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Refining Overview Part 3 Processing

Chapter 12 Gasoline Manufacturing Overview

CHAPTER 12
GASOLINE MANUFACTURING OVERVIEW
About This Chapter
This chapter provides an overview of gasoline manufacturing and the factors that ultimately influence refinery
configuration. Gasoline has been characterized as the most important product of the refinery and accounts for
almost 45% of the total demand for refined products. This percentage has not changed much in the last fifty
years. Instead what has changed is the complexity of the specifications.
The composition of gasoline addresses two main issues: performance and emissions. The strategy of the
manufacturer is to provide the proper gasoline composition to meet both goals. The table summarizes the
organization of this chapter. It lists the desirable characteristics of gasoline, the parameters they affect, and the
blending streams that the gasoline manufacturer configures to produce gasoline. Although this chapter focuses
on gasoline manufacturing, engine design and gasoline composition are intimately related and some relations
are discussed.
AIR POLLUTANTS

GASOLINE
CHARACTERISTICS

Criteria Pollutants

Lead (Pb)
Particulate Matter (PM)
Carbon Monoxide (CO)
Sulfur Dioxide (SO2)
Nitrogen Oxides (NOx)
Ozone (O3)

Hazardous Air Pollutants (HAPs or Air


Toxics)
Total of 189 compounds including
benzene and formaldehyde.

Emission

Tetra ethyl lead (TEL)


Aromatics
Benzene
Olefins
Sulfur
Oxygen
Vapor Pressure
T-90
Performance

ENGINE PERFORMANCE

Antiknock
Vapor lock
Fuel Consumption
Engine deposits

Octane
Vapor Pressure
Additives

GASOLINE BLENDING
STREAMS

Butane
Isomerate (from

Isomerization Unit)
Catalytic Cracker Naphtha
(Cat Gasoline)
Reformate (from Catalytic
Reformer)
Alkylate (from Alkylation
Unit)
Coker Naphtha
Visbreaking Naphtha
Oxygenates

Performance and Emissions Parameters: Why They are Important


The operation of an internal combustion automobile engine must not only provide acceptable performance but
must meet emission criteria. This section discusses the performance and emission parameters and why they are
important.
Engine Perfomance Parameters
Although there are many more important parameters, only several major performance factors are discussed.

