Aromatic

Hydrocarbons
Benzene, Toluene and Xylene
Physical properties

Overview
Productions of aromatic compounds

i. Physical processes: solvent extraction, azeotropic/

extractive distillation, fractional distillation, solid
adsorption and crystalization

ii. Chemical treatments: dehydrogenation,

dehydroisomerization, and dehydrocyclization (and
hydrodesulphurisation)

Reactions of aromatic compounds – alkylation,

halogenation, oxidation, nitration, sulfonation etc.
Benzene, Toluene and Xylene
 History Background

Earlier – solvent mixture

1850 – as an individual compound

Mostly side product from coal carbonization to produce coke

The yield is rather small portion

Demand for WWI – production of TNT

Because of limited production from coal carbonization, other

methods have been used – catalytic reforming, pyrolysis etc

During WWII – increase demand for benzene

7.7 million tonnes per annum – US capacity

 Properties

Benzene, toluene and xylene from coal carbonization

Hydrocarbon Kg / tonne coal carbonized

Benzene 2 -8

Toluene 0.5 – 2

Xylene 0.1 – 0.5

 IUPAC name: Benzene
Other names: Benzol, Cyclohexa-1,3,5-triene

Molecular formula: C6H6

Molar mass: 78.1121 g/mol

Appearance: Colorless liquid
Density: 0.8786 g/cm3, liquid
Melting point: 5.5 oC
Boiling point: 80.1 oC

Solubility in water: 1.79 g/L (25 oC)

Viscosity: 0.652 cP (20 oC)

Dipole moment: OD
Main hazards: Carcinogenic, toxic
Flash point: -11 oC
 IUPAC name: Methylbenzene
Other names: Toluene, Phenylmethane, Toluol

Molecular formula: C7H8 (C6H5CH3)

Molar mass: 92.14 g/mol

Appearance: Clear colorless liquid
Density: 0.8669 g/cm3, liquid
Melting point: -93 oC
Boiling point: 110.6 oC

Solubility in water: 0.053 g/100 ml (20 - 25 oC)

Viscosity: 0.590 cP (20 oC)

Dipole moment: O.36 D
Hazards: Highly flammable
Flash point: 4 oC
 IUPAC name: 1,2-dimethylbenzene 1,3-dimethylbenzene 1,4-dimethylbenzene
Common name: o-xylene m-xylene p-xylene
Other names: o-xylol, Orthoxylene m-xylol, Metaxylene p-xylol, Paraxylene

Molecular
C8H10 (C6H4C2H6)
formula:

Molar mass: 106.16 g/mol

Appearance: Clear colorless liquid
Density: 0.88 g/cm3, liquid 0.86 g/cm3, liquid 0.86 g/cm3, liquid
Melting point: -25 oC -48 oC 13 oC
Boiling point: 144 oC 139 oC 138 oC

Solubility in
Practically insoluble
water:

Viscosity: 0.812 (20 oC) 0.62 (20 oC) 0.34 cP (20 oC)

Dipole moment: -

Hazards: Harmful
Flash point: 17 oC 25 oC 25 oC
Production of
Aromatics
Physical Processes
 Separation of Aromatics
Physical methods
1. Fractional distillation
2. Azeotropic distillation
3. Extractive distillation
4. Solvent extraction
5. Solid adsorption
6. Crystallization

Consideration
1. Close or identical boiling points
2. Reversible condition under reforming reactions
3. Solubility and miscibility
 Fractional Distillation

Separate toluene Aromatics separation plants:

Benzene forms azeotropic mixture Reformate moves up

with naphthenes and paraffins
Solvent moves down

Products from catalytic reforming Solvent extracted out to a

process is separated light fraction – stripper
boiling point at 180 – 250 oC
Separate from alkanes and
Further separation at above 225 oC to cycloalkanes
produce 90% toluene and 10%
azeotropic mixture of benzene, Further separation by
naphthenes and paraffin fractional distillation
 Aromatics Separation Plant

?
 Separation of C8 Aromatics
o-xylene separate by fractional distillation

Not possible for m- and p-xylene (preferred methods is

crystallization or isomerization)

Crystallization
or adsorption
C8 stream Residual C8s

p-xylene
o-xylene
distillation
p-xylene
separation Isomerisation
C8 stream

p-xylene
o-xylene
 Azeotropic Distillation
The process requires specific solvent or azeotropic agent
As a volatile component in the mixture
Increase the rate of volatility – change the properties and
encounter the separation problem

Example: separation of toluene

Azeotropic agents:
1.
2.
?
3.
4.
Increase the volatility of toluene
Distill off from benzene and xylene

See FIG. 3. and TABLE 3

 Extractive Distillation
 In the presence of a solvent that reduced the volatility rate of the
compounds to be separated
 Lower the boiling point of the component
 The added solvent must fit the properties:
1.
2.
3.
? 4.
5.
6.

