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AROMATICS

OUTLINE:
I.

Definition

II.

Aromatic Compounds
A. Benzene
B. Toluene
C. Xylene

III.

Production
A. Feedstock Consideration
B. Reforming Process
C. Solvent Extraction

IV.

Intermediates
A. Ethylbenzene
1. Manufacturing Process
2. Chemical Reactions
B. Styrene
1. Manufacturing Process
2. Chemical Reaction
C. Cumene
1. Manufacturing Process
2. Chemical Reaction
D. Phenol
1. Manufacturing Process
2. Chemical Reaction

Table of Contents

Aromatics

Aromatic Compounds

Benzene

Toluene

Xylene

Production

Feedstock Consideration

Reforming Process

Solvent Extraction

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Intermediates

13

Ethylbenzene

14

Styrene

14

Cumene

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Phenol

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Aromatics
An aromatic hydrocarbon or arene (or sometimes aryl hydrocarbon) is
a hydrocarbon with alternating double and single bonds between
carbon atoms forming rings. The term 'aromatic' was assigned
before the physical mechanism determining aromaticity was
discovered; the term was coined as such simply because many
of the compounds have a sweet or pleasant odor. The
configuration of six carbon atoms in aromatic compounds is known as a benzene
ring, after the simplest possible such hydrocarbon, benzene

Aromatic Compounds
1. Benzene
Benzene is an organic chemical compound with the molecular
formula C6H6. Its molecule is composed of 6 carbon atoms joined in a ring,
with 1 hydrogen atom attached to each carbon atom. Because its molecules
contain

only

carbon

and

hydrogen

atoms,

benzene

is

classed

as

a hydrocarbon.
Benzene is a natural constituent of crude oil, and is one of the most
elementary petrochemicals. Benzene is an aromatic hydrocarbon. It is
sometimes abbreviated PhH (Phenyl- Hydrogen). It is a colorless and
highly flammable liquid with a sweet smell. It is mainly used as a precursor
to heavy chemicals, such as ethylbenzene and cumene, which are produced
on a billion kilogram scale. Because it has a high octane number, it is an
important component of gasoline, comprising a few percent of its mass. Most
non-industrial applications have been limited by benzene's carcinogenicity.

2. Tolueue
Toluene, formerly known as toluol is a
clear, water-insoluble liquid with the typical smell
of

paint

thinners.

It

is

mono-

substituted benzene derivative, i.e., one in which a


single hydrogen atom from a group of six atoms
from the benzene molecule has been replaced by a
univalent group, in this case CH3. As such, its IUPAC systematic name
is methylbenzene.
It is an aromatic hydrocarbon that is widely used as an
industrial feedstock and as a solvent. Like other solvents, toluene is
sometimes also used as an inhalant drug for its intoxicating properties;
however, inhaling toluene has potential to cause severe neurological
harm. Toluene is an important organic solvent, but is also capable of
dissolving a number of notable inorganic chemicals such as sulfur, iodine,
bromine, phosphorus, and other non-polar covalent substances.

3. Xylene
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A xylene or dimethyl benzene (from Greek word xylo which means


"wood") is an aromatic hydrocarbon consisting of a benzene ring with two
methyl substituents. The three isomeric xylenes each have a molecular
formula

of

C8H10,

formula

C6H4(CH3)2

though
is

also

the

more

used

informative

commonly.

semi-structural

The

xylenes

are

major petrochemicals, produced by catalytic reforming and also by coal


carbonisation in the manufacture of coke fuel. Representing about 0.51%
of crude oil (depending on the source), xylenes are found in small
quantities in gasoline and airplane fuels. Xylenes are mainly produced as
part of the BTX aromatics (benzene, toluene and xylenes) extracted from
the product of catalytic reforming known as "reformate".