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Detonation, Pre-ignition and Engine Performance. The single most important property of gasoline is its
resistance to detonation and pre-ignition, which we hear as knocking. This resistance to knocking is expressed
as octane number. Knocking limits the power that can be developed by the engine/fuel combination.
Detonation is the spontaneous explosion of the residual fuel/air in the combustion chamber as the normal
smoothly burning combustion nears completion. It is a very fast free radical oxidation chain reaction. The
knocking occurs when this second flame front/pressure wave collides with the normal combustion flame
front/pressure wave.
A much more destructive form of knocking is pre-ignition, which is the spontaneous ignition of the fuel/air
charge before the ignition spark. It is caused by the fast moving compression wave front outrunning the
combustion flame front. As the unburned gases are compressed in the cylinder, the temperature increases. If
the autoignition temperature is attained before the flame front ignites the mixture, the mixture will
spontaneously pre-ignite. Pre-ignition usually causes major engine damage in just a few seconds or minutes,
while an engine may endure light or moderate detonation for long periods without obvious damage.
Increasing humidity, cooler ambient air temperature, and altitude (3 RON per thousand feet at constant spark
setting) reduce requirements for anti-knock. Combustion chamber deposits, a major variable over time,
increase octane requirements.
Volatility and Engine Performance. Another important characteristic of gasoline is its volatility. The fuel
must be volatile enough to provide engine cold-starting capability at the lowest temperatures expected in
service. Too low a volatility and the engine will not start or it has poor driveability and stalls easily. On the
other hand, the fuel must not generate too excessive vapor in the fuel system at the highest expected service
temperatures and altitude. Too high a volatility, and vapor forms in the fuel pumps and lines, causing vaporlocking and stalling.
Fuel Economy and Engine Performance. Among other factors, fuel economy is strongly affected by
thermal efficiency. As the compression ratio of the engine increases, the efficiency increases, but so does the
requirement for fuels that do not knock. Automobiles, starting in the 1980s, have been adding electronic engine
management systems that incorporate knock sensors to continuously adjust the ignition timing. Electronic
engine management systems are designed to adjust the timing of the spark so that it fires in advance of the
piston reaching the top of its travel, or top dead center. Advanced firing increases the fuel economy but also
intensifies the frequency of pre-ignition. The electronic system controls the firing advance to contain knock and
maximize performance and fuel economy depending on the fuel utilized. Computers provide the necessary
combustion stability in engines operating at lean air to fuel ratios (or the actual air/fuel ratio is greater than the
stoichiometric air/fuel ratio), thus increasing fuel economy while maintaining low emissions of nitrogen oxides.
Such lean mixture combustion is difficult to achieve with mechanical controls.
Engine Deposits and Engine Performance. Engine deposits affect fuel economy and emissions. Deposits
are of particular concern in the carburetor, fuel injectors, inlet valves, and combustion chamber. These deposits
are affected by component design, primarily injectors, valves, and combustion chambers. Inlet valve
temperatures, airflow, and oil coverage also are fundamental to avoid deposits.
Air Pollution Parameters
Air pollution is an important yet complicated factor in fuel composition design. Air pollutants are identified by
their affects on health, property and environmental damage, as determined by epidemiological studies. There
are two main types of air pollutants of interest to transportation fuels manufacturing.
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Hazardous air pollutants (HAPs) or air toxics are air pollutants that increase a persons statistical
probability of developing cancer, immune and neurological damage, respiratory irritation, and endocrine and
reproductive disorders. In general, these are pollutants that are believed to have essentially no threshold and are
harmful at even small concentrations. EPA has been regulating air toxics since the 1977 Clean Air Act. There
are 189 hazardous air pollutants. Benzene, formaldehyde, acetaldehyde, and 1,3-butadiene are formed in
combustion. Mobile sources account for the majority of the emissions of benzene (both from fuel and
combustion) and 1,3-butadiene in the United States.
Criteria air pollutants are pollutants that can injure health, harm the environment, and cause property
damage. In general, these are pollutants that are believed to have a threshold level above which harmful effects
are manifested. Criteria air pollutants are regulated through the National Ambient Air Quality Standards
(NAAQS), which are legal limits placed on the levels of criteria pollutants in the atmospheric air. The
Environmental Protection Agency (EPA) labels these pollutants as criteria air pollutants because the bases for
setting standards are developed from health-based criteria. One set of limits (primary standard) protects health;
another set of limits (secondary standard) is intended to prevent environmental and property damage. A
geographic area that meets or does better than the primary standard is called an attainment area; areas that don't
meet the primary standard are called non-attainment areas. The Environmental Protection Agency has been
