to those specied in ASTM D 4814. In Canada, the Canadian General Standards Board (CGSB) serves the functions of ASTM and issues CGSB 3.5-99. The European Committee for Standardization (CEN) issues EN specications in Europe, which are then translated into national specications for each country such as BS EN 228 (UK), NF EN 228 (France),
DIN EN 228 (Germany), DS/EN 228 (Denmark), NS-EN 228 (Norway), and UNI EN228 (Italy).
than API Gravity or Relative Density.
38
The Japan Standards Association (JSA) issues gasoline specication JIS K 2202 and test methods.
Chapter 3
Test methods in Europe are supported by ISO, CEN, and the national institutes such as DIN (Germany), AFNOR (France), and BS (UK).
ASTM International Committee D-2 on Petroleum Products and Lubri-
Figure 3-5 ASTM D 4814 Properties Property

Schedule of Seasonal and Geographic Volatility Classes, which includes:
Intent To ensure good driveability. (see Chapter 1)
cants is responsible for gasoline specications and test methods. A large number of groups are interested in and/or affected by the specications. Their viewpoints are brought to the D-2 forum by representatives who also are members of ASTM: Individual reners American Petroleum Institute (API), an association of petroleum reners Petroleum marketing organizations Vehicle and engine manufacturers Alliance of Automobile Manufacturers (AAM), an association of vehicle manufacturers Automotive equipment suppliers Governmental regulatory agencies like the United States Environmental Protection Agency, California Air Resources Board, and state weightsand-measures agencies Independent research laboratories and consultants SAE International (formerly the Society of Automotive Engineers) Coordinating Research Council (CRC), an organization that directs, through committee action, engineering and environmental studies on the interaction between automotive equipment and petroleum products The ASTM specication for gasoline, D 4814 Standard Specication for Automotive Spark-Ignition Engine Fuel, is widely recognized.2 It has been written into federal regulations and most state specications for gasoline.
D 4814 species nine gasoline properties (Figure 3-5). These do not
Vapor Pressure/Distillation Class Vapor Lock Protection Class

Solvent Washed Gum Content
To protect against the presence of gums formed by oxidation, which can contribute to fuel system deposits. To protect against the formation of additional gum by air oxidation during storage. To protect against the phase separation of dissolved water at colder temperatures. Not ususally a problem for hydrocarbon blends but can be for some oxygenated blends (see page 50). To protect against engine wear, deterioration of engine oil, corrosion of exhaust system parts and a temporary reduction in the efciency of the converter catalyst. To protect against corrosion of fuel system parts due to reactive sulfur compounds. To ensure that unleaded gasolines are free of lead. To ensure product is visually free of undissolved water, sediment, and suspended matter.
Oxidation Stability
Water Tolerance
Sulfur Content
Copper Strip Test
Lead Content
include octane number or antiknock index, which are set by gasoline reners and marketers based on their perception of the technical and competitive needs in the market.3
D 4814 references more than 30 other ASTM standards that describe how
Appearance
to sample gasoline and how to run specic test methods. These associated methods are essential. Specifying a property has no value unless everyone measuring the property uses the same procedure and, for a given material, gets the same answer within the dened precision. D 4814 also contains six appendices, including one that discusses the signicance of specications and another that summarizes EPAs gasoline regulations.
2 The hyphenated sufx associated with the method number indicates the year the method was last updated and the version within the year, e.g., D 4814-03a. 3 ASTM D 4814 39
EPA and some states set additional standards for gasoline. These are not included in D 4814 unless
they involve properties traditionally covered by the method, e.g., vapor pressure, in which case,
ASTM revises D 4814 to conform to the regulations if they have been approved by EPA.
Each gasoline rener, each pipeline that ships gasoline, some states, and even the automobile manufacturers may set additional internal specications beyond ASTM D 4814, or may set more stringent limits for the D 4814 properties. But, except in the case of internal rening specications, these limits will not prevail unless all interested parties recognize their value. Federal and California reformulated gasoline have specic limits to help control emissions and also specify approved test methods to determine compliance. Terminology, requirements, test methods, applicable areas, and discussion of RFG for both federal and California programs are summarized in ASTM Committee D02 on Petroleum and Lubricants Research Report D02: 1347, Research Report on Reformulated Spark-Ignition Engine Fuel.
Test Methods
Vapor Pressure
ASTM D 323 Test Method for Vapor Pressure of Petroleum Products (Reid Method)4 ASTM D 5190 Test Method for Vapor Pressure of Petroleum Products (Automatic Method) ASTM D 5191 Test Method for Vapor Pressure of Petroleum Products (Mini Method) ASTM D 4953 Test Method for Vapor Pressure of Gasoline and Gasoline-Oxygenate Blends (Dry Method)
In all four methods, a chilled xed volume of gasoline is placed in a test chamber and heated to 38.8C (100F). Then the pressure developed by gasoline vapors is measured in units of pounds per square inch (psi) or kilopascals (kPa). The methods differ in the design of the apparatus, including the design of the test chamber. D 323 yields Reid vapor pressure (RVP), the other methods yield Dry Vapor Pressure Equivalent (DVPE).
Octane Number
ASTM D 2699 Standard Test Method for Research Octane Number of Spark-Ignition Engine Fuel ASTM D 2700 Standard Test Method for Motor Octane Number of Spark-Ignition Engine Fuel
Both these test methods employ a CRC single-cylinder, variable-compression, knock-test engine. The engine is operated under different test conditions of speed, mixture temperature, and spark advance for each method. The compression ratio of the test engine is adjusted to produce a knock of standardized intensity for the test gasoline the gasoline being rated. Then the primary reference fuel whose knock intensity matches that of the test gasoline at the set compression ratio is identied. The octane number of the reference fuel is the octane number of the test gasoline. The series of primary reference fuels are blends of normal heptane (octane number dened equal to zero) and isooctane (2,2,4-trimethylpentane an octane number dened equal to 100). The octane number of each primary reference fuel is equal to the volume percent of isooctane it contains.
40
4 D 323 cannot be used to measure the vapor pressure of gasoline containing ethanol and, therefore, no longer is recognized by D 4814.
Chapter 3
Chapter 1 discusses the signicance of Research octane number (RON), Motor octane number (MON), and Antiknock Index and how they are used to dene the antiknock quality of gasoline.
Road Octane Number (RdON)

Generally, RdON is determined by the Modied Uniontown Procedure, CRC Designation F-28. In this procedure, a test vehicle is operated on a series of primary reference fuels of increasing octane number under maximum-throttle acceleration.5 The basic timing is advanced for each reference fuel until trace knock the lowest knock level detected by the ear of the person rating the fuel is detected. The plot of basic spark timing versus RON provides a primary reference curve for the test car. Then the car is operated on the gasoline to be rated until the spark advance needed to cause trace knock under maximum throttle acceleration is found. The octane number associated with that spark timing advance in the primary reference curve is the RdON of the test gasoline. Because of the numerous variables involved, 10 to 15 test vehicles, usually different models, must be used for a statistically signicant determination. The nal RdON of the test gasoline is the average of RdONs of the individual vehicles.
Distillation Prole
ASTM D 86 Test Method for Distillation of Petroleum Products
A 100 mL sample is placed in a round bottom ask and heated at a rate specied for samples with its vapor pressure characteristics. Temperatures are recorded when the rst drop is collected (initial boiling point), at recovered volumes of 5 mL, 10 mL, every subsequent 10 mL interval to 90 mL, 95 mL and at the end of the test (end point). For gasoline samples, the temperatures associated with each incremental volume percentage recovered are converted to temperatures for each incremental volume percentage evaporated by correcting for any sample loss during the test.
Vapor-Liquid Ratio (V/L)

ASTM D 2533 Test Method for Vapor-Liquid Ratio of Spark-Ignition Engine Fuels ASTM D 5188 Test Method for Vapor-Liquid Ratio Temperature Determination of Fuels
(Evacuated Chamber Method )

ASTM D 4814, Appendix X2 Three calculation methods a computer method, linear equation
method, and nomograph method for estimating V/L from vapor pressure and distillation test results (not applicable for oxygenated gasolines). In D 2533, a measured volume of liquid fuel at 0C (32 F) is introduced into a glass buret lled with glycerol (non-oxygenated fuel) or mercury (all fuels). The buret is heated to the desired temperature and the volume of vapor in equilibrium with the liquid is recorded after the pressure of the system has been adjusted to the desired pressure, usually one atmosphere (760 mm Hg or 101.3 kPa). If the temperature corresponding to a given vapor-liquid ratio is desired usually
V/L = 20 the vapor-liquid ratio is determined at several temperatures, the results plotted, and
the temperature at the desired vapor-liquid ratio is read from the plot.
5 This test cannot be run on modern vehicles whose timing is regulated by an engine control module (see page 61) 41
In D 5188, a calculated volume of air-saturated sample (all fuels) at 0C (32F) is introduced into an evacuated, thermostatically controlled test chamber of known volume. The sample volume is calculated to obtain the desired vapor-liquid ratio in the chamber. After injection, the chamber temperature is adjusted until a stable chamber pressure of 101.3 kPa (760 mm Hg) is achieved.
API Gravity (see page 38)

ASTM D 1298 Standard Practice for Density, Relative Density (Specic Gravity), or API Gravity of
Crude Petroleum and Liquid Petroleum Products by Hydrometer Method

ASTM D 4052 Test Method for Density and Relative Density of Liquids by Digital Density Meter
For D 1298, the sample is placed in a cylinder and the appropriate hydrometer is lowered into the sample. After temperature equilibrium has been reached, the sample temperature and hydrometer scale reading are recorded. The Petroleum Measurement Tables are used to convert the recorded value to the value at a standard temperature such as 60F or 15C For D 4052, about 0.7 mL of liquid sample is introduced into an oscillating sample tube and the change in oscillating frequency caused by the change in the mass of the tube is used in conjunction with calibration data to determine the density of the sample.
Induction Period
ASTM D 525 Test Method for Oxidation Stability of Gasoline (Induction Period Method)
Fifty millilitres of gasoline are placed in a glass sample container in a pressure vessel and oxygen is introduced to a pressure of about 700 kPa (100 psi). The charged pressure vessel is placed in a 100C (212F) bath and the pressure continuously monitored. The break point of the fuel is determined when a specied drop in pressure in 15 minutes is observed. The number of minutes to the break point is reported.
Solvent Washed Gum Content

ASTM D 381 Test Method for Gum Content in Fuels by Jet Evaporation
Fifty millilitres of gasoline are evaporated under controlled conditions of temperature 155C (about 310F) and air ow for 30 minutes. The residue is weighed before and after extraction with n-heptane and the result reported as milligrams per 100 mL.
Potential Gum
ChevronTexaco Method based on ASTM D 873 Test Method for Oxidation Stability of Aviation Fuels (Potential Residue Method), which combines ASTM D 525 Test Method for Oxidation Stability of Gasoline (Induction Period Method) and ASTM D 381 Test Method for Gum Content in Fuels by Jet Evaporation. One hundred millilitres of gasoline free of deposit control additive is oxidized for four hours at 100C (212F) in a bomb initially charged with 700 kPa (100 psi) of oxygen. After this treatment, the amount of insoluble gum is collected by ltration and measured and the soluble gum is isolated by ASTM D 381 and measured. The total insoluble and soluble gum is reported as
42
potential gum in units of milligrams per 100 mL.
Chapter 3
Sulfur Content
ASTM D 1266 Test Method for Sulfur in Petroleum Products (Lamp Method ) ASTM D 2622 Test Method for Sulfur in Petroleum Products by X-Ray Spectrometry ASTM D 3120 Test Method for Trace Quantities of Sulfur in Light Liquid Hydrocarbons by
Oxidative Microcoulometry
ASTM D 4045 Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric
Colorimetry
ASTM D 4294 Test Method for Sulfur in Petroleum and Petroleum Products by Energy-Dispersive
X-ray Fluorescence Spectrometry

ASTM D 5453 Test Method for Determination of Total Sulfur in Light Hydrocarbons, Motor
Fuels and Oil by Ultraviolet Fluorescence

ASTM D 6334 Test Method for Sulfur in Gasoline by Wavelength Dispersive X-Ray Fluorescence ASTM D 6445 Test Method for Sulfur in Gasoline by Energy-Dispersive X-ray Fluorescence
Spectrometry As the sulfur test method names indicate, there are several technologies used to determine the sulfur content of gasoline. Some of the methods are applicable only to high sulfur levels, others cover a broad range, and some can be used only for low sulfur levels. Specic test methods need to be reviewed for applicability before selecting one to use.
Copper Strip Corrosion

ASTM D 130 Test Method for Detection of Copper Corrosion from Petroleum Products by the
Copper Strip Tarnish Test

