Hydrocarbon Fractions from Petroleum

boiling range size range name and use

Fossil Fuels: of fraction (o C)

Many alkanes occur in below 20 C1 to C4 natural gas, bottled

nature, primarily in gas, petrochemicals
natural gas and 20 to 60 C5 to C6 petroleum "ether".
petroleum. solvents
Natural gas is com-posed 60 to 100 C6 to C7 ligroin, solvents
largely of methane, with
lesser amounts of ethane, 40 to 200 C5 to C10 straight-run gasoline
propane and butane.
175 to 325 C12 to C18 kerosene and jet fuel
gas oil, fuel oil
250 to 400 C12 and higher
Petroleum is a complex mixture of compounds, most of which are hydrocarbons and diesel oil
containing one to forty carbon atoms. Distilling crude petroleum (called refining), nonvolatile mineral oil,
separates it into usable fractions that differ in boiling point. liquids C20 and higher
lubricating oil
gasoline: C5H12—C12H26 paraffin w ax,
nonvolatile C20 and higher
kerosene: C12H26—C16H34 solids asphalt, tar
diesel fuel: C15H32—C18H38
3 6

Petroleum Technologies

Technologies exist to interconvert the various hydrocarbons using

catalysts.
Sources of Alkanes: Petroleum and Natural Gas
Cracking is a process for breaking down larger alkanes into
smaller alkanes by heating. The mixture of larger alkanes is
Petroleum is the source of alkanes. It is a complex mixture of heated in the absence of oxygen at high temperatures (~500oC) for
mostly alkanes and aromatic hydrocarbons with smaller amounts only a few minutes in the presence of catalysts. By this method,
of oxygen-, nitrogen-, and sulfur-containing compounds. alkanes of size C12 and larger can be turned into gasoline-size
alkanes (C5 to C10).
Natural gas is a gaseous mixture of hydrocarbons recovered from Isomerization
natural sources. It is mostly methane (CH4, BP -162oC) with small
amounts of ethane (C2H6, BP -88oC) and propane (C3H8, BP -42o). Since the 1920s, it has been known that highly branched alkanes
perform better in the internal combustion engine than straight-
Petroleum Refining chain alkanes. Catalytic isomerization changes straight-chain
alkanes into the more useful branched alkanes.
Liquid petroleum and natural gas are usually separated at the
acid catalyst CH3CH2CH2CHCH3
wellhead and shipped independently to processing (refining) plants. CH3CH2CH2CH2CH2CH3
+ CH3
The liquid petroleum (crude) is separated by distillation according to
hexane CH3CH2CHCH2CH3
the volatility (BPs) of the different size hydrocarbons. The fractions
collected by refining are still mixtures of hydrocarbons that have CH3
branched alkanes
commercial value. 4 7

Refining crude petroleum into usable fuel and other petroleum products.
(a) An oil refinery. At an oil refinery, crude petroleum is separated into Catalytic Reforming
fractions of similar boiling point by the process of distillation.
(b) Schematic of a refinery tower. As crude petroleum is heated, the lower-
boiling, more volatile components distill first, followed by fractions of Alkanes are transformed into cycloalkanes and aromatic
progressively higher boiling point. hydrocarbons by catalytic reforming.

CH3
silica-alumina
CH3CH2CH2CH2CH2CH2CH3
catalyst, 500oC + 4H2
heptane
20 atm H2

The aromatic hydrocarbons produced by catalytic reforming

are used as additives in gasoline and as starting materials for
the petrochemical industry. Production of these aromatics is in
the billions of pounds per year in the United States.

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Petroleum Products

An Overview of Petroleum Refining

smaller alkanes

straight-
chain Cracking
Crude
alkanes Isomerization
Petroleum Refining
of Reforming
different
sizes

branched alkanes aromatics

Gasoline Performance: The Octane Rating

The combustion of alkanes is a complicated reaction probably
involving free radicals. Much attention has been directed towards
the combustion of hydrocarbons in the internal combustion engine.
Since the 1920s, it has been known that some hydrocarbons tend to
give better performance during combustion. Some fuels cause
"knocking", the premature ignition of the fuel before the piston is
in the firing position for a power stroke. Knocking causes loss of
power.
Branched hydrocarbons were found to perform better than straight-
chain alkanes in the internal combustion engine. In 1927, an
arbitrary engineering performance standard was developed called
"the octane rating." The performance of the branched alkane
"isooctane" (actually 2,2,4-trimethylpentane) in a specific internal
combustion engine was given a rating of 100. Heptane, which
causes severe knocking, was given a rating of 0.
A fuel with a
CH3 CH3 performance equivalent
CH3CCH2CHCH3 CH3CH2CH2CH2CH2CH2CH3 to a mixture of 75%
CH3 isooctane and 25%
"isooctane" heptane
heptane is given an
100 0 octane rating of 75.
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