regulating criteria air pollutants since the 1970 Clean Air Act. More information may be found at the Office of
Air and Radiation <www.epa.gov/oar>. There are six criteria air pollutants:
Lead emissions have been known to be toxic for several thousand years and adversely affects the
kidneys, liver, nervous system and other organs and leads to neurological impairment, learning deficits and
behavioral disorders. Tetra ethyl lead (TEL) is not available for on-road motor vehicles.
Carbon monoxide (CO) is a colorless, odorless and poisonous gas produced from incomplete
combustion of carbon in fuel. Carbon monoxide acts to block oxygen absorption into the human
bloodstream by reacting with hemoglobin to reduce oxygen-carrying capacity. Elevated exposures are
serious for those suffering from cardiovascular disease and lead to visual impairment, poor learning ability,
loss of manual dexterity and the ability to perform complex tasks. At high enough levels, acute effects
include depressed cardiac activity and respiration, convulsions, coma, and even death. Over half the carbon
monoxide emissions are from motor vehicles.
Sulfur Dioxide (SO2) is formed during burning of sulfur containing fuel and other industrial processes.
Short tem exposure to high concentrations lead to reduced lung function and for longer exposures, are
associated with respiratory illness and aggravation of cardiovascular disease. Sulfur dioxide, along with
nitrogen oxide, is a major contributor to acid deposition (as sulfuric acid rain), which causes acidification
of streams and lakes, damages crops and trees, and accelerates corrosion of building materials and coatings.
Additionally, sulfur dioxide is a major precursor to particulate matter, primarily 2.5 microns diameter,
which is a further health concern as well as a component of haze. The NAAQS have levels for both health
and environmental damage. Motor vehicles are a minor source for sulfur oxides although sulfur in gasoline
damages catalytic converters and causes engine wear and engine oil deterioration.
Nitrogen dioxide (NO2) is the brown gas formed by high temperature combustion of fuels. The family
of nitrogen-oxygen compound includes NO and NO2 and is often treated as one species NOx. Nitrogen
dioxide is a severe irritant to the lungs and can cause respiratory infections, pneumonia and bronchitis.
Nitrogen dioxide, along with sulfur dioxide, is a major contributor to acid deposition (as nitric acid rain),
Additionally, nitrogen dioxide is a major precursor to particulate matter, primarily 2.5 microns diameter.
But nitrogen dioxide is additionally known as the principal contributor, with volatile organic compound
(VOCs), of ozone, the main component of smog.
Particulate matter include dust, dirt, smoke and liquid droplets, some formed in the atmosphere by
condensation of sulfates, nitrates and hydrocarbons. Course particles with diameters larger than 10
microns (micrometers) generally originate from materials handling, construction and windblown
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dust. Fine particles with diameters less than 2.5 microns are emitted during combustion from industrial
facilities and motor vehicles. Gasoline internal combustion engines do not emit significant levels of
particulate matter as opposed to diesel engines. Particulate matter aggravates existing respiratory and
cardiovascular disease, damages lung tissue and the bodys defense system against foreign matter, and may
cause cancer. Fine particles 2.5 microns (micrometers) in diameter or less are considered more serious
since they can penetrate easily into the respiratory tract and are retained longer. Particulate matter,
especially condensed liquids, also contributes to haze.
Ozone (O3) is a photochemical oxidant that is found in both the troposphere (ground level to 6 miles
above the earths surface) and the stratosphere (6 to 30 miles above the earths surface). As ground level
ozone it is the principal constituent of smog and is formed by a series of complex atmospheric chemical
reactions primarily involving nitrogen oxides (NOx) and volatile organic compounds (VOCs) and sunlight.
Volatile organic compounds, for air pollution meaning, are a specific group of compounds that participate
in ozone formation and are called ozone precursors. Not all hydrocarbons are VOCs - the most common
excluded are methane and ethane, the primary compounds in natural gas. Ozone as a strong oxidant
damages lung tissue and reduces lung function, which is accompanied by chest pain, coughing and
pulmonary congestion in both healthy persons and those with impaired respiratory function. The toxicity of
ozone is such that the NAAQS and the workplace threshold limit established by the Occupational Safety
and Health Act (OSHA) are very similar.
Photochemical Smog and Haze. Several of the most commonly known manifestations of air pollutants are
photochemical smog and haze.
Photochemical smog is a mixture of pollutants including ozone, nitrogen oxides, hydrocarbons,
particulates, and other components including a variety of organic and acidic compounds such aldehydes,
ketones, and peroxyacetyl nitrate. Smog is measured by the concentration of ozone in the ground-level air
since ozone is a major component of photochemical smog. The health effects of smog are similar to those
of the constituents. Smog tends to form a diffuse blanket at low levels and in the presence of temperature
inversions it can be trapped and accumulate.
The chemistry of smog is very complex but a gross simplification can reveal the essence. There are two
chains of reactions. The first group of reactions generates ozone and nitrogen oxide in what is essentially a
reversible reaction.
NO2