D 130 can be used to detect the presence of free sulfur or reactive sulfur compounds. In this test
method, a polished copper strip is immersed in 30 mL of gasoline and heated to 50C (122F) for 3 hours. The test strip is compared to standard strips and reported on a scale of one to four (one being best). It is becoming clear that as sulfur levels in gasolines are forced lower, many sulfur species that actually provided protection for copper surfaces are being greatly reduced or eliminated. In extremely low sulfur content reformulated gasolines, levels of free sulfur or reactive sulfur compounds that would not have caused a failed copper strip test in conventional gasolines may now cause a failure. This factor increases the urgency for minimizing contamination with even minor levels of free sulfur or reactive sulfur compounds in processing at the renery.
Appearance
ASTM D 4176 Test Method for Free Water and Particulate Contamination in Distillate Fuels
(Visual Inspection Procedure) can be used for determining appearance. The sample in a clear glass jar is visually inspected for undissolved water, sediment, and suspended matter. For gasoline it is done at ambient temperature or 21C (70F), whichever is higher. The fuel is reported to be clear and bright and free of suspended material.
43
4 Oxygenated gasoline
Introduction
In the 1990s, air quality regulations required gasolines in some parts of the U.S. to be oxygenated either in the winter or year-round gasolines in carbon monoxide (CO) nonattainment areas and federal Phase I and California Phase 2 reformulated gasolines (RFG) (see pages 24 and 25). But oxygenated gasoline is not new. Oxygenates primarily ethanol (ethyl alcohol or grain alcohol) have been added to gasoline for decades. Widespread use of ethanol in the United States began in 1978 when a Nebraska group marketed gasoline containing 10 volume % ethanol as gasohol. The program was a means to increase gasoline availability during the oil embargo. Later, the gasohol name was abandoned, but the use of ethanol continued. By 2001, some 10 percent of all the gasoline sold in the United States contained ethanol and 58 percent of the blends contained 10 vol % ethanol. This 10 volume % ethanol blend is sometimes referred to as E10. Much of the early blend was marketed in the Midwestern states, the same region where the bulk of ethanol is produced, but after the 1990 wintertime oxygenated gasoline began, ethanol was mostly used in this program throughout the U.S. Initially, little RFG contained ethanol. The rst
EPA waiver for MTBE was issued in 1979 for 7.0 vol % and a second waiver for 15.0 vol % was
issued in 1988. Wide use of MTBE did not occur until the late 1980s and then its use expanded with the introduction of federal RFG in 1995. After the discovery of MTBE in various fresh-water resources, and because tiny amounts of MTBE affect the taste and odor of drinking water, MTBE and other ethers have been banned in California effective January 1, 2004 and many other states have passed or are considering legislation adopting similar prohibitions. Congress is considering phasing out MTBE nationwide and also is considering a renewable-fuels standard. Banning
MTBE and/or adopting a renewable-fuels standard will result in increased usage of ethanol.
Chemistry
Oxygenated gasoline is a mixture of conventional hydrocarbon-based gasoline and one or more oxygenates. Oxygenates are combustible liquids made up of carbon, hydrogen, and oxygen. All the current oxygenates belong to one of two classes of organic molecules: alcohols and ethers.1 In alcohols, a hydrocarbon group and a hydrogen atom are bonded to an oxygen atom: R-O-H, where R represents the hydrocarbon group. All alcohols contain the OH atom pair. In ethers, two hydrocarbon groups are bonded to an oxygen atom; the groups may be the same or different: R-O-R or R-O-R.
1 The word ether reminds many people of the anesthetic. Although the anesthetic commonly is called ether, its correct chemical name is diethyl ether (CH3CH2OCH2 CH3). It is not used as a gasoline oxygenate because it is too volatile.
45
Figure 4-1 Information About Oxygenates for Oxygen Content Mass % 34.73 18.15 Blending Research Octane Number (BRON)1 129 118 Maximum Concentration Approved by EPA2 Mass % Volume % Oxygen Oxygenate ( 3 . 7 0 )3 (2.74) 10.0 15.0
Name Ethanol (EtOH) Methyl Tertiary-Butyl Ether (MTBE)
Formula C 2 H6 O C 5 H 1 2O
Structure C H3 C H2 OH
CH3 | CH3 O C CH3 | CH3 CH3 | CH3 CH2 O C CH3 | CH3 CH3 | CH3 O C CH2 CH3 | CH3
Ethyl Tertiary-Butyl Ether (ETBE)
C 6 H 1 4O
15.66
119
2.70
(17.1)
Tertiary-Amyl Methyl Ether (TAME)
C 6 H 1 4O
15.66
112
2.70
(16.6)
1 RON of the pure compound that is consistent with the RON of the oxygenate-gasoline mixture obtained by blending. 2 Values in parentheses calculated from limit using known relative density of the oxygenate and 0.74 relative density of gasoline (60/60 F).
Use
The EPA regulates which oxygenates can be added to gasoline in the U.S. and in what amounts through the Substantially Similar rule and waivers (see sidebar on page 48). The most widely used oxygenates in the U.S. are ethanol, methyl tertiary-butyl ether (MTBE) and tertiary-amyl methyl ether (TAME). Ethyl tertiary-butyl ether (ETBE) is another ether that could be used. Figure 4-1 summarizes some information about these oxygenates. Note that, on a volume basis, each ether has a different maximum concentration because each has a different oxygen content and relative density. Figure 4-2 gives the ranges of oxygenate use in terms of oxygen content of the gasoline required by the U.S. emission regulations. The regulations do not require a specific oxygenate. Any oxygenate use conforming with the EPAs Substantially Similar or Waiver conditions is acceptable. Different gasoline brands in the same area tend to contain the same oxygenate, but uniformity is not required. Here are a few of the many factors that determine a refiners oxygenate choice: What are the economics? Ethanol can be more economical than the ethers because there is a federal excise tax exemption for its use, and about one-third of the states also offer a tax exemption or other incentive. These incentives are designed to encourage the development of an agriculturally based fuel ethanol industry. What is the availability? The bulk of the ethanol is produced in the Midwest. Some ether plants are in or adjacent to refineries and use refinery streams as feed.
46
Chapter 4
Oxygenated Gasoline
Figure 4-2 Oxygen Content Required by U.S. Emissions Regulations Oxygen Content, Mass Regulation
CO Nonattainment Areas
2 1
Methanol Is Not Ethanol Ethanol and methanol should not be confused; they are different compounds. While limited Maximum amounts of gasoline oxygenated with methanol and its cosolvents have been available in the past, its use in the future is likely to be minimal. Minimum
Average
(4 or 5 Winter Months) California Other States

Federal RFG
4,5
1.8 2.7
2.2 3 3.7
Gasoline oxygenated with methanol is more corrosive toward fuel system metals and accel-
Complex Model Phase II

California Phase 3 RFG
2
2.1
1.5
4.0
erates deterioration of elastomers. Gasoline oxygenated with methanol is not approved by many vehicle owners manuals.
Summer Flat Limit Predictive Model Winter Flat Limit Predictive Model
1.8 7 0.0 1.8 8 1.8
2.2 9 3.5 2.2 9 3.5
Adding methanol to gasoline signicantly increases the vapor pressure of the blend an undesirable effect in this era of more stringent volatility controls. Methanol, unlike ethanol, is toxic.
1 Regardless of this limit, specic oxygenates may not exceed their Substantially Similar or Waiver limits. For example, the Substantially Similar maximum limit for ethers like MTBE is 2.7 mass % oxygen (2.9 mass % in CO nonattainment areas in the winter). 2 Per-gallon limits. 3 The maximum winter limit for Substantially Similar oxygenates is 2.9 mass % in CO nonattainment areas. 4 Average limits. 5 CO nonattainment area oxygen limits take precedence over RFG oxygen limits in CO nonattainment areas in the winter. 6 Upper limit of valid range for oxygen content variable in model. 7 Value controlled by Predictive Model except in federal RFG areas in California where the 1.5 mass % limit applies. 8 The minimum limit only applies during specied winter months in specied CO nonattainment areas. 9 If the gasoline contains more than 3.5 mass % oxygen but no more than 10 vol % ethanol, the maximum oxygen content cap is 3.7 mass % oxygen.
What is the best blending location? At reneries, ethers usually are used because ethanol blends cannot be shipped by pipeline. It is hard to keep pipelines dry, and water in the pipeline will reduce the ethanol content of the gasoline (see page 50). The water tolerance of ethers is similar to that of gasoline. Regulations limiting the use or banning of MTBE. The adoption of a Renewable Fuels Standard. At terminals, standard practice is to blend ethanol with gasoline in the tank truck that will deliver the blend to the service station. Terminal blending involves more operating and capital expense than renery blending. Also, because oxygenates raise octane, a low-octane conventional gasoline is needed, if the resulting oxygenated gasoline is to have the AKI commonly available in the area. For RFG, the volatility of the base fuel must be adjusted so it will meet federal and state volatility requirements after the addition of ethanol. Such a base fuel is referred to as RBOB (reformulated gasoline blendstock for oxygenate blending). In California, it is referred to as CARBOB.
47
U. S. Oxygenate Regulation and the Substantially Similar Rule The Clean Air Act Amendments of 1977 control the use of oxygenates in unleaded gasoline. The purpose is to ensure that oxygenate use wont contribute to emission control system failures that could result in increased emissions. The regulations that the EPA developed to implement the law prohibit the introduction or increase in concentration of a fuel or fuel additive that is not substantially similar to any fuel or fuel additive used in the certication of any 1975 or subsequent model year vehicle. In 1981, the EPA issued the Substantially Similar Ruling recognizing that the use of certain types of oxygenates was safe below a specied oxygen content. The rule, as revised in 1991, allows aliphatic alcohols (excluding methanol) and/or aliphatic ethers to be blended into gasoline up to a concentration that would result in 2.7 mass % oxygen in the blend. The rule requires the nished blend to possess all the physical and chemical characteristics of an unleaded gasoline specied by ASTM D 4814-88 for at least one of the seasonal and geographic volatility classes. (continued on next page)
Oxygenates may be used in areas of the U.S. where they are not required as long as EPAs concentration limits are observed. Because all oxygenates are more expensive than the conventional gasoline they displace, ethanols tax incentives make it the only one likely to be used near its concentration limit. The other oxygenates will be used at lower concentrations (17 vol %) only when the octane of the gasoline needs enhancement and when adding oxygenates is the most economical solution. The information available to the retail consumer about the oxygenate composition of the gasoline varies. There is no federal labeling regulation; this is an area controlled by state regulations. Some states require dispenser labels for oxygenated gasolines in wintertime CO nonattainment areas and RFG gasolines. A typical label reads: The gasoline dispensed from this pump is oxygenated and will reduce carbon monoxide pollution from motor vehicles. Some labels, like this one, do not provide any information on which oxygenate(s) the blend contains; others do. Few, if any, states require labeling for gasolines containing low levels of ethers added to increase octane. A national association of state weights-and-measures agencies responsible for dispenser calibration and labeling issued a revised standard guideline for dispenser labeling in 1996. Several states recently have dropped ethanol labeling requirements and some are now requiring labeling for MTBE. Outside the U.S., the EN 228 specication limits the maximum amounts of various oxygenates as shown in Figure 4-3. The European Union has set targets for each member state for the market share of biofuels. These targets will be based on the challenging benchmarks set by Directive 2003/ 30/EC: 2 percent market share by December 2005; 5.75 percent market share by December 2010. The JIS K 2202 standard allows MTBE only up to 7 volume % maximum. Canada limits methanol to 0.3 volume %, other oxygenates to 2.7 mass % oxygen, and ethanol specically to 3.7 mass % oxygen (nominally 10 volume % ethanol). Brazil allows up to 24 volume % ethanol, but the vehicles are calibrated to use this high level.
Sources
Figure 4-3 EN 228: Oxygenates Requirements Oxygenate Methanol Ethanol Isopropyl Alcohol Isobutyl Alcohol tert-Butyl Alcohol Ether (5 or more C atoms) Other Oxygenates Maximum, Vol % 3 5 10 10 7 15 10
Ethanol can be synthesized from petroleum by hydrating ethylene, but most of it (94 percent in
1993) is derived from the fermentation of carbohydrates, principally corn in the U.S., although
sugarcane is used in many parts of the world. The process involves distillation to separate it from the fermentation residues, dehydration to remove the water that codistills with the alcohol and, for fuel ethanol, the addition of a noxious or toxic material (denaturing) to make it unt for human consumption. MTBE is derived from methanol and isobutylene. A catalyst is used to assist the reaction.
CH3 CH3 OH e CH2 C CH3
Catalyst 200F 250 psi
CH3 CH3 O C CH3 CH3
48
Chapter 4
Oxygenated Gasoline
Most methanol is produced from natural gas (methane). Isobutylene is obtained from petroleum, either as a by-product of the rening process or from butane. Although it is made from methanol,
MTBE is a different material with different properties. It doesnt have methanols corrosivity and
(continued from previous page) The EPA regulations also created a process by which a waiver could be granted for an oxygenate recipe that the applicant had demonstrated would not cause or contribute to the failure of any emission control device or system. The EPA has granted waivers for concentrations of ethanol in gasoline
toxicity defects (see sidebar on page 47). The other ethers are made by the similar processes. ETBE is derived from ethanol and isobutylene.
TAME is derived from methanol and isoamylenes.
Specications
ASTM D 4806 Specication for Denatured Fuel Ethanol for Blending with Gasolines for Use as
up to 10 volume %. (The mass % oxygen content of this blend depends on the density of the gasoline; it is 3.7 mass % for pure ethanol added to gasoline with the typical relative density of 0.74 at 60/60F (15.6/15.6C); it is 3.5 mass % for a mixture of 90 vol % gasoline and 10 volume % denatured ethanol.) The EPA also has ruled that gasolines containing up to 2.0 vol % MTBE not purposely added that are subsequently blended with 10 volume % ethanol (4.0 mass % oxygen total for pure ethanol) do not violate the ethanol
Automotive Spark-Ignition Engine Fuel is used to specify product quality for ethanol in the U.S. The California Air Resources Board species D 4806 with additional limits on sulfur content, aromatics content, benzene content, and olens content for use in California Phase 3 RFG. D 4806 limits denaturants to hydrocarbons boiling in the gasoline range because of harmful side effect concerns for other materials.
ASTM D 5983 Specication for Methyl Tertiary-Butyl Ether (MTBE) for Downstream Blending
with Automotive Spark-Ignition Engine Fuel is used for merchant MTBE in the U.S.
Performance Issues
Fuel Leaning Oxygenated gasoline leans the air-fuel mixture of carbureted engines and fuel
waiver. This was to assure an adequate supply of base gasoline for blending with ethanol. The EPA also has granted waivers for blends of gasoline and gasoline-grade tertiary-butyl alcohol (TBA) up to 3.5 mass % oxygen content (16 vol % TBA) and for various blends of methanol and gasoline-grade TBA or other higher-molecularweight alcohols (cosolvents). Further, any fuel or fuel additive registered with EPA also has to have a supplemental registration involving toxicity that may require additional toxicity testing. None of the methanol-containing waivers has a supplemental registration.
injected engines that dont have an electronic control module (ECM) (see page 60). Engines with
ECMs become fuel lean when the ECM is not controlling when the engine is cold or the vehicle
is being accelerated rapidly. The rest of the time, the ECM adjusts the air-fuel ratio to compensate for the oxygen in the fuel. If a carburetor is set to provide a very fuel-rich mixture, fuel leaning might improve performance. Otherwise, fuel leaning can degrade driveability; the extent depends on the engines calibration. Ethanol has a higher heat of vaporization than ethers. Some of the degradation in driveability of gasoline oxygenated with ethanol can be attributed to the additional heat needed to vaporize the fuel.
Volatility Adding ethanol to a conventional gasoline not designed for alcohol blending can
produce a blend that is too volatile. Ethanol can increase the vapor pressure 6.9 kPa (1.0 psi) for a conventional gasoline with a vapor pressure of 62 kPa (9.0 psi) and 9.0 kPa (1.3 psi) for an RBOB with a vapor pressure of 44.8 kPa (6.5 psi). This increase, coupled with the corresponding reduction in mid-range distillation properties, lowers the V/L = 20 temperature, reducing vapor lock protection. Blend volatility is increased only slightly by MTBE and not at all by ETBE and TAME. Ethanol has not been the oxygenate of choice for summer RFGs because the volatility increase makes it more difcult to meet the very tight vapor pressure limits of these gasolines. Now, with many RFG areas banning MTBE, more volatile hydrocarbons will have to be removed at the renery to make RBOB.
49
Another volatility situation can occur if ethanol-blended fuel is mixed with hydrocarbon-only fuel in a vehicle fuel tank. This event is called commingling. In effect, the ethanol in the ethanol blend is increasing the vapor pressure of the hydrocarbon-only gasoline. The increase in vapor pressure is dependent on the ratio of the two components and the amount of ethanol in the blend. The maximum effect of about 6.2 kPa (0.9 psi) increase occurs for a 5.7 volume % ethanol blend when the mixture contains about 75% hydrocarbon-only gasoline where both fuels initially have a vapor pressure of 48.3 kPa (7.0 psi).
Water Tolerance Conventional gasoline, depending on its aromatics content, can dissolve up to
150 parts per million (ppm) water at 21C (70F). Oxygenating gasoline with ethers can increase water solubility to 600 ppm. Contacting either conventional gasoline or ether-oxygenated gasoline with additional water will not affect the properties of the gasoline but can make it hazy in appearance. Cooling water-saturated blends turns them hazy because some of the water becomes insoluble. However, the water that is released does not contain much ether and there is not enough water to cause performance problems. The situation is different for gasoline oxygenated with 10 vol % ethanol. The gasoline-alcohol blend can dissolve more water (6000 7000 ppm at 21C/70F). When this blend is cooled, both the water and some of the ethanol become insoluble. Contacting the blend with more water also draws ethanol from the blend. The result, in both cases, is two layers of liquid: an upper ethanoldecient gasoline layer and a lower ethanol-rich (up to 75% ethanol) water layer. The process is called phase separation and it occurs because ethanol is completely soluble in water but only marginally soluble in hydrocarbons. After phase separation, the gasoline layer will have a lower octane number and may knock in an engine. The fuel also is less volatile. The engine will not run on the water/ethanol layer. As the concentration of ethanol is decreased, the aromatics content of the gasoline is decreased, and as temperature is decreased, less water is required to cause a phase separation. The potential for phase separation requires that gasoline oxygenated with ethanol not be exposed to water during its distribution or use in a vehicle. Because of this requirement, gasoline oxygenated with ethanol is not transported in pipelines, which sometimes contain water. Rather, the ethanol is added to tanker trucks at the terminal immediately before delivery to the service station. Housekeeping at the service station is very important to prevent water contamination. This water sensitivity also means that extra care should be taken when gasoline oxygenated with ethanol is used as a fuel for boat engines. Ethanol blends are hygroscopic (absorb moister from the air) and in time can phase separate during storage if the tank is vented to the atmosphere and is subject to breathing as a result of temperature changes.
Material Compatibility Some fuel system metal components will rust or corrode in the presence
of water or acidic compounds. The additional water dissolved in oxygenated gasolines does not cause rusting or corrosion, but water from the phase separation of gasoline oxygenated with ethanol will, given time.
50
Chapter 4
Oxygenated Gasoline
Oxygenates can swell and soften natural and some synthetic rubbers (elastomers). Oxygenated gasolines affect elastomers less, the extent of which also depends on the hydrocarbon chemistry of the gasoline, particularly the aromatics content. The effect is of potential concern because fuel systems contain elastomers in hoses, connectors (O rings), valves and diaphragms. The elastomeric materials used in todays vehicles in the U.S. have been selected to be compatible with oxygenated gasolines. Owners manuals approve the use of gasoline oxygenated with 10 vol % ethanol or 15 vol % MTBE. (The compatibility of the other ethers is the same as that of MTBE.) Automobile manufacturers upgraded their fuel system elastomers at different times. Elastomers in pre-1975 U.S. vehicles may be sensitive to oxygenated and high-aromatics gasolines. Elastomers in
1975 to 1980 vehicles were upgraded but not to the same extent as in later models.2 Elastomer
compatibility in other parts of the world may not be the same as in the U.S. ChevronTexacos experience is that there is not a signicant compatibility problem between oxygenated gasolines and elastomers in older U.S. cars. There was not an increase in problems when oxygenated gasoline was introduced in 39 metropolitan areas in the winter of 1992. This held true for the Western states, which tend to have more older cars in their vehicle populations and for areas where different oxygenates were used (MTBE throughout California; ethanol in Portland, Oregon and Seattle/Tacoma, Washington.
Fuel Economy The effect of oxygenated gasoline on fuel economy is discussed on page 9. Permeability In this phenomenon, gasoline components diffuse through elastomeric hoses and
seals and through plastic fuel tank surfaces and contribute to evaporative emissions. There is concern that the addition of ethanol to gasoline results in ethanol permeating non-metal fuel system components and carrying additional hydrocarbons with it.
2 Changes in Gasoline II, Downstream Alternatives, Inc., Bremen, Indiana. 51
5 Gasoline Engines and Selected Systems
Introduction
Understanding the performance of a gasoline-powered vehicle not only requires knowing something about gasoline but knowing something about the engine and related systems.1 Two types of engine technology will be described: conventional and developing or advanced technology. For conventional engine technology, which encompasses most of the vehicles on the road today, it is useful to understand the combustion cycle and engine structure as well as the set of interconnected systems. Four major systems of a gasoline-powered engine will be covered here the air, fuel, exhaust, and engine/emission control systems. The air system delivers the intake air-fuel mixture to the engine. The fuel system provides for gasoline storage in the vehicle, delivers gasoline to the intake air system and mixes the air and gasoline in the correct proportion so the mixture burns well in the engine. The exhaust system routes the combustion gases to the atmosphere. In modern vehicles, a complex, computerized control system balances the often conicting goals of high power, good fuel economy and low emissions. There is a worldwide effort to reduce vehicle exhaust emissions to improve ambient air quality and fuel consumption to conserve natural resources and lower greenhouse gas emissions. As a result, several new technologies for the conventional engine are being developed and are starting to appear on new vehicles. In addition, advanced technologies such as gasoline-electric hybrid and fuel cell powertrains are also under various stages of development as alternatives to conventional engines.
Conventional Engine Technology Combustion Cycle