Aromatics Production and Use


An aromatics complex is a combination of process units that can be used
to convert petroleum naphtha and pyrolysis gasoline (pygas) into the basic
petrochemical intermediates: Benzene Toluene and Xylenes (BTX).
Benzene is a versatile petrochemical building block used in the production
of more than 250 different products. Ethylbenzene, cumene, and cyclohexane
are the most important benzene derivatives.
The xylenes product, also known as mixed xylenes, contains three
different aromatic isomers: para-xylene, ortho-xylene and meta-xylene. Small
amounts of mixed xylenes are used for solvent applications, but most xylenes
are processed further within the complex to produce one or more of the
individual isomers. The most important C8 aromatic isomer is para-xylene,
which is used almost exclusively for the production of polyester fibres, resins,
and films. In recent years, polyester fibres have shown growth rates of 5 to 6
percent per year and resin has shown growth rates of 10 to 15 percent per year,
corresponding to the emergence of PET (polyethylene terephthalate) containers.
A small amount of toluene is recovered for use in solvent applications and
derivatives, but most toluene is used to produce benzene and xylenes. Toluene
is becoming increasingly important for the production of xylenes through toluene
disproportionation and transalkylation with C9 aromatics.
Aromatics complexes can have many different configurations. The simplest
complex produces only benzene, toluene, and mixed xylenes and consists of the
following major process units: naphtha hydrotreating for the removal of sulphur
and nitrogen contaminants; catalytic reforming for the production of aromatics
from naphtha; aromatics extraction for the extraction of BTX.
An aromatics complex may be configured in many different ways,
depending on the available feedstocks, the desired products, and the amount of
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investment capital available. Because of this wide flexibility, the product slate
can be varied to match downstream processing requirements.

Feedstock considerations
Petroleum naphtha is by far the most popular feedstock for aromatics
production. Reformed naphtha, or reformate, accounts for 70% of total world
BTX supply. The pygas by-product from ethylene plants is the next-largest
source at 23%. Coal liquids from coke ovens account for the remaining 7%.

BTX from different feedstock


Reformed naphtha

70%

Pygas by product

23%

(from ethylene plant)


Coal liquids

7%

Pygas and coal liquids are important sources of benzene that may be used
only for benzene production or may be combined with reformate and fed to an
integrated aromatics complex. Mixed xylenes are also actively traded and can be
used to feed a stand-alone Parex-Isomar loop or to provide supplemental
feedstock for an integrated complex.

Process
Over the last 50 years, the vast majority of benzene, methylbenzenes and
ethylbenzene have been manufactured from the cracking and reforming of
fractions obtained from the distillation of oil.

The figure above shows how crude oil is processed in plants to produce variety
of product:
1. A reactor in which the C6-C8 stream is being dehydrogenated to form
aromatic hydrocarbons, including benzene and the toluene and
xylene, an example of reforming.
2. A reactor in which isomerisation reactions are taking place, for example
to form branched chain alkanes from naphtha.
3.

A reactor in which cracking is taking place, long chain alkanes being


cracked to smaller alkanes and alkenes.
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4.

Separation

of

hydrogen

and

C1-C4

hydrocarbons

from

higher

hydrocarbons.
5.

Removal of sulphur-containing compounds.

6.

A distillation column separating C5-C6 from C7-C9 hydrocarbons.

7.

A stack to remove combustion gases from the furnace

The Reforming Process


During the reforming of naphtha, mainly straight chain alkanes, with 6
8 carbon atoms, are re-formed into molecules with the same number of carbon
atoms but different structures.
The naphtha is first purified to remove sulphur, which would poison the
catalyst, and then mixed with recycled hydrogen and heated to about 500C, a
process known as hydroforming.
This mixture passes into a series of reactors containing a catalyst,
normally platinum/alumina. Older processes operate at 20 atmospheres
pressure, but modern plants run at a lower pressure of 5 atmospheres and use
continuous catalyst regeneration. This means the catalyst is withdrawn on a
continuous basis and conveyed through a regeneration system before being
returned to the reactor.
A typical composition of BTX obtained by reforming is benzene (15%),
toluene (40%) and xylene (45%) Aromatic compounds are separated from the
non-aromatic compounds by solvent extraction (and are then fractionally
distilled into benzene, toluene and xylene.