ultraviolet light

O + O2

NO + O
O3

NO + O3

NO2 + O2

However, the second set of reactions involving volatile organic compounds (VOCs) upset the reverse
reaction such that NO can be converted to NO2 without consuming ozone. Ozone forms an excited oxygen
molecule, which in turn reacts with water molecules to form OH radicals. The OH radicals then react in an
elaborate sequence that involves oxidation of VOCs to the following overall reaction. The R refers to any
length of hydrocarbon.
VOC hydrocarbons + O2 + 2NO2

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VOCs have varying reactivities with OH radicals. In general, internally bonded olefins are the most
reactive with OH radicals followed in descending order by multi-alkyl aromatics (xylenes in particular),
mono-alkyl aromatics (with toluene at the bottom of that reactivity list) and pentane-plus paraffins. Oddly,
acetylene, ethylene and benzene are not very reactive in producing smog. The more complex VOC
molecules form a variety of acetyl radicals CH3(CO) which react with oxygen and nitrogen dioxide to form
peroxyacetyl nitrate - the notorious eye irritant in smog. Additionally VOCs also react directly with ozone
to form a variety of aldehydes.
O + O3 + hydrocarbons
hydrocarbons + O2 + NO2

aldehydes
peroxyacetyl nitrate + other compounds

Haze is generic term for fine particles, from 0.1 microns to 2 microns (micrometer) in diameter, formed
primarily by liquid condensation of nitrates and sulfates and combined with water vapor and dust on which
are adsorbed hydrocarbons, sulfates and nitrates. Haze is not only a health problem but is also a serious
visibility problem. The Environmental Protection Agency is integrating standards on particulate matter
(haze) with ozone (smog) because they share common characteristics.
Gasoline Characteristics: How They Affect Performance and Emissions
The previous section described the most important parameters for internal combustion automobile engines in
terms of performance and air emissions. This section will describe important gasoline characteristics.
The links between the characteristics of gasoline, such as the vapor pressure or amount of sulfur, and the
performance and emissions from internal combustion engines have been studied extensively in what is
generically called the Auto/Oil studies, both in Europe and in the United States. One of the first studies, started
in 1989 by a coalition of United States auto companies and fuel manufacturers as the Coordinating Research
Council, was the Auto/Oil Air Quality Improvement Research Program. Since then many studies have
reevaluated the results. In general, the studies looked at both fuel composition (gasoline and diesel) and engine
design and the effects on performance and emissions. The studies form the scientific basis for fuel
reformulations and therefore manufacturing configuration.
Octane number for anti-knock. Providing fuels with sufficient octane rating prevents knock. There are
two tests for octane: the Motor Octane Number (MON) and Research Octane Number (RON). Both are
measured in a standard test engine but at different speeds and fuel temperatures. Motor Octane Number is
considered representative of open road driving and determined at 900 RPM; Research Octane Number Number
is considered representative of city, slow speed driving and determined at 600 RPM. Typically RON is 5 to 10
numbers above MON reflecting the greater demands on the engine. The average M+R/2 (PON) is commonly
used. For years this was known as the Pump Octane Number and also as the Road Octane Number in
government publications. It is currently officially known as the Anti-knock Index. M+R/2 (PON) is the label
on station pumps and one will usually find three grades: 87, 89 and 93. Octane of gasoline is determined by
running in a standard ASTM test engine and comparing the knocking tendency with blends of n-heptane and
2,2,4- trimethyl pentane. Normal heptane is assumed to be zero octane. Isooctane 2,2,4- trimethyl pentane is
assumed to have an octane number of 100. In increasing order of octane are normal paraffins, olefins,
aromatics and branched isoparaffins. Oxygenates such as MTBE have excellent octane ratings in excess of 100.
The blending of streams to maintain sufficient anti-knock capability is discussed in the next section.
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Lead is a currently minor problem in the United States in terms of auto emissions since tetra ethyl lead is not
available in on-road fuel. It was first limited in gasoline by the Surgeon General in 1926 to 3.0 milliliters of
TEL/gallon of gasoline (3.17 grams Pb/gal). Due to its toxicity and interference with the operation of catalytic
converters, lead was phased from gasoline starting in 1975 and eliminated as of January 1, 1996. However, lead
is still present in aviation gasoline for piston engine aircraft, off-road vehicles, farm equipment, marine engines,
on-road automobile fuel in other countries, and is found in the atmosphere due to various generation sources.
Reducing aromatics and benzene reduce hydrocarbons, carbon monoxide, benzene and NOx in emissions.
However, the effect on NOx is quite complex and several trends are observed. Additionally the effect on other
air toxics such as formaldehyde, acetaldehyde, and 1,3 butadiene are mixed. Tailpipe emissions of carbon