Gasoline-powered automotive engines are internal combustion, spark-ignition engines that burn fuel in an enclosed chamber the cylinder that is integral to the engine. (Diesel-powered engines also are internal combustion engines, but they dont involve spark-ignition; the fuel ignites spontaneously at the higher pressures and temperatures at which the engine operates.) The engines power is generated by the rapid expansion of gases formed by the combustion of a compressed air-fuel mixture. Most automotive engines are reciprocating-piston type devices in which a piston slides back and forth in a cylinder. Power from the motion of the piston is transmitted through a connecting rod to a crankshaft, which is coupled to the drive wheels via a drivetrain. Most automotive gasoline engines operate in a four-stroke cycle. For a piston engine, each stroke is one motion of the piston, either up or down. A piston that is all the way at the top of its travel, relative to the cylinder head, is at top dead center (TDC). Conversely, a piston that is all the way at the bottom of its travel is at bottom dead center (BDC). The four strokes occur over two complete revolutions (720) of crankshaft rotation. Valves are used to control gas ow into or out of the cylinder volume above the piston. This volume is called the combustion chamber. The compression ratio of an engine is the ratio between the volume in the combustion chamber when the piston is at BDC and the volume in the chamber when the piston is at TDC. The swept volume of a cylinder is the region
1 Some of the information in this chapter was drawn from the vehicle references listed in Sources of More Information (see page 83).
53
Figure 5-1 The Four Strokes of a Gasoline Internal Combustion Engine Intake valve Exhaust valve
above the piston at BDC but below the piston top when it is at TDC. The engines displacement is the total swept volume of all the cylinders. Figure 5-1 pictorially summarizes the four strokes intake, compression, power and exhaust. The rst downward motion of the piston in the fourstroke cycle the intake stroke draws the air-fuel mixture into the combustion chamber through the open intake valves. As the piston reverses direction and begins to move back up, the intake valves close. This upward motion of the piston is the compression stroke. Compression raises the pressure and temperature of the mixture. Near the top of the compression stroke, the spark plug produces a spark, igniting the mixture. The mixture burns and expands, which drives the piston downward for the third or power stroke. As the piston passes BDC and begins to move back up again, the exhaust valves open, beginning the exhaust stroke. The upward motion of the piston pushes the burned gases out of the engine into the exhaust manifold and eventually out the exhaust pipe. For combustion to occur, the fuel must be in the vapor state (see page 1). In addition, the relative amounts of air and fuel vapor are very important. In the ideal mixture for complete combustion of gasoline the stoichiometric mixture the ratio of air mass to fuel mass is 14.7:1. A mixture with less air and more fuel is fuel-rich, and a ratio with more air and less fuel is fuel-lean. Control of the air-fuel ratio (A/F) is a critical element of good emis-
Spark plug
Piston
Intake
Compression
Power
Exhaust
sions performance. Since CO and VOC emissions increase under fuelrich operation, while NOX emissions rise during fuel-lean operation, most modern vehicles strive to maintain the stoichiometric A/F. The Control section (later) describes how this is accomplished.
Engine Structure
Engines generally are separated into two distinct pieces, the cylinder head and the block (Figure 5-2). The head, or top, of the modern vehicle engine, controls the gas ow through the engine and also holds the spark plugs. Poppet intake valves and exhaust valves allow for precisely timed intake and exhaust ows. Spring-closed poppet valves can be opened and closed very quickly, an essential feature for optimum performance at high engine speeds. The valve seats are hardened to withstand the high temperatures of the combustion gases and to prevent abrasion due to valve contact and rotation. The movement of the valves is controlled by means of a shaft with elliptical lobes on it called a camshaft. As the camshaft rotates, the lobes push against the rocker arms to open the valves against spring pressure either directly or via pushrods. Engines with a camshaft mounted in the head above the valves are of an overhead cam (OHC) design, and engines with the camshafts mounted below the valves, on the block, are of a pushrod design. Pushrods transmit the valve opening force from the tappets, which ride on the camshaft lobes, up to the rocker arms. If each cylinder head has two camshafts overhead,
54
Chapter 5
Gasoline Engines and Selected Systems
the engine is a dual overhead cam (DOHC) design. An overhead camshaft is driven off the crankshaft by either a timing belt or a timing chain; a block-mounted camshaft is driven by either a timing chain or a gear. Engines typically have one to three intake valves and one or two exhaust valves per cylinder (Figure 5-3). An engine with two intake and two exhaust valves per cylinder is of a four-valve head design. More valves per cylinder are preferred for better breathing. Usually the exhaust valves are slightly smaller in diameter than the intake valves. It is easier to push out exhaust gases pressurized above atmospheric pressure than to draw in air-fuel mixture at atmospheric pressure. The block, or bottom of the engine, contains the power-producing mechanical components. Cylinders in the block contain the engines pistons. Typically each piston has at least three rings mounted in grooves in its perimeter to create a seal for the combustion chamber. The top of the piston is the surface that the expanding combustion gases push against. Each piston is supported by a wrist pin, which is attached to a connecting rod. All of the connecting rods are attached to the engines crankshaft. As the air-fuel mixture ignites and expands, it forces the piston down, which moves the connecting rod and turns the crankshaft. The crankshaft is mounted at the bottom of the engine in a volume called the crankcase. The oil pan forms the bottom of the crankcase. Oil is drawn from here by the oil pump and distributed throughout the engine, including the valve train in the head.
Figure 5-2 Cutaway of a Four-Cylinder Overhead-Cam Gasoline Internal Combustion Engine
Camshaft
Cylinder
Engine head
Exhaust valve Intake valve Piston
Engine block
Crankshaft
Figure 5-3 Poppet Valve
Passenger car engines may have as few as three cylinders or as many as 12. Engines with fewer than six cylinders often will have them in a row an in-line conguration. Engines with six or more cylinders usually have two rows, or banks, of cylinders, arranged with the central axis of the cylinders in each bank at an angle to the other bank. These are usually termed V engines (e.g., V-6). Engine design is one way to reduce emissions. When there is an understanding of how pollutants are created, changes often can be implemented to minimize them at the source. For example, exhaust VOC emissions can be reduced by careful mechanical design of the combustion chamber and the air and fuel intake systems.
Stem Retainer grooves
Air System
Air is drawn into the engine through the intake system. An air lter is used to keep dust and contaminants (e.g., insects) out of the engine. To control engine speed, a throttle is mounted in the air intake. This is simply a disk attached to a shaft to block air ow into the engine. The accelerator pedal is mechanically or electronically linked to the throttle. Depressing the accelerator pedal tilts the disk, reducing the blocked area and allowing more air to enter the engine. With more air, the engine can use more fuel and produce more power to accelerate, climb a hill or maintain a higher cruising speed.
55 Poppet Valve Tulip
Intake Air Pressurizing

