Chemical Industries Technologies Ⅰ

Chapter 2:
Hydrocarbon Intermediates

Dr. Asma Eskhan

 Chapter 2: Hydrocarbon Intermediates

Outline:

• Paraffinic Hydrocarbons
• Olefinic Hydrocarbons
• Dienes
• Aromatic Hydrocarbons
• Liquid Petroleum Fractions and Residues
 Paraffinic Hydrocarbons
• Natural gas and crude oils are the main sources for hydrocarbon
intermediates or secondary raw materials for the production of
petrochemicals

1- Paraffinic hydrocarbons
• Paraffinic hydrocarbons used for producing petrochemicals range from
the simplest hydrocarbon, methane, to heavier hydrocarbon gases and
liquid mixtures present in crude oil fractions and residues.
• Paraffins are relatively inactive compared to olefins, diolefins, and
aromatics. Few chemicals could be obtained from the direct reaction of
paraffins with other reagents.
 Paraffinic Hydrocarbons: Methane
• However, these compounds are the precursors for olefins through
cracking processes.
• The C6–C9 paraffins and cycloparaffins are especially important for the
production of aromatics through reforming.
• Examples of C1–C4 paraffins are:
(a) Methane (CH4):
• Methane is the first member of the alkane series and is the main
component of natural gas. It is also a by-product in all gas streams from
processing crude oils.
• It is a colorless, odorless gas that is lighter than air.
• As a chemical compound, methane is not very reactive. It does not react
with acids or bases under normal conditions.
 Paraffinic Hydrocarbons: Methane
• However, it reacts, with a limited number of reagents such as oxygen
and chlorine under specific conditions. For example, it is partially
oxidized with a limited amount of oxygen to a carbon monoxide-
hydrogen mixture at high temperatures in presence of a catalyst. The
mixture (synthesis gas) is an important building block for many
chemicals.
• Methane is mainly used as a clean fuel gas. It is also an important
source for carbon black.
• Methane may be liquefied under very high pressures and low
temperatures. Liquefaction of natural gas (methane), allows its
transportation to long distances through cryogenic tankers.
 Paraffinic Hydrocarbons: Ethane
(b) Ethane (CH3-CH3):
• Ethane is an important paraffinic hydrocarbon intermediate for the
production of olefins, especially ethylene. It is the second member of
the alkanes and is mainly recovered from natural gas liquids.
• Ethane, like methane, is a colorless gas that is insoluble in water.
• It does not react with acids and bases, and is not very reactive toward
many reagents.
• It can also be partially oxidized to a carbon monoxide and hydrogen
mixture or chlorinated under conditions similar to those used for
methane.
• Ethane's relation with petrochemicals is mainly through its cracking to
ethylene.
 Paraffinic Hydrocarbons: Propane
(c) Propane (CH3-CH2-CH3):
• Propane is a more reactive paraffin than ethane and methane.
• Propane is obtained from natural gas liquids or from refinery gas
streams. Liquefied petroleum gas (LPG) which is a mixture of propane
and butane is mainly used as a fuel.
• LPG is also an important feedstock for the production of olefins for
petrochemical use.
• A new process was recently developed for the dehydrogenation of
propane to propylene for petrochemical use.
 Paraffinic Hydrocarbons: Butanes
(d) Butanes (C4H10):
• Butanes are obtained from natural gas liquids and from refinery gas
streams.
• The C4 acyclic paraffin consists of two isomers: n-butane and isobutane
(2-methylpropane). The physical and the chemical properties of the two
isomers are quite different due to structural differences.

• Isobutane is a much more

reactive than n-butane due to the
presence of a tertiary hydrogen.

• Butane is primarily used as a fuel gas within the LPG mixture.

 Paraffinic Hydrocarbons: Butanes
• Like ethane and propane, the main chemical use of butane is as
feedstock for steam cracking units for olefin production.
• Dehydrogenation of n-butane to butenes and to butadiene is an
important route for the production of synthetic rubber.
 Olefinic Hydrocarbons
• The most important olefins used for the production of petrochemicals
are ethylene, propylene, the butylenes, and isoprene.
• These olefins are usually coproduced with ethylene by steam cracking
ethane, LPG, liquid petroleum fractions, and residues.
• Olefins are characterized by their higher reactivities compared to
paraffinic hydrocarbons. They can easily react with inexpensive reagents
such as water, oxygen, hydrochloric acid, and chlorine to form valuable
chemicals.
• Olefins can even add to themselves to produce important polymers
such as polyethylene and polypropylene.
 Olefinic Hydrocarbons: Ethylene
(a) Ethylene (CH2=CH2)
• Ethylene (ethene) is a colorless gas with a sweet odor. It is slightly
soluble in water and alcohol.
• The main source for ethylene is the steam cracking of hydrocarbons.
• It is a highly active compound that reacts easily by addition to many
chemical reagents.
• It can be used as a
precursor in the
manufacture of many
petrochemical products
such as polymers,
plastics, synthetic fibers.
 Olefinic Hydrocarbons: Propylene
(b) Propylene (CH3CH=CH2)
• Propylene (propene) is a reactive alkene that can be obtained from
refinery gas streams, especially those from cracking processes.
• The main source of propylene, however, is steam cracking of
hydrocarbons, where it is coproduced with ethylene.
• There is no special process for propylene production except the
dehydrogenation of propane.