monoxide, nitrogen oxides, and volatile hydrocarbons are predominately controlled by three-way catalytic
converters.
Reducing olefins primarily reduce NOx and the air toxic 1,3 butadiene.
Reducing sulfur compounds has several effects. Sulfur in gasoline greatly affects the concentration of
hydrocarbons, carbon monoxide, and NOx in exhaust emissions although internal combustion engines are a
minor source for sulfur dioxide. Sulfur oxides reduce the efficiency of the catalyst in catalytic converters. The
loss of efficiency is immediate but it is conjectured that the efficiency loss is essentially reversible. Controlling
sulfur is a primary means of enhancing catalytic conversion. Motor vehicles are major sources for the ozone
precursors nitrogen oxides (NOx) and volatile organic compounds (VOCs). Tailpipe emissions of carbon
monoxide, nitrogen oxides, and volatile hydrocarbons are predominately controlled by three-way catalytic
converters.
Oxygenates, such as ethanol and MTBE, were initially added to gasoline to improve octane rating but now
are also intended to reduce carbon monoxide and to a lessor extent hydrocarbons. Oxygenates promote more
complete combustion because they contain some of the needed combustion oxygen, because they are simpler
molecules with straightforward combustion reactions, and because lower boiling points enhance evaporation
and efficient mixing with air.
Reducing vapor pressure reduces carbon monoxide and hydrocarbon emission. In the past, over half of the
vehicle emissions have been attributed to evaporation losses such as filling losses at the pump, under hood
evaporation losses, and incomplete combustion losses. The effect on air toxics is similar but air toxics (1,3
butadiene, formaldehyde, and acetaldehyde) account for less than 5% of total hydrocarbon tailpipe emissions.
On the other hand, the correct vapor pressure is important for engine operation. Specifications to assure
appropriate vaporization are addressed in standard ASTM D 439, which defines five volatility classes intended
to provide satisfactory fuel performance over the temperatures and atmospheric pressures expected for the
region and season. The standard is applied based on historical temperature profiles determined state-by-state
and month-by-month, although the volatility limits are adjusted in various areas to minimize gasoline
evaporative emissions. Volatility is defined in terms of distillation and Reid Vapor Pressure (RVP), which is
roughly the true vapor pressure of the gasoline at 100F. Winter RVP is approximately 1.5 psig higher than the
summer RVP. The RVP increased over the period of years between 1945 and 1975 to provide higher octane
rating before emission control led to a limitation to minimize gasoline evaporative emissions.
Reducing T-90 greatly reduces hydrocarbons and air toxics. T-90 is the temperature at which 90% of the
material has flashed off in a distillation. T-90 is an indication of the amount of heavier materials in gasoline,
essentially C9 plus aromatic compounds.
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Fuel additives have been effective in reducing deposits and emissions and increasing fuel economy. In the
1950s, the first gasoline detergent additives were developed to control carburetor deposits. Inlet valve deposits
were managed in the 1970s by a new series of additives. And in the 1980s the introduction of fuel injection
required the development of improved detergent additives.
The Manufacture of Gasoline: Providing the Gasoline Characteristics
To meet the performance and emission attributes, manufacturers adjust gasoline characteristics. The
formulations of these fuels are based on the EPA Complex Model formulas that predict tailpipe emission as a
function of gasoline characteristics.
Prior to 1990, EPA had sought to correct emissions problems by mandating changes in automobiles with
mileage efficiency and addition of catalytic exhaust systems. But the 1990 Clean Air Act addressed fuel
composition as factor. The Reformulated Fuel Gasoline (RFG) program was offered by the petroleum and
oxygenate industries as a substitute for certain provisions of the 1990 Clean Air Act on the argument that
emission reductions would follow immediately after introduction of reformulated gasoline. The program was
accepted and the final legislation set emission performance requirements for reformulated fuels. Phase I of the
federal reformulated gasoline program was introduced in 1995. Phase II is introduced in 2000. More
information made be found at the EPA Office of Transportation and Mobile Sources <www.epa.gov/oms>.
Gasoline Blending Characteristics
Critical to the proper gasoline composition is the processing of each gasoline streams to optimize desirable
gasoline characteristics. The following summaries are estimates of each blending stream characteristics. These
estimates form the basis for the discussions in the following section on general options for reducing and
maintaining characteristics, such as lower sulfur or higher octane.
Gasoline Blending Streams and Characteristics

Butane
Straight Run
Isomerate from
Isomerization Unit
Cat Gasoline or
Catalytic Cracker
naphtha
Refomate from
refomer
Alkylate from
Alkylation Unit
Coker Naphtha
Visbreaking Naphtha
Oxygenates
MTBE