An engine that uses intake air at atmospheric pressure is said to be naturally aspirated. The amount of air a naturally aspirated engine can use is limited by the local air density (barometric pressure) and pressure losses in the intake system. To get more air into an engine, small compressors sometimes are used to pressurize the intake air. If the compressor is driven off the engine crankshaft, it is called a supercharger. Superchargers usually are belt driven, either directly or through a clutch. Positive displacement superchargers generally are used on small- and medium-displacement engines in which the balance between supercharger size and increase in engine power is acceptable. Another way to power the compressor is to put it on a common shaft with a turbine driven by the engines exhaust gas. This arrangement is called turbocharging. Turbochargers are more compact than superchargers and can be used on all sizes of engines. To maintain boost pressure at a relatively constant amount over a wide range of engine speeds, some sort of pressure regulator is needed. A wastegate is the typical solution. The wastegate opens to divert some of the exhaust ow around the turbine when boost pressure is at the desired level.
Positive Crankcase Ventilation

Positive Crankcase Ventilation (PCV) was one of the rst techniques employed to reduce unburned
VOC emissions from gasoline-powered vehicles. It was required initially on California vehicles in
1961. Because the gases in the combustion chamber are under high pressure while combustion is
taking place, a small fraction leaks past the rings that seal the gap between the piston and the cylinder wall. These blow-by gases end up in the crankcase. They are a mixture of unburned fuel, air and combustion products. As the blow-by gases accumulate in the crankcase, they must be vented to avoid pressurizing the crankcase, which would force oil out of the engine. PCV systems consist of tubing and a control valve that meters the ow of the blow-by gases from the crankcase back into the engines intake air system, from which they are drawn into the cylinders and burned. Prior to the use of PCV, blow-by was vented to the atmosphere, providing a signicant source of VOCs.
Fuel System
Carburetors
In the intake system, air is mixed with a small amount of vaporized gasoline to produce a homogeneous air-fuel mixture. Many different devices have been used for this purpose; historically, the carburetor was the most common (Figure 5-4) on older-technology engines. A carburetor employs a venturi to discharge the correct amount of fuel into the intake air stream. A venturi is a convergingdiverging nozzle. The diameter of the nozzle decreases to a minimum at the throat and then increases to the discharge end. As air passes through the venturi, its velocity increases up to the narrowest portion (throat) because the ow area decreases. As the air velocity increases, its pressure decreases, creating a vacuum that draws fuel out of the carburetors fuel bowl through a tiny orice called a jet. Additional jets are used to enrich the mixture during acceleration and to supply sufcient fuel at idle. A choke plate or valve is used to enrich the mixture when the engine is cold by reducing the amount of air available to the engine. The choke is above the venturi and the throttle is below the venturi on downdraft carburetors.
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Chapter 5
Modern carburetors usually have two venturis, often referred to as barrels. A two-barrel carburetor on an in-line engine has two sets of staged venturis. The primary venturi is used for moderate driving and keeps fuel consumption at a minimum. The second venturi is brought into operation to provide greater air and fuel flow for more power. Larger, more powerful V engines require four-barrel carburetors. One set of venturis is usually larger than the other. The smaller set is used alone at low loads; both sets are high loads. Carburetors have been replaced by fuel injectors on new vehicles sold throughout the world because carburetors do not control fuel ow precisely enough to meet exhaust emission requirements. In part this is because they are volume-ow based and difcult to calibrate for all of the vehicles operating conditions.
Figure 5-4 Intake System of a Gasoline Internal Combustion Engine With a Two-barrel Carburator Choke flap Fuel filter To fuel tank Venturis Carburetor Camshaft
Throttle plates Poppet intake valve Intake manifold Combustion chamber Piston
Reprinted with permission from Robert Bosch Corporation.
Injectors
To overcome the carburetors limitations, engine builders switched to fuel injectors. Fuel injection systems can be categorized into three broad groups depending on where the injectors are installed. A system that has the injector in the throttle body, mounted on the air intake manifold, is called a throttle body injection (TBI) system. A system that uses one injector at the intake port of each cylinder, where it sprays on the intake valves, is called a port fuel injection (PFI) system (Figure 5-5). To enrich the mixture during cold starts, an additional cold-start injector may be used. This injector provides additional fuel to the intake air for a short period of time while the engine warms up. A central port fuel injection system uses a central distribution valve connected to springloaded poppet nozzles by tubes that run down each inlet manifold leg to spray fuel on the intake valves.
Figure 5-5 Fuel and Control Systems of a Port-Fuel-Injected (PFI) Gasoline Internal Combustion Engine
Fuel tank Fuel filter Fuel pump

Spark plug
ECM
Mass air flow sensor
Intake Exhaust O2 sensor Fuel injector
Distributor Battery Ignition switch

Engine
57
Figure 5-6 Section View of a Port Fuel Injector for a Gasoline Internal Combustion Engine
An electrically powered fuel pump provides fuel at low pressure (207 345 kPa/30 50 psi) to either the central injection units or the individual port injectors. A fuel lter is installed in the line after the pump to remove particulate matter from the fuel and prevent injector clog-
Winding
Needle
From Source Pintle
ging. Often another lter is used in the port fuel injector itself to catch any particles that may have escaped the main lter. A diaphragm pressure regulator maintains pressure and routes excess fuel back to the fuel tank. In some port injector systems (returnless), fuel is not returned to the tank but remains in the distribution rail
To Engine Control Module
when the injectors are closed. This is done to minimize evaporative hot soak and running losses but increases the chance for hot start and vapor lock problems. Fuel injectors meter the amount of fuel delivered to the inlet air; one type of port fuel injector is shown in Figure 5-6. When the injector is off, the spring keeps the needle against the seat, preventing fuel ow. Energizing a solenoid winding pulls the needle back against spring pressure (it moves only about 0.15 mm/0.006 in.), allowing fuel to ow through the annular passage around the needle and out through the injector tip. The needle tip, the pintle, is designed to break up the liquid fuel into a ne spray to promote rapid formation of vapor and enhance the mixing of fuel and air. Another type of port injector that is widely used is the director plate injector, which substitutes a at plate with several tiny holes for the pintle as the fuel metering and spray directing device. Several strategies are used to time fuel injection. Some older throttle body injectors and PFI systems inject fuel almost continuously, much like a carburetor. Intermittent injection systems re the injectors simultaneously to deliver the same quantity of fuel to each cylinder. These systems sometimes deliver fuel twice per cycle. Sequential injection systems re injectors sequentially at the same crankshaft angle on each cycle. Fuel quantity is metered by controlling the time the injector is open (pulse width).
Storage
A vehicle has a fuel tank for on-board fuel storage. Modern fuel tanks are sized to provide a vehicle range of between 450 and 650 kilometers (275 and 400 miles). Historically, most fuel tanks were made of steel, which can be corroded rapidly by water in combination with organic acids from the gasoline. As protection, tanks are lined with a corrosion-resistant material, commonly a plating of a tin-lead (terneplate) or zinc-nickel alloy. Organic coatings also have been used. Mercedes introduced an all-aluminum tank in 1991, and Volkswagen pioneered the use of a plastic fuel tank in 1976. Plastics can be formed in complex shapes to increase fuel storage capacity and are used on a large portion of todays vehicles. A signicant problem with plastic tanks is their permeability to fuel vapor.
58
Chapter 5
High-density polyethylene tanks must be lined with a low-permeability material or the vehicles evaporative emissions will be too high (see page 19). Evaporative emissions control systems have been employed on all gasoline passenger cars sold in California since 1970 and in the United States since 1971. They collect vapor resulting from the evaporation of gasoline in the fuel tank and introduce it into the engine later. The heart of the system is a canister containing activated carbon. It is in the line through which the tank breathes drawing in air from the atmosphere when gasoline is consumed or the tank temperature drops and emitting air when the tank temperature rises. The activated carbon absorbs gasoline vapor in the emitted air like a sponge absorbs water, preventing the vapor from reaching the atmosphere. The canister also is connected to the engines intake system by the purge control valve, which is opened at certain times to allow the accumulated vapors to be purged from the canister and burned in the engine. For the system to work, the canister must be the tanks only vent to the atmosphere. The ller tube must be sealed by a functional, properly tightened gas cap. Other sources of fuel-related emissions, such as those resulting from fuel leaks or seepage, and from gasoline permeation through hoses and tanks, are best controlled through proper component design and choice of hose, fuel tank, and gasket materials, as well as prompt repair of defective components.
Exhaust System
Combustion gases are routed out of the engine by the exhaust system. It has four parts exhaust manifold, exhaust pipe, catalytic converter, and mufer. The exhaust manifold collects exhaust gases from several cylinders and combines them into one ow stream. The exhaust pipe runs from the exhaust manifold underneath the vehicle to the rear. The catalytic converter and mufer, which reduces engine noise, are mounted in the exhaust pipe.
Catalytic Converter
A catalytic converter may be the most important emissions control device on a vehicle, and converters have been installed on gasoline-powered vehicles since 1975 in the U.S. Catalysts containing precious metals such as platinum, palladium, and rhodium are used to convert pollutants in the engine exhaust into nonpolluting compounds. The rst catalysts were oxidation catalysts. As the name indicates, they were designed to oxidize CO and VOCs in the exhaust into carbon dioxide and water. To work properly, the catalyst requires excess oxygen in the exhaust, which can be achieved either by operating the engine lean or by injecting air directly into the exhaust stream between the engine and the catalyst. Three-way catalysts, introduced about 1980 and now used almost exclusively, perform the oxidation function described above but also reduce NOX into nitrogen and oxygen. Because excess oxygen interferes with the reduction reaction, the three-way catalyst performs best when the A/F is very near the stoichiometric value. Thus, careful control of A/F is doubly important on modern cars, rst, to minimize the formation of CO and VOCs in the engine, and, second, to assure that the catalytic converter operates at maximum efciency.
59
To meet ever more stringent exhaust emission requirements, some engines use additional converters mounted at the exit of the exhaust manifold before the underoor converter. Others use a single converter but move it closer to the exhaust manifold. This is done so that the converters warm up more rapidly and light off quicker to reduce emissions after the engine starts. Some systems also use insulated exhaust pipes to assure faster warm-up of the converters. Most catalytic converters today consist of a monolith substrate brick coated with a catalytically active material such as platinum. Traditional catalysts have had cell densities (number of ow channels through the catalyst) of 400 or fewer cells per square inch. To meet more stringent emission levels of the future, cell densities are likely to increase to 600, 900, or even 1200 per square inch. This gives more channels with more active surface area for the exhaust gases to pass through and be treated more effectively to reduce emissions. But these smaller cells are also more prone to plug with exhaust particles.
Exhaust Gas Recirculation