 See FIG. 4
 Extractive Distillation
 Examples:

compound solvent

Xylene cresol

Benzene and toluene phenol

 Requires additional process for purification

1.Benzene treated with sulphuric acid; washed with caustic soda,

water; separate polymers and sulphonate sludges in the re-run
tower

2.Toluene treated with maleic anhydride, caustic soda, water; dried

under calcium chloride
 Solvent Extraction
 Solvent has highly selectivity for aromatics against non-
aromatics
 Fit the following characters:
1.Form two phase system, able to separate at reasonable
range of temperature
2.Non-corrosive
3.Non-reactive to the feed and the product
4.Thermally stable

 Examples:
 Udex Plant – aqueous diethylene glycol
 Refinery of Humble Oil – SO2 extraction-double solvent
extraction
 Solvent Extraction
UDEX Plant

Separate benzene, toluene and xylene in a plant

Main component: an extractor, a water wash, a heater, a

contact clay treater and distillation columns

Diethylene glycol-water increase the selectivity

More water will decrease the solubility

See FIG. 5, TABLE 4

 Solvent Extraction
SO2 Extraction-Double Solvent Extraction
 Toluene separation
 First extraction: separate aromatics from non-aromatics by
adding SO2

 Second extraction: oil wash, then separate raffinate (SO2, oil wash
and some non-aromatics) by extraction
 SO2 and oil wash are reused

 After removal of SO2 and oil wash to obtain 99.5% toluene

 After acid wash to obtain 100% toluene

 See FIG. 6
 Solid Adsorption
Aromatics and
Adsorption of organic compounds non-aromatics
on compressed silica gel

Aromatics prefer to adsorb

Washing silica gel with xylene to

remove aromatics from non- xylenes
aromatics
Xylenes +
The silica gel can be reused by aromatics
washing with a paraffin solvent

Commercially known as Arosorb

Washing with
process paraffin
 Boiling points of isomers of xylene are very close each other:

Ethylbenzene: 136.2 oC

Crystallization
p-xylene: 138.2 oC

m-xylene: 139.1 oC

o-xylene: 144.4 oC

Separation by fractional distillation is impossible

Freezing temperatures of isomers of xylene

Ethylbenzene: -95.0 oC

p-xylene: 13.3 oC

m-xylene: -47.9 oC

o-xylene: -25.2 oC

Process: dried over activated alumina, cooled in two stages (first

crystallisation of p-xylene at 13.3 oC in ‘waiting tank’, centrifuge,
second crystallization)

Product: 95%, with 60-70% recovery

Production of
Aromatics
Chemical Processes
An Overview
1. Catalytic reforming
2. Dehydrogenation
3. Dehydroisomerisation
4. Pyrolysis Gasoline
5. Isomerisation
6. Hydrodealkylation
7. Disproportionation
8. Desulfuration
 Catalytic Reforming
Also known as ‘hydrogen reforming’
Purposely to obtain main aromatic compounds (benzene,
toluene, and xylenes) as much as possible

Three main types:

Dehydrogenation of cyclohexane and homologues
Dehydroisomerisation of methyl cyclopentane and
homologues
Dehydrocyclisation of alkanes

Other related processes

Pyrolysis gasoline
Hydrodealkylation
Isomerisation
Desulfuration
 Mostly the feedstocks are from naphthenes and homologues

Dehydrogenation
‘Hydroforming’ process
Condition: ~500 oC, ~15 atm, dehydrogenation catalyst, a flow of
hydrogen gas
Catalysts: molybdenum oxide, chromic oxide, Pt, Cu (mono-function
catalyst)

Fisher and Welty

Feedstock: methyl cyclohexane,
Product: toluene
See attachment FIG. 1: Hydroformer

?
 Dehydroisomerisation
Combination of isomerisation and dehydrogenation processes
Mostly from substituted cyclopentanes
Examples: methyl cyclopentane, dimethyl cyclopentane etc.
Condition: ~500 oC, ~15 atm, hydrogen atmosphere
Catalyst: molybdenum oxide, chromic oxide, Pt, Cu

?
 Dehydroisomerisation
Hartley

Feedstock: mixture of methyl cyclopentane and cyclohexane

Product: benzene

Reason: the rate of isomerisation is slower than dehydrogenation, so

that cyclohexane form benzene very quickly

Feedstock: dimethyl cyclopentanes, ethyl cyclopentane

Primary product: methyl cyclohexane (isomerisation)

Secondary product: toluene (dehydrogenation)

Greensfelder and Fuller

Dehydroisomerisation
Feedstock: methyl cyclopentane
Condition: 490 oC, 10 – 20 atm, a flow of hydrogen
Catalyst: MoO3 on activated alumina
Product: benzene (no cyclohexane)

Platforming
Feedstocks: straight run gasoline containing methyl
cyclopentane, cyclohexane, and other C6 and C8
naphthenes
Condition: 475 oC, hydrogen atmosphere, 720 psi
Catalyst: Pt on alumina
Reactor: pellitized Pt working at 250 – 275 oC
Product: mixture of benzene and other aromatics
See attachment: FIG. 2: Platformer
 Dehydroisomerisation
Fulton

Feedstocks: mixture of paraffins (13.4 %), isoparaffins (29.3 %),

naphthenes (33.3 %), aromatics (6.1 %)