Volume
in Pool
%
1
0-5
15

Octane
(R+M)/2
92
65
85

Aromatics
Vol% in
stream
0
10
0

Benzene
Vol% in
stream
0
0
0

Olefins
Vol% in
stream
0
2
0

35

85

25

30

90

60

20

95

1
1
1.7

80
110

Sulfur
PPM (wt)
20
2
2

Oxygen
Vol% in
stream
0
0
0

Reid Vapor
Pressure
60
12
15

35

1,200

10

40

1,100

10

0
0
20

13

1
1
0

Besides the characteristics of each blending stream, an estimate of the average gasoline pool is instructive.
However, the pool differs greatly since the average is a function of the season, location, gasoline grade and

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brand limited by maximums on characteristics. Following is a general guideline for an average reformulated
fuel with an octane of 89. With the introduction of Phase II RFG, United States average sulfur levels are
expected to be lowered to 30 ppm with a not to exceed level of 80 ppm. European sulfur levels are also being
greatly reduced.
Reformulated Fuel Typical Properties 89 Octane
T-90
(F)
320

Aromatics
Vol% in
stream
23

Benzene
Vol% in stream

Olefins
Vol% in stream

Sulfur
PPM (wt)

0.8

300

Oxygen
Vol% in stream
(as MTBE)
8 - 15

Reid Vapor Pressure


(psi)
8

Reducing Aromatics and Benzene in Gasoline


Environmental pressures have made it desirable to reduce aromatics in the gasoline pool. The most stringent
environmental limitation imposed with regard to aromatics is on benzene in gasoline. Benzene is being reduced
to levels of about 0.8% (vol) maximum in motor gasoline. This makes for the challenging problems of
processing fractions to desired petrochemical products, and of reducing the residual aromatics in the gasoline
pool for compliance with automotive emission standards. There are several approaches to reducing benzene
and other aromatics.
Saturation of Benzene and Isomerization of naphthenes to isoparaffins. One common approach to reducing
benzene is the diverting of benzene and cyclohexane normally left in the naphtha fraction to Straight Run
Gasoline.
The pentane/hexane portion of crude oil is referred to as Straight Run Gasoline or Light Straight Run Gasoline.
In early years it was blended in gasoline without upgrading even as gasoline octane number increased. Later
Straight Run was upgraded by addition of tetra ethyl lead (TEL) to the gasoline. When TEL was eliminated
from gasoline many refiners incorporated isomerization of normal paraffins to isoparaffins to upgrade Straight
Run octane number. The benzene and cyclohexane in naphtha are diverted to the lighter boiling Straight Run
Gasoline fraction by raising the cut-point between Straight Run and naphtha at the atmospheric crude unit.
Benzene is then hydrogenated to cyclohexane and the cyclohexane may be isomerized to increase the octane
rating before going to the gasoline pool.
Reducing reforming severity to reduce benzene and heavier aromatics. If the quality of the gasoline pool will
permit it, reforming severity can be reduced thereby producing less aromatics, particularly the aromatics heavier
than benzene. Benzene is then excluded by diversion to Straight Run gasoline.
Reducing aromatics in gasoline by reducing its final boiling point. Reducing the final boiling point of
reformate not only diverts xylenes and C9s to kerosene/jet fuel, it reduces vapor pressure of the gasoline pool,
which also is desirable in terms of complying with environmental regulations.
Reducing aromatics from the Catalytic Cracker. Catalytic gasoline is high in olefin content in the front end
and high in aromatics in the back end. By lowering the catalytic cracked gasoline final boiling point on the
catalytic cracker fractionator, more of the higher boiling aromatics are diverted from gasoline to heating oil and
diesel. Since catalytic cracker gasoline is high in sulfur, diverting catalytic gasoline to diesel also reduces the
sulfur level in the gasoline pool. But diverting aromatics from catalytic gasoline to heating oil/diesel is
normally limited by quality considerations of those products. In particular, aromatics hurt diesel cetane number
and excess sulfur may impact sulfur specifications.
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Extraction of aromatics in the Aromatics Complex. The Aromatics Complex can be part of the operations to
control benzene and other aromatics in gasoline. These operations maximize aromatics in reformate and then
remove them for petrochemical outlets. The Gulf Coast, Midwest and Great Lakes refineries tend to have
aromatics removal operations devoted to aromatics production and purification. The refiners on the West Coast
normally must resort to the other benzene and aromatics reduction schemes mentioned above. Aromatics
extraction is practiced in about half of the largest fifty refineries but in almost none of the smaller ones.
Reducing Olefins
Almost all the olefins in the gasoline pool, and most of the sulfur, come from catalytic cracker gasoline. Some
olefins and sulfur come from Delayed Coker naphtha.
The front end of catalytic cracker gasoline is rich in olefins and sulfur while the back end is rich in aromatics
and sulfur. The C-5 olefins can be fractionated out, subjected to simple chemical treating for sulfur removal,
and alkylated to produce good octane C9s. The C9 isoparaffins with lower volatility and higher octane will
offset some of the loss of heavier aromatics in gasoline blends. Alternatively, the light olefins via etherification
could be converted to the oxygenate tertiary amyl methyl ether (TAME).
Catalytic cracker gasoline does not contain much C-6 and even less C-7 olefins since these olefins are very
reactive and enter into cracking and combining reactions forming light olefins and aromatics. These olefins
may be removed from the heavy fraction by hydrogenation for sulfur removal but it may be necessary to
isomerize the fraction to improve the octane number since the hydrogenation will produce normal paraffins of
lower octane number.

