Petrochemical industry
Eng/Bassem Fathalla
Hydrocarbon Intermediates
Natural gas and crude oils are the main sources for hydrocarbon
intermediates or secondary raw materials for the production of
petrochemicals.
From natural gas, ethane and LPG are recovered for use as
intermediates in the production of olefins and diolefins. Important
chemicals such as methanol and ammonia are also based on
methane via synthesis gas.
On the other hand, refinery gases from different crude oil
processing schemes are important sources for olefins and LPG.
Crude oil distillates and residues are precursors for olefins and
aromatics via cracking and reforming processes.
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. 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.
Methane (cH4)
As a chemical compound, methane is not very reactive. It does not
react with acids or bases under normal conditions. It reacts, however,
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.
Ethane (CH3-CH3)
Ethane is an important paraffinic hydrocarbon intermediate for the
production of olefins, especially ethylene.
Ethane's relation with petrochemicals is mainly through its cracking to
ethylene.
Propane (CH3CH2CH3)
Propane is a more reactive paraffin than ethane and methane. This is
due to the presence of two secondary hydrogens that could be easily
substituted.
Chemicals directly based on propane are few, although as mentioned,
propane and LPG are important feedstocks for the production of
olefins.
Butanes (C H ) 4 10
Dehydrogenation of isobutane produces isobutene, which is a reactant
for the synthesis of methyl tertiary butyl ether (MTBE).
This compound is currently in high demand for preparing unleaded
gasoline due to its high octane rating and clean burning properties.
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.
Ethylene is the most important olefin for producing petrochemicals, and
therefore, many sources have been sought for its production.
Ethylene (CH =CH ) 2 2
Ethylene (ethene), the first member of the alkenes, is a colorless gas
with a sweet odor. It is slightly soluble in water and alcohol. It is a
highly active compound that reacts easily by addition to many
chemical reagents.
For example, ethylene with water forms ethyl alcohol. Addition of
chlorine to ethylene produces ethylene dichloride (1,2-
dichloroethane), which is cracked to vinyl chloride. Vinyl chloride is
an important plastic precursor.
Ethylene is also an active alkylating agent. Alkylation of benzene
with ethylene produces ethyl benzene, which is dehydrogenated to
styrene.
Styrene is a monomer used in the manufacture of many commercial
polymers and copolymers. Ethylene can be polymerized to different
grades of polyethylenes or copolymerized with other olefins.
Catalytic oxidation of ethylene produces ethylene oxide, which is
hydrolyzed to ethylene glycol. Ethylene glycol is a monomer for the
production of synthetic fibers.
The main source for ethylene is the steam cracking of hydrocarbons
(Chapter 3).
Table 2-2 shows the world ethylene production by source until the
year 2000.4 U.S. production
Propylene (CH CH=CH ) 3 2
Propylene can be polymerized alone or copolymerized with
other monomers such as ethylene.
Many important chemicals are based on propylene such as
isopropanol, allyl alcohol, glycerol, and acrylonitrile.
Butylenes (C H )
4 8
There are four butene isomers:
1) Three unbranched,
2) “normal” butenes (n-butenes) and
3) A branched isobutene (2-methylpropene).
The three nbutenes are 1-butene and cis- and trans- 2-butene. The
following shows the four butylene isomers:
The 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.
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.
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.
Isoprene (2-methyl-1,3-butadiene) is a colorless liquid, soluble in alcohol
but not in water. Its boiling temperature is 34.1°C. Isoprene is the second
important conjugated diene for synthetic rubber production. The main
source for isoprene is the dehydrogenation of C5 olefins (tertiary
amylenes) obtained by the extraction of a C5 fraction from catalytic
cracking units. It can also be produced through several synthetic routes
using reactive chemicals such as isobutene, formaldehyde, and propene.
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).
Accordingly, they do not easily add to reagents such as halogens and
acids as do alkenes.
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.
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 glycol.
These solvents are characterized by a high affinity for aromatics,
good thermal stability, and rapid phase separation.
Benzene
Benzene (C6H6) 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.
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:
Benzene is an important chemical intermediate and is the precursor for
many commercial chemicals and polymers such as phenol, styrene for
poly-styrenics, and caprolactom for nylon 6.
Ethylbenzene
Ethylbenzene (C6H5CH2CH3) 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.
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.
Only a small amount of the total toluene and xylenes available from
these sources is separated and used to produce petrochemicals.
Liquid petroleum fractions and residues
Naphtha:
Naphtha from atmospheric distillation is characterized by an absence
of olefinic compounds. Its main constituents are straight and
branchedchain paraffins, cycloparaffins (naphthenes), and aromatics,
and the ratios of these components are mainly a function of the crude
origin.
Naphthas obtained from cracking units generally contain variable
amounts of olefins, higher ratios of aromatics, and branched paraffins.
Due to presence of unsaturated compounds, they are less stable than
straight-run naphthas. On the other hand, the absence of olefins
increases the stability of naphthas produced by distilation units.
In refining operations, however, it is customary to blend one type of
naphtha with another to obtain a required product or feedstock.
Selecting the naphtha type can be an important processing procedure.
For example, a paraffinic-base naphtha is a better feedstock for steam
cracking units because paraffins are cracked at relatively lower
temperatures than cycloparaffins.
Alternately, a naphtha rich in cycloparaffins would be a better
feedstock to catalytic reforming units because cycloparaffins are
easily dehydrogenated to aromatic compounds.