Exhaust Gas Recirculation (EGR) is a strategy employed on many modern gasoline engines to reduce NOX emissions. The principle is relatively simple. Exhaust gas, being already burned, is essentially inert. If some of this exhaust gas is introduced into the intake manifold (recirculated) along with air and fuel, it wont participate in the combustion reactions. However, the exhaust gas can absorb some of the heat produced, thereby lowering the cylinder temperature. Since NOX production is favored strongly by higher temperatures, EGR reduces NOX emissions substantially. The mechanics of EGR involve appropriate piping between the engines exhaust and inlet systems and a control valve to regulate the amount of exhaust that is recirculated. When implemented properly, EGR can increase fuel economy under cruise conditions.
Control Systems
Fuel Control
To meet the conicting goals of high power, good fuel economy and low emissions, engine designers have had to develop high-speed, computerized engine control systems. Sensors monitor various conditions and an electronic control module (ECM ) collects the information and uses it to determine a response to the drivers input. Figure 5-7 lists the conditions the ECM may monitor in newer vehicles and the functions it may control. One of the ECMs most important functions is air-fuel mixture control. The air-fuel mixture must be kept very close to stoichiometric for optimum performance of the three-way catalyst. The amount of air in the mixture is determined by throttle position and engine speed; the ECM must command the injectors to provide the corresponding amount of fuel. It does this based on input from a sensor in the intake manifold that measures the mass of intake air and feedback from the oxygen sensors that measure the amount of oxygen in the engine exhaust. When the ECM is using these and other inputs to control the amount of fuel, it is described as operating in a closed-loop mode. When an engine is cold-started, the ECM is in the open loop mode it is not using oxygen feedback to control engine operations because the oxygen sensors are not warm enough to be operational. After a short time when the ECM detects that the oxygen sensors are operating, it switches to the closed-loop mode.
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Chapter 5
Under steady-state conditions, closed-loop control based on direct oxygen sensor input works ne, but it breaks down under transient conditions. When the driver suddenly opens the throttle to accelerate, there is a delay before the feedback from the oxygen sensor reects the new situation: It takes time for the fuel mixture to be burned in the engine, for the oxygen sensor to measure the oxygen content of the exhaust and for the ECM to command the injectors to inject more fuel. During the delay, the air-fuel mixture would be fuel-lean, which could cause driveability and emissions problems. Therefore, under transient conditions, the
ECM uses an anticipatory control strategy that
Figure 5-7 Conditions Monitored and Functions Controlled by the Electronic Control Module (ECM) Conditions That May Be Monitored Mass ow of intake air* Intake manifold air pressure Intake manifold air temperature Throttle position Angular rate of change of throttle position Engine speed Camshaft or crankshaft position Quantity of oxygen in the exhaust Spark knock Engine coolant temperature Vehicle speed Gear selection Transmission controller State of air conditioner
* Measuring the mass of the intake air eliminates the need to compensate for the change of air density with altitude.
Functions That May Be Controlled Mass of fuel injected for steady state, accelerating, and enrichment conditions Idle speed Cold start injector, if equipped Evaporative emissions control system (e.g., when to purge the charcoal canister) Amount of exhaust gas recirculation (EGR) Spark timing Amount of boost for turbocharged vehicles Input to the Automatic Braking System (ABS) computer for traction control Transmission shift points
uses engine load and RPM to determine the approximate fuel requirement.2 The ECM consults a data table (map) in its memory to determine the amount of fuel to inject for the transient combination of engine load and RPM. The map is developed by the engine manufacturer by system modeling and engine testing.
Because of production variations among engines, changes due to wear and aging and variations in fuel characteristics, the factory-installed map cant represent the best answer. So the ECM is equipped with an adaptive learning feature, which enables it to use oxygen sensor input to generate a second engine load/RPM map for the specic current conditions. This second map continually is being updated. The next time the engine reaches the same load/RPM operating point, the anticipatory control value will be closer to the correct value for the specic engine and fuel. Several special situations require different fuel control strategies. An engine needs extra fuel mixture enrichment for starting, for hard acceleration and at wide-open throttle (WOT) operation. When the engine is cold, fuel vaporizes more slowly. So extra fuel is needed to ensure that combustion will occur (A/F = 13 :1 for optimum startability). Some injector systems use an additional cold-start injector to provide the extra fuel. The cold-start injector typically operates for only a few seconds until a stable idle is achieved. Other designs simply program the port fuel injectors to inject more fuel. Another form of mixture enrichment, called commanded enrichment, is used under hard acceleration and at WOT to keep the gas temperatures in the combustion chamber from becoming too hot. This helps reduce the potential for knocking and avoids overheating the catalytic converter. EPA concerns
2 Ronald K. Jurgen, Editor-in-Chief, Automotive Electronic Handbook, McGraw-Hill Inc. New York, 1995
61
about excessive hydrocarbon and carbon monoxide emissions while a vehicle is under hard acceleration may end the use of commanded enrichment. Earlier-model vehicles used only one oxygen sensor mounted in the exhaust pipe before the underoor catalytic converter. More recent vehicles use two oxygen sensors in each exhaust pipe, one before and another after the underoor catalytic converter. The purpose of this is to allow more precise fuel control during closed-loop operation and for monitoring the condition of the catalytic converter as part of the on-board diagnostics, as will be described later. Idle is a common operating condition, especially in city driving. To reduce fuel consumption, it should be as slow as possible. Idle control is usually accomplished by adjusting the amount of ow of the air-fuel mixture, although it also can be controlled by adjusting the ignition timing.
Spark Control
In modern conventional engines, the initiation of a spark at the tip of the spark plug is controlled electronically by the ECM. A variety of sensors are used to decide when to initiate the spark, based on engine load (manifold air pressure), speed, coolant temperature, and atmospheric pressure. In addition, most new cars come equipped with a device called a knock-sensor that detects knock and provides a signal to the ECM. To eliminate the knock when it is detected, the ECM retards the engines spark timing, that is, it res the spark plug later in the compression stroke. This reduces the peak cylinder pressure and, as a result, the tendency for autoignition. The downside of timing retardation is a decrease in power. When knock is sensed in a turbocharged engine, the ECM also decreases the amount of boost to further reduce peak cylinder pressure. Boost reduction signicantly decreases power. Loss of power due to the ECMs knock-elimination strategies can be prevented by using a gasoline with a higher AKI or RON. Some knock sensor systems have the capability to advance the spark timing (as long as no knock occurs) to account for gasoline with a higher AKI or RON and provide some additional power.
Figure 5-8 Systems That On-Board Diagnostics Analyze to Monitor for Malfunction Overall catalyst system efciency Evaporative control system leakage (fuel tank vapor space and vapor lines) Ignition misre Secondary air injection system operation Fuel delivery system effect on emissions Oxygen sensor performance EGR system ow rate Electronic powertrain components that can affect emissions or are used for emission diagnostic strategies Air conditioning system refrigerant loss
On-Board Diagnostics (OBD)

Many countries around the world now require new vehicles to be able to detect faults in certain emissions-critical equipment and control systems: catalyst, oxygen sensor, spark plugs, EGR system, coolant system and evaporative emission control system. When a defect is detected, the ECM turns on a malfunction indicator light (MIL) often the check engine light on the dashboard and stores a fault code in computer memory. The code, which can be retrieved by a repair technician with the proper equipment, helps the technician identify the faulty component. Figure 5-8 lists the OBD monitoring requirements for systems used in the U.S. These OBD systems should substantially reduce the number of vehicles on the road with poorly running engines or defective emissions control systems.
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Chapter 5
Advanced Engine Technology

To reduce exhaust emissions and fuel consumption, technology is being developed either to modify conventional engines or to provide alternatives to conventional engines. Selected items in each of these areas will be discussed in the following paragraphs.
Figure 5-9 Direct Fuel Injection
Intake port
Exhaust port
Conventional Engine Modications

Direct Injection(DI)
Some gasoline engines are already available with direct fuel injection, with the fuel injector mounted directly into the cylinder head combustion chamber as shown in Figure 5-9. These engines are called direct injection spark ignition (DISI) engines. DISI injection system requires much higher-pressure fuel than port injectors (to overcome the in-cylinder compressed air pressure). The combustion process generally used with direct injection is a combination of homogeneous and stratied charge. Homogeneous charge is used for heavy accelerations and wide-open throttle operation where fuel is injected during the intake stroke to provide near stoichiometric mixtures for combustion. For light loads and cruising conditions, a stratied charge is used, which consists of pockets of combustible mixture within a larger volume of fuel-lean mixture. The combustible mixture layer is concentrated around the spark plug. This approach results in higher thermal efciency (lower fuel consumption and lower CO2 emissions) than possible with a conventional engine with port fuel injection. But the overall fuel lean mixtures can increase the formation of NOX and the favored method of control for DI engines in meeting ultra-low NOX emission standards is a lean NOX Trap. The trap is essentially a catalytic converter device that stores NOX under high emitting conditions and then momentary combustion of slightly rich mixtures is used to reduce the stored NOX. This trap technology is still under development to enable good long-term durability. Low sulfur levels in the fuel are important to extend the life of the lean NOX trap.
Reprinted with permission from Toyota Motor Corporation.
Fuel injector
Piston
Variable Valve Timing

Another approach to reduce fuel consumption and exhaust emissions of conventional engines is
ECM-controlled variable valve timing. The timing of the intake valve opening is varied depending
on engine load conditions advanced under light load to increase overlap time with the exhaust valve for decreased pumping loss and internal EGR and delayed under acceleration and heavy load to reduce or eliminate overlap for maximum power output. Some systems combine variable valve timing with variable valve lift to further reduce pumping losses, approaching an unthrottled condition at light loads.
Cylinder Deactivation
To meet customer demands for high fuel economy and high performance, cylinder deactivation is sometimes used to allow a large V-8 engine to operate like a small V-6 engine under light load conditions. An ECM-controlled solenoid deactivates one or more intake valves at low load conditions, where engines operate most of the time, to effectively reduce the size of the engine (i.e., from eight cylinders to six or even four), which reduces fuel consumption. Under high load
63
Figure 5-10 Types of Hybrid Powertrain Systems

Series Hybrid System
acceleration conditions when more power is needed, more intake valves are allowed to operate as with a conventional V-8 engine.
Variable Compression Ratio

To allow higher specic output from a smaller engine with inherently better fuel consumption characteristics, technology is being developed to vary the compression ratio for different operating conditions. Often this technology is combined with super- or turbo-charging to further increase the specic power output. One approach for varying the compression ratio is to hinge the cylinder and upper block to the lower block and crankshaft, so the two components can move relative to each other. Another approach is to use eccentric positioning of the crankshaft axis to change the compression ratio. This technology still is being developed and still is very complex, so such engines arent expected to be widely available in the near future.
Engine
Generator Controls/ Power Electronics Electric Motor Battery
Wheels
Parallel Hybrid System
Controlled Autoignition (CAI) Combustion

At this time, CAI is largely a concept being actively explored for potential fuel economy and exhaust emission control advantages. A premixed air-fuel mixture is compressed to a temperature so high that autoignition occurs. This type of autoignition differs from one that produces knocking combustion because it happens at a controlled, much slower rate. CAI is synonymous with homogeneous charge compression ignition (HCCI), usually referred to when this concept is applied to a diesel engine. CAI is difcult to control at high loads, so conventional spark ignition (SI) is usually used when high
Wheels
Engine Electric Motor/ Generator
Controls/ Power Electronics Battery
Transmission
engine load occurs. Signicant hurdles still to be overcome for application of CAI include: fuel type, cold starting, control during transient operation, and smooth transition between CAI and SI modes of operation.
Alternative Engine Technology

Hybrid Gasoline-Electric
To reduce exhaust emissions and decrease fuel consumption, some hybrid vehicles are already available and more are being developed for introduction to the marketplace. A hybrid powertrain combines a gasoline (or diesel) internal combustion engine with an electric motor, generator and storage battery. There are two types of hybrid drive systems, series and parallel (Figure 5-10). In the series conguration, a gasoline engine drives a generator to provide electrical energy for storage batteries and an electric motor, but only the electric motor drives the vehicle. In the parallel conguration, the gasoline engine drives a generator and the vehicle under low-load conditions and the electric motor is used to provide additional power for driving the vehicle under higher-load conditions. Both types of systems recover energy normally lost during decelerations and braking and use it to charge the storage batteries. The hybrids being offered today and those under development are typically parallel hybrids. Hybrid vehicles can meet customer expectations with very low emissions and good fuel economy, but the cost of the extra complexity and hardware compared to a conventional powertrain cannot presently be recovered by fuel cost savings alone over the life of the vehicle in the U.S.
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Chapter 5
Fuel Cell Electric

Perhaps the most technically advanced alternative powertrain for vehicles is the fuel cell electric. It has the potential for highest efciency (two to three times that of conventional powertrains; less compared to advanced hybrid-electric internal combustion engine powertrains) and lowest emissions (near zero) but is the furthest away from commercial reality. Besides a fuel cell stack that converts hydrogen to electrical energy, a fuel cell powertrain consists of an electrical motor/generator drive unit, storage battery, and hydrogen fuel storage with high-pressure, liquid, or hydride options. Alternatively, an onboard fuel reformer fed by liquid hydrocarbon fuels might be used to produce the hydrogen. A fuel cell can be thought of as a type of battery that converts chemical energy to electrical energy with electrodes (Figure 5-11). Hydrogen as the fuel is supplied to a platinum-coated anode. Oxygen from the air is fed to a platinum-coated cathode. A chemical reaction between the electrodes generates electrical current to drive a motor or store in a battery. The only emission products from the fuel cell to the atmosphere are water and heat although signicant emissions can also occur in making and providing the hydrogen, depending on source. Many individual fuel cells are combined to form a fuel cell stack of sufcient capacity to drive a vehicle. Although fuel cells are under intense development, they have many hurdles to overcome so it is not clear when they could appear in high-production-volume vehicles. A typical estimate is sometime after 2020, although there is a wide range of opinion. Signicant hurdles include: cost (about 10 times that of a conventional engine), size and weight, low temperature (sub-freezing) operation, hydrogen fuel storage and distribution infrastructure, and hydrogen cost.
Figure 5-11 Fuel Cell Power System
Fuel cell stack

LA R PL A
H H H H H HH
BI
PO
TE
Single fuel cell
OO
H H H H
OO
ST E ALY OD AT AN M C ST U E IN LY YT AT TA OL PL CA E TR M HOD EC U L E IN T AT CA PL
OO H
HYDROGEN IN
H2
O O O
OXYGEN IN
WATER OUT
Electric motor
O2
Reprinted with permission from Fuel Cell 2000, Breakthrough Technologies.
BI
H H
H H O
PO
LA
H2O
PL
AT
O H H H O
65
6 Gasoline Vehicles Deposit Control
Introduction
Almost without exception, harmful deposits would build up inside an engine if commercial gasolines did not contain effective deposit control additives. The best of todays additives not only can keep engines clean, they also can remove existing deposits to help restore the original performance designed into the engine. Because almost all base gasolines are formulated to the same regulated specications (see page 38), the performance of the deposit control additive is one of the most important features that differentiates one brand of gasoline from another.
Engine Deposits and Performance