• Many important chemicals are based on propylene such as isopropanol,

allyl alcohol, glycerol, and acrylonitrile.
 Olefinic Hydrocarbons: Butylenes
(c) Butylenes (C4H8)
• Butylenes (butenes) are by-products of refinery cracking processes and
steam cracking units for ethylene production.
• Dehydrogenation of butanes is a second source of butenes. However, this
source is becoming more important because isobutylene (a butene
isomer) is currently highly demanded for the production of oxygenates as
gasoline additives.
• There are four butene isomers: three unbranched, “normal” butenes (n-
butenes) and a branched isobutene (2-methylpropene). The three n-
butenes are 1-butene and cis- and trans- 2-butene (Table 2-3).
• The industrial reactions involving cis- and trans-2-butene are the same
and produce the same products. There are also addition reactions where
both1-butene and 2-butene give the same product.
 Olefinic Hydrocarbons: Butylenes
• For this reason, it is
economically feasible to
isomerize 1-butene to 2-
butene (cis and trans)
and then separate the
mixture. The
isomerization reaction
yields two streams, one
of 2-butene and the
other of isobutene,
which are separated by
fractional distillation.
 Olefinic Hydrocarbons: Butylenes
• An alternative method for separating the butenes is by extracting
isobutene (due to its higher reactivity) in cold sulfuric acid, which
polymerizes it to di- and triisobutylene. The dimer and trimer of isobutene
have high octane ratings and are added to the gasoline pool.
• Figure 2-1 shows the two processes for the separation of n-butenes from
isobutene.
 Dienes
• Dienes are aliphatic compounds having two double bonds.
• When the double bonds are separated by only one single bond, the
compound is a conjugated diene (conjugated diolefin). Nonconjugated
diolefins have the double bonds separated (isolated) by more than one
single bond. This latter class is of little industrial importance.
 Dienes: Butadiene
Butadiene (CH2=CH-CH=CH2)
• Butadiene is by far the most important monomer for synthetic rubber
production.
• It can be polymerized to polybutadiene or copolymerized with styrene to
styrene-butadiene rubber (SBR).
• Butadiene is an important intermediate for the synthesis of many
chemicals such as hexamethylenediamine and adipic acid. Both are
monomers for producing nylon.
• Chloroprene is another butadiene derivative for the synthesis of neoprene
rubber.
• The unique role of butadiene among other conjugated diolefins lies in its
high reactivity as well as its low cost.
 Dienes: Butadiene
• Butadiene is obtained mainly as a coproduct with other light olefins from
steam cracking units for ethylene production.
• Other sources of butadiene are the catalytic dehydrogenation of butanes
and butenes, and dehydration of 1,4-butanediol.
• Butadiene is a colorless gas with a mild aromatic odor.
 Dienes: Isoprene
• Isoprene (2-methyl-1,3-butadiene) is a colorless liquid, soluble in alcohol
but not in water.
• Isoprene is the second important conjugated diene for synthetic rubber
production.
• The main source for isoprene is the
dehydrogenation of C5 olefins
obtained by the extraction of a C5
fraction from catalytic cracking units.
• The main use of isoprene is the
production of polyisoprene. It is also
a comonomer with isobutene for
butyl rubber production.
 Aromatic Hydrocarbons
• Benzene, toluene, xylenes (BTX), and ethylbenzene are the aromatic
hydrocarbons with a widespread use as petrochemicals.
• They are important precursors for many commercial chemicals and
polymers such as phenol, trinitrotoluene (TNT), nylons, and plastics.
• Aromatic compounds are characterized by having a stable ring structure
due to the overlap of the π-orbitals (resonance).
• Aromatic hydrocarbons are generally nonpolar. They are not soluble in
water, but they dissolve in organic solvents such as hexane, diethyl ether,
and carbon tetrachloride.
 Aromatic Hydrocarbons
Extraction of Aromatics
• Benzene, toluene, xylenes (BTX), and ethylbenzene are obtained mainly
from the catalytic reforming of heavy naphtha. The product reformate is
rich in C6, C7, and C8 aromatics, which could be extracted by a suitable
solvent such as sulfolane or ethylene.
• These solvents are characterized by a high affinity for aromatics, good
thermal stability, and rapid phase separation.
• The Tetra extraction process by Union Carbide (Figure 2-2) uses
tetraethylene glycol as a solvent. The feed (reformate), which contains a
mixture of aromatics, paraffins and naphthenes, after heat exchange with
hot raffinate, is countercurrentIy contacted with an aqueous
tetraethylene glycol solution in the extraction column.
 Aromatic Hydrocarbons
• The extract, which is composed of BTX and ethylbenzene, is then fractionated.
Benzene and toluene are recovered separately, and ethylbenzene and xylenes are
obtained as a mixture (C8 aromatics).
• Due to the narrow range of the boiling points of C8 aromatics, separation by fractional
distillation is difficult. A superfractionation technique is used to segregate
ethylbenzene from the xylene mixture.
• Because p-xylene is the most valuable isomer for producing synthetic fibers, it is
usually recovered from the xylene mixture. Fractional crystallization used to be the
method for separating the isomers, but the yield was only 60%. Currently, industry
uses continuous liquid-phase adsorption separation processes.
• The overall yield of p-xylene is increased by incorporating an isomerization unit to
isomerize o- and m-xylenes to p-xylene. An overall yield of 90% p-xylene could be
achieved.
 Aromatic Hydrocarbons: Benzene
Benzene (C6H6):
• Benzene is the simplest aromatic hydrocarbon and by far the most widely
used one.
• Before 1940, the main source of benzene and substituted benzene was
coal tar. Currently, it is mainly obtained from catalytic reforming. Other
sources are pyrolysis gasolines and coal liquids.
• Benzene has a unique structure due to the presence of six delocalized π
electrons that encompass the six carbon atoms of the hexagonal ring
 Aromatic Hydrocarbons: Benzene
• Aromatic hydrocarbons, like paraffin hydrocarbons, react by substitution,
but by a different reaction mechanism and under milder conditions.
• Aromatic compounds react by addition only under severe conditions. For
example, electrophilic substitution of benzene using nitric acid produces
nitrobenzene under normal conditions, while the addition of hydrogen to
benzene occurs in presence of catalyst only under high pressure to give
cyclohexane:
 Aromatic Hydrocarbons: Benzene
• Monosubstitution can occur at any one of the six equivalent carbons of
the ring. Most of the monosubstituted benzenes have common names
such as toluene (methylbenzene), phenol (hydroxybenzene), and aniline
(aminobenzene).
Aromatic Hydrocarbons: Benzene
• When two hydrogens in the
ring are substituted by the
same reagent, three
isomers are possible. The
prefixes ortho, meta, and
para are used to indicate
the location of the
substituents in 1,2-; 1,3-;
or 1,4-positions.