Reformates are the main source for extracting C6-C8 aromatics
used for petrochemicals.
Naphtha is also a major feedstock to steam cracking units for
the production of olefins.
This route to olefins is especially important in places such as
Europe, where ethane is not readily available as a feedstock
because most gas reservoirs produce non-associated gas with a
low ethane content.
Naphtha could also serve as a feedstock for steam reforming
units forthe production of synthesis gas for methanol.
Kerosine
Kerosines with a high normal-paraffin content are suitable feedstocks
for extracting C12-C14 n-paraffins, which are used for producing
biodegradable detergents. Currently, kerosine is mainly used to
produce jet fuels,
PRODUCTION OF OLEFINS
The most important olefins and diolefins used to manufacture
petrochemicals are ethylene, propylene, butylenes, and butadiene.
Butadiene, a conjugated diolefin, is normally coproduced with C2–C4
olefins from different cracking processes.
Separation of these olefins from catalytic and thermal cracking gas
streams could be achieved using physical and chemical separation
methods.
However, the petrochemical demand for olefins is much greater than
the amounts these operations produce. Most olefins and butadienes
are produced by steam cracking hydrocarbons.
STEAM CRACKING OF HYDROCARBONS
(Production of Olefins)
Steam Cracking Process
A typical ethane cracker has several identical pyrolysis furnaces in
which fresh ethane feed and recycled ethane are cracked with steam
as a diluent.
Figure 3-12 is a block diagram for ethylene from ethane. The outlet
temperature is usually in the 800°C range. The furnace effluent is
quenched in a heat exchanger and further cooled by direct contact in a
water quench tower where steam is condensed and recycled to the
pyrolysis furnace.
After the cracked gas is treated to remove acid gases, hydrogen and
methane are separated from the pyrolysis products in the
demethanizer.
The effluent is then treated to remove acetylene, and ethylene is
separated from ethane and heavier in the ethylene fractionator.
The bottom fraction is separated in the deethanizer into ethane and C3+
fraction. Ethane is then recycled to the pyrolysis furnace.
Process Variables:
The important process variables are reactor temperature, residence
time, and steam/hydrocarbon ratio. Feed characteristics are also
considered, since they influence the process severity.
1. Temperature:
Steam cracking reactions are highly endothermic. Increasing
temperature favors the formation of olefins, high molecular weight
olefins, and aromatics. Optimum temperatures are usually selected to
maximize olefin production and minimize formation of carbon
deposits.
2. Residence Time:
In steam cracking processes, olefins are formed as primary products.
Aromatics and higher hydrocarbon compounds result from secondary
reactions of the formed olefins. Accordingly, short residence times are
required for high olefin yield.
When ethane and light hydrocarbon gases are used as feeds, shorter
residence times are used to maximize olefin production and minimize
BTX and liquid yields; residence times of
0.5–1.2 sec are typical.
Cracking liquid feedstocks for the dual purpose of producing olefins
plus BTX aromatics requires relatively longer residence times than for
ethane.
However, residence time is a compromise between the reaction
temperature and other variables.
3. Steam/Hydrocarbon Ratio:
A higher steam/hydrocarbon ratio favors olefin formation.
Steam reduces the partial pressure of the hydrocarbon mixture
and increases the yield of olefins.
Heavier hydrocarbon feeds require more steam than gaseous
feeds to additionally reduce coke deposition in the furnace
tubes.
• Steam to hydrocarbon weight ratios range between 0.2–1 for
ethane and approximately 1–1.2 for liquid feeds.
4. Feedstocks:
Feeds to steam cracking units vary appreciably, from light
hydrocarbon gases to petroleum residues. Due to the difference in the
cracking rates of the various hydrocarbons, the reactor temperature and
residence time vary.
As mentioned before, long chain hydrocarbons crack more easily than
shorter chain compounds and require lower cracking temperatures.
For example, it was found that the temperature and residence time that
gave 60% conversion for ethane yielded 90% conversion for propane.
Feedstock composition also determines operation parameters. The
rates of cracking hydrocarbons differ according to structure
Paraffinic hydrocarbons are easier to crack than cycloparaffins, and
aromatics tend to pass through unaffected.
Isoparaffins such as isobutane and isopentane give high yields of
propylene. This is expected, because cracking at a tertiary carbon is
easier.
Cracking Liquid Feeds
Liquid feedstocks for olefin production are light naphtha, full range
naphtha, reformer raffinate, atmospheric gas oil, vacuum gas oil,
residues, and crude oils. The ratio of olefins produced from steam
cracking of these feeds depends mainly on the feed type and, to a
lesser extent, on the operation variables.
For example, steam cracking light naphtha produces about twice the
amount of ethylene obtained from steam cracking vacuum gas oil
under nearly similar conditions.
Liquid feeds are usually cracked with lower residence times and
higher steam dilution ratios than those used for gas feedstocks.
Production of diolefins
The most important industrial diolefinic hydrocarbons are butadiene
and isoprene.
Butadiene (CH = CH-CH = CH ) 2 2
Butadiene is the raw material for the most widely used synthetic
rubber, a copolymer of butadiene and styrene (SBR).
In addition to its utility in the synthetic rubber and plastic industries
(over 90% of butadiene produced), many chemicals could also be
synthesized from butadiene.