The schematic in Figure 6-1 shows the critical areas of deposit formation and the associated performance impacts.
Fuel Injectors and Carburetors Fuel injectors are designed to accu-
Figure 6-1 Location and Performance Effects of Engine Deposits
rately meter fuel to the engine and to deliver it in a precise pattern of ne droplets. Because the fuel passages are small, injectors are highly sensitive to small amounts of deposits in the critical regions where the fuel is metered and atomized. These deposits can reduce fuel ow and alter the spray pattern, degrading driveability, decreasing power and fuel economy and increasing exhaust emissions. Deposits cause similar problems for carbureted engines because carburetors also use a number of small channels and orices to meter fuel. Port fuel injector (PFI) deposits form during the hot soak period after the engine has been turned off. The stationary gasoline trapped in the injector tip is exposed to a higher temperature for a longer time than the gasoline that owed through the injector when the engine was running. The heat degrades the gasoline, initiating deposit formation. In the absence of an effective additive, injector deposits can form quite rapidly if the base gasoline is relatively unstable and if a vehicle is used predominantly for short trips. Figure 6-2 shows a close-up of deposits in the metering holes of a gasoline injector tip.
Intake Valves and Ports Deposits form on intake valves and ports
Intake valve deposits Driveability Power loss Exhaust emissions
Injector pintle deposits Driveability Power loss Exhaust emissions Fuel economy
Combustion chamber deposits Octane requirement increase Exhaust emissions Deposit interference
Figure 6-2 Port Fuel Injector Director Plate Deposits
because they operate at high temperatures in a very reactive environment whenever the engine is running. If the deposits become heavy, they reduce engine power because they restrict air ow and alter air flow patterns within the cylinder. In some sensitive fuel-injected engines, even low levels of intake valve deposits can hurt performance. Cold-start and warm-up driveability (see page 3) can be adversely affected and exhaust emissions increase. The magnitude of the emissions increase
High detergency No additive Deposits restrict fuel ow and disrupt spray pattern.
67
Figure 6-3 Intake Valve Deposits (IVD) Increase Tailpipe Emissions
can be surprisingly large (Figure 6-3). This occurs because the deposits act somewhat like a sponge, momentarily absorbing then releasing fuel, which upsets the delicate air/fuel ratio, particularly during transients. This not only increases emissions coming out of the engine but hurts the conversion efciency of the catalytic converter as well. Other valve deposit problems include valve sticking because deposits interfere with the valve stem sliding in its guide and burned valves because severe deposits prevent the valve from seating properly. Figure 6-4 shows different levels of intake valve deposits common in todays engines.
Combustion Chamber When an engine is brand-new, its octane number
0.6 Hydrocarbons (HC), g/mile 0.5 0.4 0.3 0.2 0.1 0 6 7 8 CRC IVD Rating (10 = clean) 9
requirement (ONR) is determined by its design and the quality of its manufacture. Generally, it will not knock when operated on gasoline with the antiknock quality prescribed by the manufacturer. However, the engines ONR increases as combustion chamber deposits form during the rst several thousand miles of operation (see page 7 and Figure 6-5). If the increase is large enough, the recommended gasoline AKI may not prevent knocking or, if the vehicle is equipped with a knock sensor, the loss of power that accompanies knock suppression (see page 62). Combustion chamber deposits increase ONR in two ways. They increase the combustion temperature both by transferring more heat
6 7 8 CRC IVD Rating (10 = clean) 9
5 Carbon Monoxide (CO), g/mile 4 3 2 1 0
to the incoming mixture and slowing the transfer of heat from the combustion gases (thermal insulation). They increase the compression ratio because their bulk volume reduces the volume of the combustion chamber at TDC. The increase in compression ratio has a much smaller effect on ORI than the heating effect. Research has shown that precursors for combustion chamber deposits come from the fuel, some fuel additives and the engine oil, and that certain fuel and engine oil components form more deposits than others. So far, the only quick, effective means of removing these deposits is to
Oxides of Nitrogen (NOx ), g/mile
0.5 0.4 0.3 0.2 0.1 0 6 7 8 9
treat the gasoline with an aftermarket deposit control additive concentrate based on polyether amine chemistry. The treat level is 10 to 20 times higher than that in service station gasolines. At this elevated concentration, one tankful of gasoline can decrease ORI 30 to 40 percent. Periodic treatment is required because the deposits re-form with additional driving and the ONR gradually returns to the previous equilibrium level.
CRC IVD Rating (10 = clean)
Emmissions were measured by Federal Test Procedure Cycle (FTP 75); results are average results for a 20-car fleet.
Reprinted with permission from SAE Paper No. 922259 1992 Society of Automotive Engineers, Inc.
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Chapter 6
Gasoline Vehicles Deposit Control
Combustion chamber deposit interference (CCDI) and combustion chamber deposit aking (CCDF) are two other problems which sometimes occur in certain modern engine designs. CCDI is the result of physical contact between deposits on the piston top and cylinder head and is manifested as a loud, metallic banging sound when the engine is cold.
CCDI is limited to the engines that have been designed, primarily to
Figure 6-4 Typical Intake Valve Deposits Common in Todays Engines
reduce emissions, with minimal clearance 1 millimeter or less between some areas of the piston top and the cylinder head (squish areas) when the piston is at top dead center. Combustion chamber deposit aking causes low compression pressures due to improper sealing of the valves. This problem occurs when pieces of CCD ake off and end up lodged between the valve face and the valve seat. Symptoms of CCDF are difculty in starting and rough running when cold.
High detergency LAC detergency No additive
Historical Development of Deposit Control Additives 1

Carburetor Detergent This class of additives consists of relatively inexpensive low-molecular-
Figure 6-5 Typical Combustion Chamber Deposits
weight surfactants used at low concentrations. When introduced in 1954, they were effective in preventing and, in many cases, removing deposits from carburetor throttle bodies. But they could not handle deposits in other parts of the carburetor, like the air bleeds, or in the rest of the engine intake system. The introduction of PCV and EGR emission control systems in the
1960s and 1970s increased deposit levels in the whole intake system (see pages 56 and 60). As
a result, carburetor detergents were not as effective as they were in the simpler 1950s vehicles.
Detergent-Dispersants This class of additives consists of polybutene succinimides. Additives with
similar chemistry had been used widely as engine oil dispersants before the chemistry was applied to gasoline in 1968. Detergent-dispersants are higher-molecular-weight materials used at concentrations three to ve times higher than carburetor detergents. Their performance was sometimes improved by using them in combination with a petroleum carrier oil. They provide keep-clean performance for the intake manifold and intake ports. But they couldnt control intake valve deposits and have poor carburetor and fuel injector cleanup performance.
1 L.M. Gibbs, Gasoline Additives When and Why, Paper No. 902104, Society of Automotive Engineers, October 1990. 69
Performance Categories There are two performance categories for deposit control additives: keep-clean and cleanup. Keep-clean indicates that when additized fuel is tested in a clean engine, the part of interest still will be relatively clean at the end of the test. Cleanup indicates that when additized fuel is tested in an engine where deposits have been built up on the part of interest (by previously running the engine on a lower-quality gasoline), the deposits on the part will be signicantly reduced at the end of the test. Cleanup performance is more demanding than keep-clean performance.
Deposit Control (DC) Additives The rst additive of this class was introduced in 1970. It was based
on polybutene amine chemistry and was used in combination with a carrier oil. While they have to be used at higher concentrations than detergent-dispersants, DC additives provide benets throughout the engine intake system. They clean up and keep clean the throttle body and upper areas of the carburetor, fuel injectors, intake manifold, intake ports, and intake valves. Lead salts are a combustion catalyst for carbon, so the shift to unleaded gasoline changed the nature of combustion chamber deposits. When the rst generation DC additives were used in unleaded gasoline, they continued to control intake system deposits, but increased combustion chamber deposits. In response, a second-generation DC additive designed specically for use with unleaded gasoline was developed and introduced in 1980. It was based on new polyether amine chemistry, which provides excellent deposit control performance throughout the intake system without contributing to combustion chamber deposits or causing any other adverse side effects.
No Harm and Compatibility

DC additives are used at concentrations that are 20 to 50 times higher than the concentrations of other gasoline additives (see page 36). At these higher concentrations, they have the potential to affect gasoline properties, fuel system materials and engine oils. So DC additives are tested for the absence of negative attributes (no harm) as well as for the positive attribute of controlling deposits. The additized fuel must be fully compatible with the elastomers and metals it will contact. Also it must have good water tolerance, and not contribute to spark plug fouling, crankcase sludge formation, or intake or exhaust valve sticking and be compatible with other gasoline additives.
Deposits Affect Emissions

At some level, carburetor, injector, intake port and valve and combustion chamber deposits all increase engine emissions (see Chapter 2). For example, Figure 6-3 illustrates that hydrocarbon, CO and NO X tailpipe emissions all are lower when intake valves are cleaner.
Required Additive Use

Because of this relationship between decreased deposits and decreased emissions, all motor gasoline sold in the United States must contain an additive that provides a minimum level of deposit control performance. This requirement was established by the Clean Air Act Amendments of 1990 and became effective in January 1995. A similar requirement has been in effect in California since January 1992. Additive manufacturers are required to obtain EPA certication for their additives. The certication request must include documentation of the additives effectiveness in specied fuel injector keep-clean and intake valve keep-clean tests (see sidebar) when evaluated with specied test fuels. A similar detergency requirement exists in Thailand. Before selling any gasoline, gasoline marketers must add a certied deposit control additive to their gasoline at the certication concentration level or higher. Experience has shown that the
70
Chapter 6
Gasoline Vehicles Deposit Control
minimum certication dosage is not very effective in controlling deposits in certain fuels and engines. This minimum level is referred to as the lowest additive concentration or LAC. Higher concentrations provide improved performance; for instance, changing keep-clean performance to cleanup performance. Historically, some gasoline brands have provided much higher deposit control performance than the minimum level of certication performance required by the EPA. For competitive reasons, they probably will continue to do so.
Additive Certication Tests The fuel injector keep-clean test was developed by the Coordinating Research Council (CRC) ( see page 39) and established as ASTM D 5598 Test Method For Evaluating Unleaded Automotive Spark-Ignition Engine Fuel for Electronic Port Fuel Injector Fouling. The method uses a 1985-1987
Aftermarket Additives 2
Engine deposits are affected by engine design, driving conditions, gasoline base fuel quality, and gasoline additives. Although all gasoline must contain a deposit control additive, some additives are less effective than others or are used at minimum concentration levels that are not very effective. In addition, some engine designs form heavier deposits than others, and some engine designs are extremely sensitive to deposits that do form. Aftermarket deposit control additives are available that can clean up deposits that have formed due to these circumstances. Treating one tankful of gasoline with the aftermarket additive is often sufcient. However, additive chemistry and dosage play large roles in determining the effectiveness of the product. Polyether amine-based aftermarket additives have been shown to be particularly effective at providing both excellent intake system and combustion chamber deposit cleanup.
model Chrysler vehicle equipped with a 2.2-liter, 4-cylinder, turbocharged engine. After the vehicle has been operated through more than 720 onehour cycles for a total of 10,000 miles, no injector may have greater than a 5 percent ow restriction. The intake valve keep-clean test was adapted from one developed by BMW and the Southwest Research Institute and established as ASTM D 5500 Test Method for Vehicle Evaluation of Unleaded Automotive Spark-Ignition Engine Fuel for Intake Valve Deposit Formation. The method uses a 1985 model BMW 318i vehicle. After the vehicle has been operated through a cycle of mixed city, suburban, and highway driving for 10,000 miles, the average intake valve deposit weight must not exceed 100 mg per valve to meet federal requirements and 50 mg per valve to meet California requirements. California places an additional requirement on CCD using this same test procedure.
2 Aftermarket additives are intended to be added by the customer to a gasoline (or oil) already in the customers vehicle.
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Handling Gasoline Safely
Introduction
Gasoline is dangerous. First, and foremost, it is highly ammable it is easy to ignite and it burns explosively. Second, exposure to gasoline liquid or vapor can cause adverse health effects. All companies in the U.S. are required to develop and make available safety information on their products. You may obtain a Material Safety Data Sheet (MSDS) for ChevronTexaco gasoline by calling 1-800-689-3998 or at http://www.chevron.com/prodserv/fuels/. Click MSDS and search for gasoline. The MSDS provides detailed information on the hazards associated with gasoline and the appropriate responses. ChevronTexacos MSDS for gasoline contains the following human health warnings:
DANGER!
Harmful or fatal if swallowed can enter lungs and cause damage. Vapor harmful. Long-term exposure to vapor has caused cancer in laboratory animals. May cause eye and skin irritation. Extremely ammable. Keep out of reach of children.
Fueling Your Vehicle

Safety tips when fueling the vehicle: Shut off the vehicles engine. Do not smoke. Use only the refueling hold-open latch provided on the dispenser nozzle. Never jam the refueling latch on the nozzle with any object (e.g., gas cap, etc.). Never leave the nozzle unattended. Do not overll or top off your tank. Never let children fuel the vehicle. Leave cell phones and other electronic devices turned off and in the vehicle. Although a rare event, static electricity-related res while lling a vehicle can cause injury and property damage. Static electricity is more likely to build up on your person in cold, dry climatic conditions. After exiting a vehicle to refuel it, always touch a metal part of your vehicle (such as the door or fender away from the gas tank opening) with a bare hand before you begin fueling. To avoid a buildup of static electricity, do not get back into your vehicle during refueling. If you cannot avoid getting back into the vehicle, upon exiting always touch a metal part of the vehicle away from the ll point before handling the nozzle. In the unlikely event a re occurs when refueling, leave the nozzle in the ll pipe and back away from the vehicle. Notify the station attendant immediately so that all dispensing devices and pumps can be shut off with emergency controls. Use the emergency shutdown button located on the building exterior and/or canopy columns to shut off the pump.
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Filling a Container
Several res have started at service stations when customers placed portable containers on plastic bed liners in pickup trucks while lling the containers with gasoline. Filling a container is a special situation that requires extra precautions: Use only a UL-approved plastic or metal container. Shut off the vehicles engine. Place the container on the ground a safe distance from the vehicle, other customers, and trafc. Dont ll a container in or on a car or truck. Keep the nozzle in contact with the container during lling. Manually control the nozzle valve; do not latch it open.1 Do not smoke. Avoid breathing gasoline fumes. Flowing gasoline generates a static electric charge that builds up on the gasoline in the receiving container. If the charge isnt given an opportunity to dissipate, it could jump from the container to the metal spout of the dispenser nozzle as a static spark. If a spark occurs near the open mouth of the container where the concentration of gasoline vapor and air is in the ammable range, it could ignite the gasoline. Putting the container on the ground and keeping the nozzle in contact with the container help dissipate the static charge. The charge will dissipate more slowly from a container being lled on an insulating surface carpet in the trunk of a car and on the bed of a utility vehicle or the plastic bed liner of a pickup truck. Placing the container on the ground has the secondary benet that an accidental spill wont contaminate the vehicle. Fill the container only about 95 percent full. This leaves room for gasoline to expand if it warms up in storage. Without an air space, expansion will force liquid gasoline out of the container or distort the container.
Transporting Gasoline
Before putting a container of gasoline in the trunk of a vehicle or the back of a pickup, tighten the cap of the container and the cap of the air vent, if there is one. Wipe the outside of the container to remove any liquid gasoline or gasoline residue. Secure the container in the trunk or pickup so turns or road vibrations wont cause it to slide around or tip over. Do not leave a container of gasoline in direct sun on a hot day, or in the trunk of a car that is in direct sun on a hot day. Heating the gasoline will build up pressure in the container.
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1 If the nozzle is tted with a fume-recycling device, the ller-spout seal must be compressed to activate the dispenser.
Handling Gasoline Safely
Storing and Handling Gasoline

To avoid a re, keep the gasoline away from any ignition source (ame or spark) and any ignition source away from the gasoline. There should not be an appliance pilot light or igniter within 50 feet of where gasoline is stored or handled. Gasoline fumes, which are invisible and heavier than air, can travel along the oor for some distance when they are not dispersed by air currents. If ignited, the fumes become a fuse that brings the ame back to the liquid gasoline source. To avoid eye and skin contact, wear safety glasses and gasoline-resistant gloves.2 For both re and health considerations, it is best to handle gasoline outdoors. Ignition sources are less prevalent and the fumes are diluted and dispersed more quickly.
First Aid
Eye Contact: Flush eyes immediately with fresh water for at least 15 minutes while holding the
eyelids open. Remove contact lenses, if worn. No additional rst aid should be necessary. But if irritation persists, see a doctor.
Skin Contact: Wash skin thoroughly with soap and water. Remove and wash contaminated
clothing. See a doctor if irritation is severe.

