PETROCHEMISTRY
Instructor: Dao Thi Kim Thoa
Chapter 9: Petrochemical technology based on xylenes
The term xylenes refers to a group of 3 benzene derivatives which encompasses ortho-,
meta-, and para- isomers of dimethyl benzene. The o-, m- and p- isomers specify to
which carbon atoms (of the main benzene ring) the two methyl groups are attached.
Counting the carbon atoms from one of the ring carbons bonded to a methyl group, and
counting towards the second ring carbon bonded to a methyl group, the o- isomer has
the IUPAC name of 1,2-dimethylbenzene. The m- isomer has the IUPAC name of 1,3-
dimethylbenzene. And p- isomer has the IUPAC name of 1,4-dimethylbenzene.
I. Introduction
v Xylenes: dimethyl benzene.
v Source: catalytic reforming, steam cracking, catalytic cracking.
v p-Xylene: the most important: make terephthalic acid for polyester.
v m-Xylene: less usage: but more in aromatic mixture, normally it is isomerized to p-
xylene.
v Chemical is mainly based on methyl group, oxidation.
v 65% of xylenes is used for chemicals synthesis.
v The rest: is used as solvent or gasoline blend.
It is a colorless, sweet-smelling liquid that is very flammable. It occurs naturally in
petroleum and coal tar and is formed during forest fires. The chemical properties differ
slightly from isomer to isomer. The melting point is between −47.87 °C (m-xylene) and
13.26 °C (p-xylene). The boiling point is for each isomer at around 140 °C. The density
is at around 0.87 kg/L and thus is less dense than water. Xylene in air can be smelled at
0.08 to 3.7 parts of xylene per million parts of air (ppm) and can begin to be tasted in
water at 0.53 to 1.8 ppm.
p-Xylene
p-Xylene has become the large
volume petrochemical since the
early 1970.
Why p-Xylene?
Applications: production of polyester fibers,
films, and resins such as PET.
Demand: increased tenfold since 1970 to about 26.106 t/year.
This additional production mostly come from UOP ParexTM process.
Demand of p-xylene comes directly from the demand of polyester: PET
for packaging of carbonated beverages and bottled water; production of
textile fibers and engineering thermoplastics.
(*): Zeolites in Industrial Separation and Catalysis, Santi Kulprathipanja
ZEOLITES
• Zeolites have been used in the industrial adsorptive purification of aromatic
petrochemicals since the early 1970s.
Why zeolites?
- Separation by distillation can not reach high purity.
- The high volume aromatics stream from naphtha reforming and naphtha steam
cracking is quite free from heteroatom contaminants and contains mainly simplest
aromatics.
- There is the subtle difference in adsorptive affinity between the various aromatics
onto the zeolite.
(*): Zeolites in Industrial Separation and Catalysis, Santi Kulprathipanja
II. Chemicals based on xylenes:
1. Terephthalic acid (HOOC-C6H4 -COOH ) (TPA)
Terephthalic acid is one isomer of the three phthalic acids. It finds important use
as a commodity chemical, principally as a starting compound for the manufacture
of polyester (specifically PET), used in clothing and to make plastic bottles. It is
also known as 1,4-benzenedicarboxylic acid, and it has the chemical formula
C6H4(COOH)2.
CH3 CH3 + 3/2 O2 CH3 COOH + HO
2
CH3 COOH + 3 O2 + 2CH3-OH CH3OOC COO-CH3 + 4H O
2
Dimethyl terephthalate (DMT)
CH3OOC COO-CH3 + 2H O
2
COOH COOH + 2 CH3-OH
Usage of TPA and DMT: making polyester for producing synthetic fiber and film.
Properties
It is almost insoluble in water, alcohol and ether; it
sublimes rather than melting when heated. This
insolubility makes it relatively awkward to work with,
and up until around 1970 much crude terephthalic acid
was converted to the dimethyl ester for purification.
Phthalic anhydride
Phthalic anhydride is the anhydride of phthalic acid.
It dissolves in alcohol and some other organic
solvents.
Phthalic anhydride is obtained either by catalytic
oxidation of ortho-xylene with O2 or by catalytic
oxidation of naphthalene. The biproducts of the
naphthalene reaction are carbon dioxide and water.
It is hydrolyzed by hot water, forming ortho-phthalic
acid.
Phthalic anhydride is widely used in industry in the
production of dyes (rhodamine, anthraquinone
derivatives), insecticides, plasticizers, in pharmacy, in
analytic chemistry, etc.
O
CH3 C
+ 3 O2 O + 3H2O
CH3 C
O
Currently, phthalic anhydride is mainly from oxidation of o-xylene.
Catalyst: V2O5 + TiO2 /Sb2O3
T: 375 - 435 oC
P: 0.7 atm
Y: 85 % phthalic anhydride
Vapor phase reaction
Applications: making plasticizer, un-saturated polyester resin, alkyd resin.