Condition: platforming

Product: 60 % isoparaffins and 40 % aromatics

Haensel and Berger

Feedstocks: mixture of C7 – C8 paraffins (28 %), C7 – C8 naphthenes

(62 %), toluene (10 %)

Condition: platforming

Product: 53 - 56 % toluene

Edgar

Feedstock: naphthenes

Condition: 480 – 510 oC, 14 – 21 atm

Catalyst: Pt on alumina, and halides

Yield: 90 % aromatics HC
 Dehydroisomerisation
Advantages of the platforming process:

1. The naphthenes converted to aromatics

2. Isomerisation and cracking of the paraffins to improve the octane rating

3. The sulfur content is decreased

Caterole process

Introduce in England

Hydrocarbon stream heated at 600 - 700 oC with slightly above atmospheric

pressure

Catalyst: copper or copper-iron

An example of the process

Feedstock: naphtha fraction (120 – 240 oC)

Condition: 700 oC, 20 – 50 psi, straight distillation

Product: benzene (92 – 94 %)

from another fraction to obtain toluene (94 – 96 %)

Can also produce xylenes, ethylbenzene, styrene, indene, naphthalenes,

antracene etc
 Ring closure of alkanes (paraffins)

Dehydrocyclization
Usually C6 or more

Proceed via olefins

A slower reaction than the dehydrogenation and

dehydroisomerisation

Involve transformation of paraffins to olefins, ring

closure to form naphthenes, and dehydrogenation

Condition: >500 oC

Therefore, inclusive reaction of cracking of alkanes

?
 Dehydroisomerisation
Hoog, Verheus and Zuiderweg

Feedstock: olefins

Condition: 450 – 550 oC

Catalyst: Chromic oxide, or other metal oxides and

sulfides

Product: aromatics

Examples of paraffins conversion at 465 oC:

Paraffin hydrocarbon Aromatic hydrocarbon % aromatization

n-Hexane Benzene 19.5

2-Methylhexane Toluene 31

n-Heptane Toluene 36

2,5-Dimethylhexane Mostly p-xylene 52

3-Methylheptane Mainly o- and p-xylene 35

n-Octane Mainly o-xylene 46

n-Nonane Mainly methylethylbenzene 58

 Dehydroisomerisation
Shell Development Company

Feedstock: n-heptane

Condition: 490 oC, atmospheric pressure

Catalyst: 10 % Chromic oxide on alumina, cerium dioxide and

potassium oxide

Product: toluene (80 % conversion), usually maintained at 40 %

Feedstock: n-nonane

Condition: 465 oC, atmospheric pressure

Catalyst: 70 % chromic oxide, 30 % alumina with potassium oxide

Product: 71 % aromatics, 6% olefins, 23 % paraffins

Aromatics was 80 % methylethylbenzene

?
 Dehydroisomerisation
Hurley

Feedstock: heptane (90 %), air (5%), HF (5 %)

Condition: 550 oC, atmospheric pressure,

Catalyst: ferric fluoride and manganous fluoride

Product: toluene (42 %)

Dunstand, Haque, Wheeler

Feedstock: C2 to C6 paraffins

Condition: 750 – 900 oC

Product: benzene (and other liquid aromatic products)

 Dehydroisomerisation
Frey and Hepp

Suggest the mechanism of the aromatization from ethane

feedstock

Two steps; dehydrogenation (endothermic),

aromatization (exothermic)

When the process through ethylene and butadiene

?
 Pyrolysis Gasoline
A fraction from cracking process with a boiling range between 20 –
200 oC

The stream contains aromatics, alkenes, dienes, alkanes and

cycloalkanes

Most of the alkenes and dienes were removed by solvent extraction

Condition: 75 – 150 oC, 10 – 40 atm, fraction distillation

Product: C6 – C8 hydrocarbons, benzene, toluene, C8 aromatics

Typical products distribution (%):

Reformate Pyrolysis gasoline

Benzene 11 54

Toluene 55 31

C8 aromatics 34 15
 Involve 1,2-hydride or methyl shifts

A stage to produce more o- and p-xylenes

Feedstock: C8 aromatics

Isomerisation
Condition: vapour phase, 500 oC, strong acidic condition

Catalyst: silica-alumina

Product: o-xylene (20 %), m-xylene (55 %), p-xylene (25 %)

Ethylbenzene not isomerised to xylenes unless the presence of catalytic

reforming process

?
 In term of market demand, benzene is higher than toluene

Hydrodealkylation
But toluene produced in excess

Market From petroleum From coal tar

Benzene 65 10 80

Toluene 20 40 15

Xylenes 15 50 5

Transforms toluene to benzene

Feedstock: toluene

Catalytic condition: 550 – 650 oC, 35 – 70 atm

Non-catalytic condition: 650 – 750 oC, 20 – 67 atm

Yield: up to 99 %
Disproportionation
Converted toluene to benzene and o-, m-, and p-xylenes
Condition: 480 oC
Catalyst: zeolite (acidic catalyst)

Desulfuration
A process to avoid ‘poisoning’ to catalyst

Sulphurated compounds removed by this process

The feedstock pre-treated with cobalt oxide or

molybdenum oxide at 400 oC

Sulphurated compounds turn into H2S – easier to

remove