Inhalation: If respiratory irritation or nervous system effects (headache, dizziness) occur, move
the person to fresh air. If any of these effects continue, see a doctor.
Ingestion: If swallowed, give water or milk to drink and telephone for medical advice. DO NOT
make the person vomit unless directed to do so by medical personnel. If medical advice cannot be obtained, then take the person to the nearest medical emergency treatment center or hospital.
Emergency Information: Call your local Poison Control Center or ChevronTexaco Emergency
Information Center at 1-800-231-0623 (24 hours).
Using Gasoline
Gasoline should be used only as an engine fuel. It should not be used as a solvent, cleaner, barbecue starter or for any other non-engine use. Occasionally, students propose science projects involving gasoline. ChevronTexaco strongly recommends AGAINST student projects requiring the handling of gasoline. The risks are too great for people not completely familiar with the hazards. Gasoline never should be brought into the living space of a house or taken to school.
2 Gloves made of nitrile, polyurethane, Viton, or chlorinated polyethylene (CPE) are gasoline-resistant. 75
Disposing of Gasoline
Do not dispose of gasoline by pouring it onto the ground or into a sewer, street drain, or stream or river. These actions are environmentally harmful and may result in a re or explosion. Excess gasoline in good condition can be added to the fuel tank of a gasoline-powered car or truck. (Dont dispose of gasoline/oil mixtures for two-stroke cycle engines this way.) Use a funnel with a exible stem to direct the gasoline past the ap valve in the ller tube of newer vehicles. The funnel will help prevent gasoline from being spilled on the vehicle. Oxygenated gasoline can damage the nish of some vehicles. Flexible stem funnels are available at some auto supply stores. Its not as easy to get rid of gasoline that has deteriorated. Some organizations will help dispose of gasoline in an environmentally responsible way. Finding the best option may take some searching. Sources of information are your communitys re department, recycling center, and hazardous-waste disposal center. Check the government pages of your phone book to locate these organizations. Commercial organizations are listed in the Yellow Pages under Environmental & Ecological Services and Oils, Waste. You may have to pay for the disposal, but the cost should be weighed against the cost of repairing an engine damaged by bad gasoline.
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Questions and Answers
What is gasoline?
Gasoline is the fuel designed for spark-ignition internal combustion engines. In some parts of the world, it is called petrol. Conventional gasoline is a mixture of compounds, called hydrocarbons, derived from petroleum crude plus a small amount of a few additives to improve its stability, control deposit formation in engines, and modify other characteristics.
What is oxygenated gasoline?

Oxygenated gasoline is conventional gasoline to which oxygenates have been added to increase octane and/or, as required by regulation, to reduce emissions. Oxygenated gasoline is required in the U.S. during winter in those metropolitan areas that do not meet the federal air quality standard for carbon monoxide (carbon monoxide nonattainment areas). Reformulated gasolines in the U.S. also are oxygenated, but year-round. The common oxygenates are ethanol and methyl tertiarybutyl ether (MTBE). Other ethers that may be used are tertiary-amyl methyl ether (TAME) and ethyl tertiary-butyl ether (ETBE).
Will oxygenated gasoline perform as well as conventional gasoline in my vehicle?

Oxygenated gasoline will perform as well in modern vehicles with engine control systems that adjust the air-fuel ratio. Oxygenated gasoline may cause some driveability problems in carbureted cars and fuel injected cars without engine control systems because they result in an air-fuel mixture that is more fuel lean. Oxygenated gasoline reduces fuel economy, on average, by 2 to 3 percent. The odor of gasoline oxygenated with MTBE or the other ethers differs from that of conventional gasoline.
What is reformulated gasoline (RFG)?

Reformulated gasoline (RFG) in the U.S. is a gasoline blended to reduce evaporative and exhaust emissions from vehicles. The characteristics of the gasoline are specied by regulation, either directly or by a model that relates gasoline characteristics to emissions. The federal government and the state of California have somewhat different regulations for RFG. Federal RFG is required in those metropolitan areas that do not meet the federal air quality standard for ozone (ozone nonattainment areas). California RFG is required throughout the state. Federal RFG is oxygenated year-round. The California Predictive Model allows for non-oxygenated California RFG in nonfederal RFG areas.
Will RFG perform as well as conventional gasoline in my vehicle?

If the RFG is oxygenated, the answer for the performance of oxygenated gasoline applies. Oxygenated RFG will reduce fuel economy, on average, by 2 to 3 percent. Regulations require RFG to have a low vapor pressure during the summer, which could make starting a cold engine more difcult on unseasonably cold days in the spring.
77
If RFG has a lower fuel economy and more gasoline is needed to go the same number of miles, doesnt this counteract some of the emissions benet of RFG?
The emissions benets of RFGs were determined by testing them in eets of actual vehicles. The test vehicles saw the same fuel economy penalty that your car sees. Since the emissions are measured in the U.S. in units of grams per mile, the emissions benet for RFG already includes any effect of the fuel economy penalty.
Why did my fuel economy drop much more than 2 to 3 percent when I began using RFG?
The 2 to 3 percent fuel economy penalty for RFG was determined by extensive laboratory testing and has been validated by independent organizations like the California State Automobile Association. The penalty also is in line with the decrease in the heating value of RFG compared to non-oxygenated conventional gasoline. A decrease in fuel economy much greater than 2 to 3 percent probably is the result of a mistuned engine or of comparing fuel economy results obtained under different driving and/or weather conditions.
What is knocking?
Spark knock is the sound of abnormal combustion. When combustion in a spark-ignition internal combustion engine is initiated by a spark, the ame front should fan out from the spark plug and travel across the combustion chamber rapidly and smoothly. If the last part of the air-fuel mixture ignites spontaneously (autoignites) before the ame front arrives, the sudden jump in the pressure in the cylinder creates the characteristic knocking or pinging sound. Knocking occurs because the octane of the gasoline is below the antiknock requirement of the engine at that moment.
Can knocking harm my engine?

Occasional light knocking wont harm an engine. Heavy or prolonged knocking can result in loss of power, overheating of parts in the cylinder and engine damage.
What is octane?
Octane number is a measure of the antiknock quality of gasoline the ability of the gasoline to resist knocking when it is burned in an engine. There are two laboratory tests to measure octane that are run in a single-cylinder engine operated under different conditions: Research octane number (RON) and Motor octane number (MON). The octane number posted on U.S. gasoline dispensers in service stations is the antiknock index (AKI) the average of RON and MON [(RON + MON)/2, usually abbreviated (R + M)/2]. The AKI was chosen as the posted value in the U.S. because experience showed it to be the best indicator of the antiknock performance of gasoline in the majority of U.S. vehicles. In other parts of the world, RON frequently is posted on the pump.
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What octane gasoline should I use in my vehicle?

For starters, use a gasoline with the AKI or RON recommended by your owners manual. (A rule of thumb is that the RON of a gasoline equals the AKI + 5.) Using gasoline with an antiknock rating higher than that required to prevent knock will not improve a vehicles performance, including its power, unless the vehicle is equipped with a knock sensor (see below). There are three reasons why your vehicle might knock on a gasoline with the AKI or RON recommended by the owners manual. 1) The engine is at the upper end of the octane number requirement range. The octane number requirement of each engine in vehicles of the same make and model is a little different because of variations in manufacturing tolerances. 2) The octane number requirement of the engine increased more than usual because the equilibrium level of the combustion chamber deposits is higher than usual. 3) There is a mechanical or electrical problem with the engine or engine control system. In many modern vehicles, the driver may never hear knocking when the AKI or RON of the gasoline is lower than the octane number requirement of the engine because the engine is equipped with a knock sensor that temporarily retards spark timing to prevent knock. This adjustment will result in loss of power and acceleration. In this case, switching to a gasoline with a higher AKI or RON will improve performance and increase power. Before making a permanent change, it is advisable to have a mechanic determine that the emissions control system is functioning properly.
Why do the gasolines in different states have different AKI values?

The AKIs of the gasolines offered for sale are set by gasoline reners and marketers based on their perception of the technical and competitive needs in the market. Federal and most state regulations do not regulate AKI values, only that the postings on the dispensers accurately reect the AKIs of the gasolines being sold. The AKI of premium gasoline in some states is higher than it is in others. This is the result of competition. The AKI of all grades of gasoline is lower in the high-altitude areas of some Rocky Mountain states. This is because the octane requirement of older engines without engine control modules decreases with altitude. At higher altitudes, these engines perform as well on the lower-AKI gasolines as they would at sea level on higher-AKI gasolines.
What will happen if I use the wrong octane number gasoline in my vehicle?
Using a gasoline with an AKI or RON lower than that required by your vehicle will cause the engine to knock or, if the engine is equipped with a knock sensor, decrease the vehicles power and acceleration. Using a gasoline with an AKI or RON higher than that required by your vehicle is a waste of money.
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How can I stop my vehicle from knocking?

Have a mechanic determine whether your engine is in tune and the emissions control system is functioning properly. If it is, then there are two courses of action. 1) Use a gasoline with a higher
AKI or RON. 2) Treat the gasoline with an aftermarket deposit control additive concentrate
based on polyether amine chemistry. If there are combustion chamber deposits in the engine, the treatment will reduce them, which, in turn, will lower the octane requirement of the engine and decrease its tendency to knock until these deposits reform.
How can I increase the octane number of premium unleaded gasoline for use in my 1969 high-compression-ratio engine designed to use high-test (95 AKI) premium leaded gasoline?
Additives available in auto parts stores will increase the octane number of unleaded premium gasoline. The ones that contain high-octane aromatics and/or MTBE do not provide much benet because the volume being added is too small. The ones that contain a manganese antiknock additive will provide an increase in octane number that could solve your problem. But the increase likely will not be great when added to premium unleaded gasoline as suggested on the label.
What is the difference between gasolines sold by different companies?

Some companies sell gasolines with different AKI or RON values from others in some areas. Most companies use different deposit control additives. Federal regulations require that all gasolines in the U.S. contain a deposit control (DC) additive. The lowest additive concentration to pass all the
EPA required tests is called the LAC level. Many companies use the LAC level in their gasolines. As
a result, some gasolines provide better deposit control performance than others because these companies use DC additives that are more effective, have fewer side effects, and/or because they add them at higher concentrations.
Do engine deposits really make a difference?

Deposits in carburetors or on fuel injectors can affect the engines overall air-fuel ratio as well as individual cylinder air-fuel ratio, which in turn can affect fuel economy and emissions. Intake valve deposits also can affect emissions and, if heavy enough, can reduce power. Combustion chamber deposits affect octane number requirement and can affect some emissions. The federal government and the state of California require the use of deposit control additives in gasoline because of their concern that deposits can affect emissions. If the automobile manufacturers wanted deposits in their engines, they would build them that way.
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Do I need to add an aftermarket deposit control additive to the gasoline in my fuel tank?
If you regularly use a gasoline with superior quality deposit control performance, the use of an aftermarket deposit control additive should not be necessary unless your engine is particularly susceptible to deposit formation. If you regularly or occasionally use gasolines with lower quality deposit control performance, the addition of a deposit control concentrate to the gasoline in your vehicles fuel tank every 4500 kilometers (3000 miles) may reduce knocking, increase acceleration and power, and reduce emissions.
How will unleaded gasoline affect my older vehicle with an engine designed to be operated on leaded gasoline?
Pre-1971 U.S. vehicles were designed to operate on leaded gasoline. The original exhaust valve seats in these engines were not hardened or were not equipped with metal alloy inserts. The lead in the gasoline not only functioned as an antiknock additive, but served as a lubricant which kept the exhaust valves from wearing away the valve seat (exhaust valve seat recession) under certain severe operating conditions. Leaded gasoline is no longer available in the U.S. because it was completely banned from on-road gasoline in 1996. Other areas of the world have also banned lead. Driving around town or at normal highway speeds with unleaded gasoline will not result in exhaust valve seat recession. Exhaust valve seat recession may occur with unleaded gasoline at higher engine operating temperatures generated by an extended period of high-speed or uphill driving or towing a heavy load. If a trip is going to involve one or more of these situations and your pre-1971 vehicle hasnt been equipped with metal alloy exhaust valve seats, consider adding a lead substitute aftermarket additive to the gasoline in your tank during the trip. Consult your engine manufacturer before using the additive. In some countries, a lead replacement gasoline (petrol) is offered that contains protective additives.
What can I do to get better fuel economy?