Reactions
For example hexane is reformed to benzene:

Similarly, toluene and xylene are formed from heptane and octane
respectively:

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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.
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These solvents are characterized by a high affinity for aromatics,


goodthermal stability, and rapid phase separation. The Tetra extraction
processby Union Carbide (Figure above) 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. The hot, rich solvent containing BTX aromatics is cooled and introduced
into the top of a stripper column. The aromatics extract is then purified by
extractive distillation and recovered from the solvent by steam stripping .The
raffinate (constituted mainly of paraffins, isoparaffins and cycloparaffins) is
washed with water to recover traces of solvent and then sent to storage. The
solvent is recycled to the extraction tower.
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.

Intermediates of Aromatics
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Product Flow: From Aromatics to Consumer Products

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1. Ethylbenzene
Ethylbenzene is an organic compound with the formula C6H5CH2CH3. It is
a highly flammable, colorless liquid with an odor similar to that of gasoline. This
monocyclic aromatic hydrocarbon is important in the petrochemical industry as
an intermediate in the production of styrene, the precursor to polystyrene, a
common plastic material. Ethylbenzene is also used to make other chemicals, in
fuel, and as a solvent in inks, rubber adhesives, varnishes, and paints.
Ethylbenzene exposure can be determined by testing for the breakdown products
in urine.
Ethylbenzene (EB) is a colorless aromatic liquid with a boiling point of
136.2C, very close to that of p-xylene. This complicates separating it from the
C8 aromatic equilibrium mixture obtained from catalytic reforming processes.
The main process for producing EB is the catalyzed alkylation of benzene with
ethylene:

2. Styrene
Styrene, also known as ethenylbenzene, vinylbenzene, and phenylethene, is
an

organic

compound

with

the

chemical

formula

C6H5CH=CH2. This derivative of benzene is a colorless oily


liquid that evaporates easily and has a sweet smell, although
high concentrations confer a less pleasant odor. Styrene is
the precursor to polystyrene and several copolymers.

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Styrene is used predominately in the production of polystyrene plastics and


resins. Styrene is also used as an intermediate in the synthesis of materials
used for ion exchange resins and to produce copolymers.
Production of Ethylbenzene and Styrene

The process consists of two separate reactor-separator-recycle networks in


which one corresponds to the ethylbenzene flow sheet and the other corresponds
to styrene flowsheet.
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For Ethylbenzene:
a. Azeotropic Distillation
Benzene (wet) is sent first to an azeotropic distillation unit that separates
water and produces dry Benzene. Dry Benzene is required so as to avoid catalyst
as alumina can get formed.
b. Alkylation
Dry Benzene + Ethylene + Ethyl chloride + AlCl3 enter the alkylator catalyst
reactor The reactor could be a jacketed tower where water is used as a cooling
fluid in the jacket to control the reactor temperature. The reactor produces two
products namely uncondensible gases and the liquid product in which AlCl3
complex is available. This complex needs to be regenerated and sent back to the
alkylator.
The chemical reactions and operating conditions for alkylation are given
below:

Benzene + ethylene Ethyl benzene

Catalyst: AlCl3 granules

C2H5Cl provides hydrogen and chlorine free radicals

Operating conditions: 95oC and 1 atm pressure

Reaction is exothermic

c. Cooling
The alkylator product is sent to a cooler which upon cooling to 40oC
separates the aluminium chloride complex stream from the product stream. The
other stream from the cooler is the ethylbenzene rich product stream.