Delayed Coker naphtha can be treated with catalytic cracker gasoline since it is usually is much smaller that
catalytic cracker gasoline.
Reducing Sulfur Content
Almost all the sulfur in the gasoline pool comes from catalytic cracker gasoline with small amounts from
Delayed Coker naphtha. There are several approaches to changing the gasoline sulfur level.
The last 20% of catalytic cracker gasoline may be put into catalytic cracker Light Cycle Oil. Although this
does not eliminate sulfur from the refinery products, it moves the contaminants (sulfur and olefins) to jet, diesel
or heating oil.
The front end of catalytic cracker gasoline is rich in olefins and sulfur. This may be hydrogenated with
catalysts selective for desulfurization that minimize olefin saturation. There are several treating alternatives for
removing sulfur from the lighter part of catalytic gasoline using involving caustic reactions with the sulfur
compounds, such as the UOP Merox process. These alternatives have the advantage over hydrogenation
because they are cheaper and do not hydrogenate the gasoline, thereby avoid reducing the octane number.
The back end of catalytic gasoline is highly aromatic, with some olefins, and high in sulfur content.
Hydrotreating all or part of catalytic gasoline will remove sulfur, saturate olefins, and partially saturate
aromatics. Catalysts selective for desulfurization minimize olefin and aromatic saturation.
Gas oils may be deep hydrotreated for both sulfur and metals removal as well as ring saturation. This
significantly upgrades catalytic cracker unit feed stock quality, improves yields, and reduce sulfur from catalytic
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cracker products. Many refiners are now hydrotreating portions of the catalytic cracking unit gas oil feeds.
Hydrogen consumption can vary from say 300 scf/b for simple sulfur reduction at 300 psig to 1000 scf/b for
extensive sulfur removal and ring saturation at 1000 psig. Much of the heavier fraction of the gas oil has sulfur
deeply imbedded in the molecules calling for very intensive hydrotreating.
Managing Volatility
The vapor pressure of blends is a definite problem that limits the amount of high-octane butane and low octane
straight run gasoline that can be included in the blend.
Isomerization of pentane/hexanes is not as useful as it might have been because of the adverse effect on vapor
pressure and front-end distillation characteristics.
Refiners are alkylating more propylenes and butylenes since alkylate has good octane numbers, good
volatility characteristics, and no olefins.
It is expected that more refiners will alkylate amylenes (C5 olefins) to provide heavier non-aromatic highoctane blend stocks. It is not yet clear how widespread amylene alkylation might become. C-5 olefin alkylation
will remove light olefins from gasoline and will provide a high-octane C9 iso-paraffin material for gasoline
blend stock. That C9 isoparaffin will offset some of the loss of heavier aromatics in gasoline blends.
In the past some refiners used catalytic polymerization of propylene and butylenes to make an olefinic
gasoline. That now leads to objectionable olefin concentrations in gasoline that must be subsequently
hydrogenated to paraffinic structures and then isomerized to improve the octane number. Although alkylation is
expected to fully displace simple catalytic polymerization for fuel components, some catalytic polymerization
units will be operated to produce chemicals such as propylene trimer and tetramer.
Meeting Oxygen Requirements
Oxygenates were initially added to gasoline to improve octane rating but now are also intended to reduce
carbon monoxide and hydrocarbons. There are a number of oxygenates available. Following is a brief
summary of some of the most widely known.
Oxygenates
Name
Formula
Research
Reid Vapor
Oxygen
Water
Octane RON
Pressure
(wt%)
Solubility
(psi)
(wt% in water)
Methyl tertiary butyl
110 - 112
8
18%
4.3%
(CH3)3C0CH3
ether (MTBE)
Ethyl tertiary butyl
110 - 112
4
16%
1.2%
(CH3)3C0C2H5
ether (ETBE)
Tertiary amyl methyl
103 - 105
4
16%
1.2%
(CH3)2(C2H5)C0C
ether (TAME)
H3
C2H5OH
112 - 115
18
35%
100%
Ethanol (200)
The Environmental Protection Agency establishes the allowable limits for each oxygenate through a series of
waivers and interpretive rules. Blends are subject to volume % and weight % limits. For example, MTBE may
be blended up to 15% volume subject to overall 2.7% (weight) oxygen content.
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Refining Overview Part 3 Processing