Good fuel economy is a combination of good vehicle maintenance and sensible driving. Maintenance factors that contribute to good fuel economy are a properly tuned engine, a clean air lter, aligned and balanced front wheels, and tires with the correct air pressure. Since mistuned engines also result in higher emissions, the onboard diagnostic system in a modern car will alert you to an engine problem. Sensible driving involves smooth, steady acceleration rather than jackrabbit starts; driving at moderate rather than high speeds on the highway; not carrying a heavy load, using a luggage rack, or towing a trailer unnecessarily; not using the air conditioner or defroster excessively, and not idling the engine when it could be turned off. Some factors that reduce fuel economy are beyond your control: water, slush, or snow on the road, head winds, driving uphill, and driving in stop-and-go trafc.
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Will premium gasoline give better fuel economy than regular? Will one brand of gasoline give better mileage than another?
Gasolines with higher heating values give better fuel economy. Differences can exist, but they will be small compared to the benets to be derived from the maintenance and driving tips in the above answer. Traditionally, premium has had a slightly higher heating value than regular, and, thus, provided slightly better fuel economy. The difference less than 1 percent better is not large enough to offset premiums higher cost. The difference is likely to be less or nonexistent between grades of reformulated gasoline. There can be differences in heating value between batches of gasoline from the same renery or between brands of gasoline from different reneries because of compositional differences. The differences are small and there is no practical way for the consumer to identify the gasoline with a higher heating value.
How long can I store gasoline without it going bad?

Gasoline stored in a tightly closed container in a cool place will stay good for at least one year. It is better if the container or fuel tank is almost (95 percent) full. If the container or fuel tank will be in the direct sun or will be heated above 30C (80F) much of the time, add an aftermarket fuel stabilizer to the gasoline when you rst buy it. Gasoline-oil blends for two-stroke cycle engines stored under the proper conditions will keep as well as gasoline itself.
Can I use motor gasoline in my airplane?

ChevronTexaco recognizes that some older planes are certied [Supplemental Type Certicate (STC)] to use motor gasoline. The gasoline must meet the requirements of the gasoline specication (ASTM D 4814) and must not contain ethanol. ChevronTexaco strongly recommends AGAINST using motor gasoline in place of aviation gasoline. Aviation gasoline is made to different standards and, because of the serious consequences of engine failure, is distributed with extra attention to purity and cleanliness. In addition, the pilot will not always know whether the gasoline is oxygenated and, if so, what oxygenate it contains. And motor gasoline deposit control additives have not been approved for use in aviation fuels.
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Sources
Petroleum, General
Petroleum Panorama, The Oil and Gas Journal, 57 (5), January 28, 1959.
Petroleum Rening
Bill D. Berger and Kenneth E. Anderson, Renery Operation, Petroleum Publishing, Tulsa, Oklahoma, 1979. William L. Lefer, Petroleum Rening For the Nontechnical Person, 2nd Edition, PennWell, Tulsa, Oklahoma, 1985.
Gasoline
L.M. Gibbs, Automotive Fuels Gasoline, Encyclopedia of Energy, Technology and the Environment, John Wiley & Sons, New York, 1994. L.M. Gibbs, Gasoline Additives When and Why, Paper No. 902104, Society of Automotive Engineers, Warrendale, Pennsylvania, 1990. Longer-Term Storage of Gasoline, Chevron Technical Bulletin FTB-6, 1996. L.M. Gibbs, B. R. Bonazza, and R.L. Furey, Chapter 3, Automotive Gasoline, Salvator J. Rand, Editor, Manual 1 on Signicance of Tests for Petroleum Products, 7th Edition, ASTM International, West Conshohocken, Pennsylvania, 2003. Changes in Gasoline III, Downstream Alternatives, Inc., Bremen, Indiana, 1996. B. Hamilton, FAQ: Automotive Gasoline, http://www.faqs.org/faqs/autos/gasoline-faq/part1/ Gasoline For Your Car: Questions and Answers, 6th Edition, Publication 1580, American Petroleum Institute, Washington, D.C., 1996. Standard Specication for Automotive Spark-Ignition Engine Fuel, D 4814, ASTM International, West Conshohocken, Pennsylvania. Automotive Gasolines, SAE J313, Surface Vehicle Recommended Practice, SAE International, Warrendale, Pennsylvania, 2001. A Consumers Guide: Gasoline Octane for Cars, API Publication 6580, 6th Edition, American Petroleum Institute, Washington, D.C., 1996. Fuel Economy of Gasoline Vehicles, Chevron Technical Bulletin FTB-7, 1999. Use of Unleaded Gasoline in Cars Designed for Leaded Gasoline, Chevron Technical Bulletin
CTB-17, 1990.
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Oxygenated Gasoline
Oxygenated Gasolines and Fuel Economy, Chevron Technical Bulletin FTB-1, 1993. Use of Oxygenated Gasolines in Non-Automotive Engines, Chevron Technical Bulletin CTB-22, 1992. Alcohols and Ethers, A Technical Assessment of Their Application as Fuels and Fuel Components, 3rd Edition, Publication 4261, American Petroleum Institute, Washington D.C., 2001. M.J. Herman, Chapter 4, Fuel Oxygenates, Salvator J. Rand, Editor, Manual 1 on Signicance of Tests for Petroleum Products, 7th Edition, ASTM International, West Conshohocken, Pennsylvania, 2003.
Reformulated Gasoline
Federal Reformulated Gasoline, Chevron Technical Bulletin FTB-4, 1994. California Phase 2 Reformulated Gasoline, Chevron Technical Bulletin FTB-5, 1995. Cleaner Burning Gasoline Binder, California Air Resources Board, Sacramento, California, 1996
ASTM Committee D02 on Petroleum Products and Lubricants Research Report D02: 1347,
Research Report on Reformulated Spark-Ignition Engine Fuel, ASTM International, West Conshohocken, Pennsylvania, 2003.
Fuels and Energy Division
Ofce of Mobil Sources United States Environmental Protection Agency Mail Code: 6406J 401 M Street SW Washington, D.C. 20460 (202) 233-9000 http://www.epa.gov/omswww/California Air Resources Board
California Air Resources Board
P.O. Box 2815 Sacramento, California 95814 (916) 322-2990 http://www.arb.ca.gov/homepage.htm
Vehicles
Ulrich Adler, Editor, Automotive Handbook, 3rd Edition, Robert Bosch GmbH, Stuttgart, Germany, 1993. Ulrich Adler, Editor, Automotive Electric and Electronic Systems, 2nd Edition, Robert Bosch GmbH, Stuttgart, Germany, 1995.
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Sources
Paul Degobert, Automobiles and Pollution, Society of Automotive Engineers, Inc., Warrendale, Pennsylvania, 1995. T.K. Garrett, Automotive Fuels and Fuel Systems, Vol. 1: Gasoline, Society of Automotive Engineers, Inc., Warrendale, Pennsylvania, 1991. J.B. Heywood, Internal Combustion Engine Fundamentals, McGraw Hill, New York, 1988. E.F. Obert, Internal Combustion Engines and Air Pollution, Harper and Row, New York, 1973.
Federal Regulations
Fuels and Energy Division
Ofce of Mobil Sources United States Environmental Protection Agency Mail Code: 6406J 401 M Street SW Washington, D.C. 20460 (202) 233-9000 http://www.epa.gov/omswww/ Code of Federal Regulations, Title 40 Protection of Environment Part 51 Requirements For Preparation, Adoption, and Submittal of Implementation Plans Subpart S Inspection/Maintenance Program Requirements Part 79 Registration of Fuels and Fuel Additives Part 80 Regulation of Fuels and Fuel Additives Part 85 Control of Air Pollution From Motor Vehicles and Motor Vehicle Engines Part 86 Control of Air Pollution From New and In-use Motor Vehicles and New and In-use Motor Vehicle Engines: Certication and Test Procedures
National Vehicles and Fuel Emission Laboratory
Ofce of Mobile Sources United States Environmental Protection Agency 2565 Plymouth Road Ann Arbor, Michigan 48105 (313) 668-4200
California Regulations
California Air Resources Board
P.O. Box 2815 Sacramento, California 95814 (916) 322-2990 http://www.arb.ca.gov/html/homepage.htm
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Abbreviations
F C API ABS A/F AKI API ARB ASTM BDC Cn CCDI CEN CFR CO CO2 CRC DI DOHC DVPE Et ECM EGR EPA ETBE EtOH FTP 75 HC HWFET I/M JIS kPa LAC MMT MON MTBE NAAQS NMHC 86
degrees Fahrenheit, the unit of temperature in the United States customary system degrees Centigrade, the unit of temperature in the metric (SI) system degrees American Petroleum Institute, the unit of gravity in the API system automatic braking system air-fuel ratio antiknock index, the average of the Research and Motor octane numbers [(RON + MON)/2, simplied to (R + M)/2] American Petroleum Institute (California) Air Resources Board ASTM International (formerly American Society for Testing and Materials) bottom dead center, lowest position of piston in a cylinder, relative to the cylinder head carbon number of hydrocarbon whose molecule contains n carbon atoms combustion chamber deposit interference Comit Europen de Normalisation (European Committee for Standardization) Code of Federal Regulations carbon monoxide carbon dioxide Coordinating Research Council driveability index double overhead cam dry vapor pressure equivalent, the value of vapor pressure obtained by a specic method distillation prole volume percent evaporated at t temperature engine control module exhaust gas recirculation (United States) Environmental Protection Agency ethyl tertiary-butyl ether ethanol federal test procedure cycle, a dynamometer emissions test cycle hydrocarbon highway fuel economy test cycle, a dynamometer emissions test cycle inspection and maintenance program: program to check condition and performance of a vehicles emission systems Japanese Industrial Standard kilopascal, a unit of pressure in the metric (SI) system Lowest Additive Concentration (that can pass the federal deposit control additive certication tests) methylcyclopentadienyl manganese tricarbonyl, an antiknock compound Motor octane number methyl tertiary-butyl ether national ambient air quality standard non-methane hydrocarbons
Abbreviations
NMOG NO NO2 NOX OBD OHC ONR ORI PAH PCV PFI PM10 PM2.5 PNA POM psi RdON RFG RD ROG RON SI SIP SO2 SOX STC Tv TAME TBA TBI TDC TEL TML U.S. VLI V/L VOCs WOT
non-methane organic gases nitric oxide nitrogen dioxide oxides of nitrogen On-board diagnostics: the ability of engine control module to analyze and diagnose emission system malfunctions overhead cam octane number requirement (of an engine) octane requirement increase (of an engine) polynuclear aromatic hydrocarbons, aromatic hydrocarbons with several fused rings positive crankcase ventilation port fuel injector particulate matter with a particle size less than 10 microns particulate matter with a particle size less than 2.5 microns polynuclear aromatics polycyclic organic matter pounds per square inch, a unit of pressure in the U.S. customary system road octane number reformulated gasoline relative density reactive organic gases Research octane number Systme International dUnits (International System of Units), metric system of measurement state implementation plan, a plan to improve air quality sulfur dioxide sulfur oxides Supplemental Type Certicate, a certicate that can be purchased for some older planes that allows the use of motor gasoline in place of aviation gasoline distillation prole temperature at v volume percent evaporated tertiary-amyl methyl ether tertiary-butyl alcohol throttle body injector top dead center, highest position of piston in a cylinder, relative to the cylinder head tetraethyl lead, an antiknock compound tetramethyl lead, an antiknock compound United States of America vapor lock index vapor-liquid ratio volatile organic compounds wide open throttle 87
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Table of Contents

1 Gasoline and Driving Performance

160 300 250 200 80 150 100 50 0 0 10 20 30 40 50 60 70 80 90 100 40 120

Gasoline and Driving Performance

Warmup and Cool Weather Driveability Short Trip Economy

Vapor Lock Index

tion against vapor lock and hot-fuel handling problems.

54 (7.8) 61 (9.0) 69 (10.0) 79 (11.5) 93 (13.5) 103 (15.0)

70 (158) 70 (158) 65 (149) 60 (140) 55 (131) 50 (122)

Gasoline and Driving Performance

Gasoline and Driving Performance

Octane Number Requirement

formulation differences among batches and among reners. A survey of

line contains more volatile, less dense hydrocarbons.

Gasoline and Driving Performance

Factors Affecting Fuel Economy

Fuel Economy Road Test

Analogous to air conditioning on some vehicles 2.3 1.9 4.3 6 25 50

N/A 11.8 1 1 3.3 21

Unknown, but likely small

Gasoline and Driving Performance

Other Performance Factors

2 Gasoline and Air Quality

Figure 2-1 Maximum Hourly Pollutant Levels in California 1973 2002

1985 1990 Calendar year

Progress in the U.S.

Federal standard California standard

Reprinted with permission from CVS News, July 2003.

Gasoline and Air Quality

Air Quality Standards

*Indicative, not mandatory **Winter = 1 October 31 March

Gasoline and Air Quality

Figure 2-4 Emission Sources: 1998 National Man-Made VOC Emissions

Figure 2-6 Emission Sources: 1998 National Man-Made NOX Emissions

Origin of Vehicle Emissions 8

Gasoline and Air Quality

Vehicle Emissions: Limits

Gasoline and Air Quality

0.20 0.08 0.10 0.08 0.08

Inspection and Maintenance

Vehicle Emissions: Gasoline Effects

Gasoline and Air Quality

to a lesser extent can reduce exhaust VOC and CO.

evaporative and exhaust VOC emissions.

Figure 2-10 Chronology of United States Gasoline Regulations

Distillation Prole Temperatures Gasoline containing signicant

Reformulated Gasolines (RFGs)

Sulfur Content Reduce sulfur oxide emissions and particulates

additive beginning in 1995.

Leaded Fuels Banned Protect public health

EPA introduced federal Phase I RFG in 1995. It had to be used in the

Gasoline and Air Quality

Vapor pressure limits 17.1b 36.6c 27.4b 29.0c

16.5 16.5 21.5

No increase 1.5 6.8

a Optional 19951997; mandatory starting in 1998. b Northern states c Southern states

3 Gasoline Rening and Testing

Figure 3-1 Gasoline Carbon Number Distribution

Regular unleaded Premium unleaded

Figure 3-2 Distillation Prole vs. Cummulative Carbon Number Distribution

Distillation Profile Cumulative Carbon Number Distribution

CH2qCH (CH2 )3CH3

2,2,4 -Trimethylpentane (Isooctane) C8H18 CH3 CH3

Cis 1,3-dimethylcyclohexane C8H16 CH3