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d. Cracking reaction
The aluminium chloride stream is partially recycled to the alkylator so as
to maintain the required catalyst requirements. The other portion of the AlCl3
complex is sent to a dealkylator unit in which the feed is heated to 200 oC. By
doing so, the polyethylbenzenes formed in the alkylator are converted to benzene
and ethylbenzene (cracking reaction). The benzene and ethylbenzene are
returned to the cooler. The delkylator produces a residue product consisting of
tar + AlCl3 mixture.
e. Purification
From tar and AlCl3 mixture, AlCl3 is recovered using water extraction as
AlCl3 is soluble in water. From there AlCl3 is recovered from the water and
returned back to the alkylation reactor. The product stream from the cooler
consisting of ethylbenzene is mixed with 50 % NaOH to remove acidic impurities.
Eventually, after settling waste is eliminated.
f. Stripping
The purified ethylbenzene then enters a stripper that separates
ethylbenzene + benzene from the polyalkylbenzenes. The polyalkylbenzenes are
sent to a polyalkyl still that separates the benzene + ethylbenzenes from the
polyalkylbenzenes (bottom product). The polyalkyl still is operated under
vacuum. The polyalkylbenzenes are fed to the dealkylator and the benzene +
ethylbenzene rich stream is sent to a heat integrated exchanger that extracts
heat from the vent gases and then eventually enters the alkylation reactor.
g. Azeotropic Drying
- The top product from the stripper is ethylbenzene + benzene and it enters
a benzene column that separates wet benzene from crude ethylbenzene. The wet
benzene is recycled to the azeotropic dryer where it is mixed with fresh wet
benzene to enter the azeotropic dryer.
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h. Fractionation
- The crude ethylbenzene is further purified in a fractionator where the
bottom product (with benzene) is mixed with the top product of the polyalkyl still.
Thereby, the stream enters the heat integrated exchanger.
i. Drying
- The ethylbenzene is further subjected to caustic wash and finally it is
sent to a dryer to produce dry ethylbenzene.
For Styrene:
a. Dehydrogenation
The ethylbenzene (dry) is heated with superheated steam to enter the
catalytic dehydrogenator. Excess steam is used in this process. The feed preheating is carried out using the product vapour stream. The reaction is gas phase
catalytic reaction. Below are the chemical reaction and operating conditions.

Ethylbenzene Styrene + Hydrogen

Reaction is endothermic

Catalyst: SnO or FeO

Operating conditions: 800oC

b. Quenching
- The vapour stream after cooling with the feed stream in a heat integrated
exchanger is fed to a quench tower using steam quenching.

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c. Distillation
After quenching, partial condensation of the quenched vapors produces
three streams one being the vapour vent, the other being water and the third
being the organic phase rich with styrene.
The styrene rich stream is sent first to a benzene column to recover the
benzene + toluene and this is sent to a benzene-toluene distillation column to
recover benzene. The benzene is sent to the azeotropic distillation unit as a rawmaterial.
The bottom product from the benzene column enters an ethylbenzene
column

which

separates

ethylbenzene

from

the

styrene

stream.

The

ethylbenzene stream is mixed with the dry ethylbenzene to enter the catalytic
dehydrogenator.
The bottom product from the ethylbenzene column is the styrene enriched
stream and this is sent to the finishing column where styrene is further purified
from unwanted impurities such as tar. The tar is further batch distilled to recover
styrene from the tar. The styrene finishing column also produces styrene
product.
d. Cooling
Both styrene products from batch still and styrene finishing column are
mixed and cooled to store as styrene product.
All three columns namely benzene, ethylbenzene and finishing columns
are operated under vacuum.

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3. Cumene
Cumene (isopropylbenzene), a liquid, is soluble in many organic solvents
but not in water. It is a constituent of crude oil and refined fuels. It is a flammable
colorless liquid that has a boiling point of 152 C. Nearly all the cumene that is
produced as a pure compound on an industrial scale is converted to cumene
hydroperoxide, which is an intermediate in the synthesis of other industrially
important chemicals, primarily phenol and acetone.
The main process for producing cumene is a synthetic route where
benzene is alkylated with propylene to isopropylbenzene.