• Benzene is an important chemical intermediate and is the precursor for

many commercial chemicals and polymers such as phenol, styrene for
polystyrenics, and caprolactom for nylon 6.
 Aromatic Hydrocarbons: Ethylbenzene
Ethylbenzene (C6H5CH2CH3):
• Ethylbenzene is one of the C8 aromatic
constituents in reformates and pyrolysis
gasolines. It can be obtained by intensive
fractionation of the aromatic extract, but only a
small quantity of the demanded ethylbenzene
is produced by this route.
• Most ethylbenzene is obtained by the alkylation of benzene with
ethylene.
• The U.S. production of ethylbenzene was approximately 12.7 billion
pounds in 1997. Essentially, all of it was directed for the production of
styrene.
 Aromatic Hydrocarbons: Methylbenzenes
Methylbenzenes (Toluene and Xylenes):
• Methylbenzenes occur in small quantities in naphtha and higher boiling
fractions of petroleum. Those presently of commercial importance are
toluene, o-xylene, p-xylene, and to a much lesser extent m-xylene.
• The primary sources of toluene and xylenes are reformates from catalytic
reforming units, gasoline from catcracking, and pyrolysis gasoline from
steam reforming of naphtha and gas oils. As mentioned earlier, solvent
extraction is used to separate these aromatics from the reformate
mixture.
• Currently, the largest single use of toluene is to convert it to benzene.
para-Xylene is mainly used to produce terephthalic acid for polyesters. o-
Xylene is mainly used to produce phthalic anhydride for plasticizers.
 Liquid Petroleum Fractions and Residues
• Liquid Petroleum fractions are light
naphtha, heavy naphtha, kerosine
and gas oil.
• The bottom product from
distillation units is the residue.
• These mixtures are intermediates
through which other reactive
intermediates are obtained.
• Heavy naphtha is a source of
aromatics via catalytic reforming
and of olefins from steam cracking
units.
• Gas oils and residues are sources
of olefins through cracking and
pyrolysis processes.