Chapter 12 Gasoline Manufacturing Overview

The role of MTBE and other oxygenates received heightened attention when it was found in the late 1990s
some underground storage tanks for reformulated gasoline containing MTBE had not been upgraded to the 1998
federal standards for corrosion, overfilling and spills. As a consequence, tanks were leaking gasoline that
contained MTBE into groundwater and drinking water supplies. A Blue Ribbon Panel convened by the EPA to
study the problem released its recommendations in July 1999. However, in December 1999, the California Air
Resources Board voted to eliminate MTBE from gasoline by the end of 2002.
Managing Octane Needs
Octane needs are provided best by alkylate. Oxygenates are also important in providing octane but the selection
of which oxygenate is still in flux. Isomerate has a good octane level but the high vapor pressure restricts
utility. Part of the octane rating in reformate is provided by aromatics which are now limited. As a result, these
factors have held the octane level constant since approximately 1960. Reforming is still a source of isoparaffins
produced by isomerization.
Blending Gasoline
Refiners refer to their pool of gasoline blend stocks. Pool is the designator for both the individual constituents
that may be segregated in tankage and also for the average that a refiner draws on for blends.
The properties of most gasoline components do not blend arithmetically. The property is influenced by the
composition of the material in the blend. Five important criteria are octane number (R+M/2), the vapor
pressure (Reid vapor pressure), density (API gravity), aromatics content, and olefins content. Each refinery has
its own unique set of values experimentally developed for a refinery pool by preparing a set of test blends with
differing compositions. The characteristics of each component on the blend are measured, as are those for each
of the test blends. Then statistical analysis is performed on the set of data to derive the best correlations for
predicting blend properties from component properties.
As the composition of blends have become more controlled, refiners improved the precision of their gasoline
blending predictions and operations. On-line analyzers, automated in-line and automated batch blending
facilities are typical. Instrumentation systems have been developed to continuously measure and track of all the
many streams in the refinery, both in terms of quantity and quality.
Blend compositions are tightly controlled to meet performance and emission characteristics. Consolidation of
the oil industry in the 1990s prompted many integrated oil companies to enter into joint ventures with
competitors such as fuels marketing joint ventures. One basic strategy of the typical fuels operation joint
venture is to coordinate gasoline specifications to be identical for all partners so that the fuel may be sold at any
of the partners retail gasoline stations. Another factor causing gasoline specifications to narrow are the
Environmental Protection Agency complex formula regulations in terms of the calculated base emissions.
Additionally, pipeline transportation of gasoline may also help standardization of gasoline specifications.
One distinguishing feature of each gasoline brand is the additives. Additives are added as the fuel is loaded on
the tanker truck with a gallon of gasoline containing approximately 300 ppm(vol) of additives. Each brand
utilizes a different formula of additives meant to emphasize the marketing strategy for that brand.

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