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Production of Cumene

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a. Compression
Propylene obtained from refinery processes as a mixture of propylene and
propane. The mixture along with benzene is compressed to 25 atms.
b. Pre-heating
Eventually the mixture enters a heat integrated exchanger to heat the preheat the feed mixture.
c. Addition of Propylene
The feed mixture enters a packed bed reactor. The stream distribution in
the packed bed reactor corresponds to cold shot arrangement i.e., cold
propane from the distillation column in the process is added after every
reactor with the product stream so that the temperature of the stream is
controlled. Here, propylene is the limiting reactant and therefore, presumably
all propylene undergoes conversion. Propane does not react but is a diluents
or inert in the system. In that way it controls the reaction temperature. The
reactor units are maintained at about 250oC. The product vapors are cooled
using the heat integrated exchanger. The vapors then pass to a depropanizer
which separates propane from the product mixture.

The reaction is exothermic

Side reaction: C6H6 + C3H6 nC9H12

Catalyst: H3PO4 impregnated catalyst on porous carrier

Operating conditions: 25 atms pressure and 250 oC temperature.

d. Distillation
The bottom product consisting of benzene, cumene and polyalkyl benzenes
enters another distillation column which separates benzene from the mixture

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of cumene and polyalkyl benzene. The benzene stream is recycled to enter the
compressor. The bottom product from the benzene column is sent to a
cumene column which produces cumene as top product and poly alkyl
benzene as bottom product.

4. Phenol
Phenol, also known as carbolic acid, is an aromatic organic compound
with the molecular formula C6H5OH. It is a white crystalline
solid that is volatile. The molecule consists of a phenyl group
(-C6H5) bonded to a hydroxyl group (-OH). It is mildly acidic,
but requires careful handling due to its propensity to cause
chemical burns.
It is an important industrial commodity as a precursor
to many materials and useful compounds. Its major uses involve its conversion
to plastics or related materials. Phenol and its chemical derivatives are key for
building polycarbonates, epoxies, Bakelite, nylon, detergents, herbicides such as
phenoxy herbicides, and numerous pharmaceutical drugs.

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Production of Phenol

a. Drying and Chlorination


Benzene is first dried. Dry benzene and FeCl3 catalyst enters the
chlorination reactor.

Benzene + Cl2monochloro benzene

Operating temperature: 85 oC

Catalyst: Fe or FeCl3 catalyst

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b. Fractionation
After the solid-gas-liquid reaction, the products are further heated up to
enter a fractionator. The fractionator separates benzene as a top product and
monochloro benzene as the bottom product. The top product also consists of HCl
off gas that is obtained as the vapour stream from the partial condenser. The
benzene is further cooled and sent back to the reactor and also as a reflux to the
fractionator.
The bottom product monochloro benzene is mixed with 10 % NaOH
solution and diphenyl oxide to enter a high pressure pump followed with heat
integrated heat exchanger that pre-heats the feed to higher temperature.
c. Causticization
The feed then enters the causticization reactor which has cooling water
tubes to control the temperature.

Benzyl chloride + NaOH sodium benzoate

NaOH is in aqueous media

Operating conditions: 425 oC and 350 atms

Exothermic reaction

d. Hydrolysis
The product stream is cooled using heat integrated exchanger and then
enters a neutralizer that is fed with the HCl obtained from the fractionator partial
condenser.

Sodium benzoate + HCl (aq) Phenol + NaCl (aq)

Operating conditions: Nothing specific

e. Gravity Settling
After neutralization, the product phenol is separated from the aqueous
phase using gravity settling principle.
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f. Vacuum Distillation
The organic layer rich in phenol is sent to a vacuum column to separate
the phenol from diphenyl oxide (bottom product). The bottom product is partially
recycled to enter the cauticization reactor.

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