PETROCHEMISTRY

Petrochemical technology based on benzene

Instructor: DAO THI KIM THOA

 BENZENE

Benzene is an organic chemical compound with the formula C6H6. It is sometimes

abbreviated Ph-H. Benzene is a colorless and flammable liquid with a sweet smell and a
relatively high melting point. It is carcinogenic and its use as additive in gasoline is now
limited, but it is an important industrial solvent and precursor in the production of
drugs, plastics, synthetic rubber, and dyes. Benzene is a natural constituent of crude oil,
but it is usually synthesized from other compounds present in petroleum.
I. Introduction
- Source: + Catalytic reforming, catalytic cracking, steam cracking.
+ Selective extraction by solvent: sulfolane, ethylene glycol: BTX and EB.
Then, separate by distillation or crystallization, isomerization.
- Reactivities of C6, C7, C8 aromatics are mainly based on benzene ring.
- Reaction: electrophilic substitution: react with electrophilic agent. Ex: alkylation,
nitrogenation, chlorination.
- Benzene is the most important aromatic: is the feed for many chemicals which is
intermediates or final chemicals.
Ex: Hydrogenation benzene to cyclohexane.
Oxidation cyclohexane to cyclohexanone.
Cyclohexanone is used for making caprolactam to make nylon.
- Because of the resonant stability of benzene ring, it is hardly to polymerize.
However, its extract like: styrene, phenol, maleic anhydride can be easily
polymerized to form important commercial products because of the exist of
functional groups.
_ Benzene can be alkylated by several alkylation agent, hydrogenated to from
cyclohexane, nitrated or chlorinated.
 Aromatics processing

(*): Petrochemical Processes, Sami Matar, Lewis F. Hatch.

 Boiling point Freezing point
oC oC

Benzene 80.1 5.5

Toluene 110.8 -94.9

O-xylene 144.4 -25

M-xylene 139.1 -47.9

P-xylene 138.3 13.3

Ethylbenzene 136.2 -94.4

Xylenes separation and cryogenic crystallization of para-xylene

23.9oC

-67.8oC

-40oC

23.9oC
 Typical aromatics complex with UOP technology

(*): Zeolites in Industrial Separation and Catalysis, Santi Kulprathipanja

(*): 2014 Petrochemical Processes Handbook
(*): 2014 Petrochemical Processes Handbook
(*): 2014 Petrochemical Processes Handbook
(*): 2014 Petrochemical Processes Handbook
(*): 2014 Petrochemical Processes Handbook
 Approximate world demand of high-volume aromatic petrochemicals

106 t/year (2005-2008)

Benzene 40
p-Xylene 26
o-Xylene 5
m-Xylene 0.4

- Toluene is used mostly in gasoline blending.

- Ethylbenzene from reformate and pygas is typically dealkylated to
make benzene or isomerized to make xylenes.
- On-purpose production of ethylbenzene (via ethylene alkylation of
benzene) is primarily used as an intermediate in the production of
styrene monomer.
- The huge demand of benzene because it is the intermediate for the
production of polystyrene, acrylonitrile styrene butadiene rubber,
nylons, polycarbonates, and linear alkyl benzene.

(*): Zeolites in Industrial Separation and Catalysis, Santi Kulprathipanja

II. Alkylation benzene
* Benzene can be alkylated in the presence of Lewis acid.
Alkylation agent: olefins: ethylene, propylene and C12 –C14 a - olefins.
Product: benzene alkylate: highly commercial value.
*Mechanism
Step 1: Form carbonium ion +
H +
R-CH=CH2 R-CH-CH3
-
R-Cl + AlCl3 R+...AlCl4
Alkyl halide

Step 2: Carbonium ion attack into benzene ring, remove H+ to form benzene alkylate.

H _ H+
+
R + R
+ R
1. Ethyl benzene
- Ethylbenzene (EB) is a colorless liquid, boiling point 136.2 oC, is very closed to p-
xylene. It is hardly to separate from aromatic mixture from catalytic reforming.
- EB: 2 sources: catalytic reforming (less)
synthesis (mainly): alkylation of benzene.

+ CH2=CH2 CH2-CH3

_ Catalyst: AlCl3 -HCl

Liquid phase reaction
T: 40 - 100 oC
P: 2 - 8 atm
_ By-product: diethylbenzene and polyalkyl benzene: are recycled to be dealkylated to
form EB.
Badger process: is commercialized in 1980.
* Styrene
Product of dehydrogenated EB.

CH2-CH3 CH=CH2 + H2

Monsanto/Lummus Crest process.

* Besides, there are 2 ways to make styrene
Dimerization of butadiene 4-vinyl-1-cyclohexene dehydrogention of styrene.

CH2=CH-CH=CH2 CH=CH2 CH=CH2 + 2 H2

Combine oxidation of toluene stilbene disproportionation styrene + benzene

CH CH

2 CH3 + O2 + 2 H2O

stilbene

CH=CH2

High T, low yield. +

2. Cumene
- Alkylation: propylene.
- Applications: Make phenol and acetone.
One portion is used to make a - methylstyrene (monomer to mak
polymer, solvent).

CH3 CH-CH3 CH3 C=CH2

+ H2

a-methyl styrene
3. Linear alkylbenzene
- Linear alkylbenzene (LAB): is used to make bio-degradable anion cleaner.
- Alkylation agent: + Olefins C12 - C14.
+ Mono-chloroalkanes (chlorination of corresponding n-paraffin).
- In industry: alkylation by linear mono-olefin is more favorable.
- Detal process: combine dehydrogenation of n-paraffin and alkylation of benzene.
- Mono-olefins is from dehydrogenation unit to alkylation reactor (fixed bed with
heterogeneous catalyst).
- Old fashion process used HF catalyst with liquid phase reaction (40-70 oC).
R CH-CH3

+ R-CH=CH2

linear alkyl benzene (LAB)

- LAB is then sulfonated with SO3, neutralize by NaOH to form linear alkyl benzene
sulfonate (LABS), is a surfactant activity.

R R R
NaOH
SO3H SO3Na
+ SO3
III. Chlorination of benzene
Reaction: electrophile substitution
- Cl+: electrophile agent
- Catalyst: acid FeCl3
- Product: + Mixture mono- and di-chlorobenzene (ortho- & para- are more than metha-).
+ Mono-chloro/dichloro ratio: benzene/Cl2 ratio.
contact time.
+ Isomer ratio: o-/p-/m- depends on reaction temperature, contact time.

Cl Cl Cl
Cl
+ + + 5 HCl
3 + 5 Cl2

Cl
- Reaction condition: + Liquid phase, catalyst FeCl3
+ T: 80 - 100 oC
+ P: 1 atm
- High benzene/Cl2 : 80 % mono-chlorobenzene
15 % p-di-chlorobenzene
5 % o-di-chlorobenzene
IV. Nitrogenation of benzene
- Like akylation and chlorination of benzene, nitrogenation of benzene is also
electrophile substitution.
- Nitrogenation agent: NO2+
- Reaction in liquid phase
Catalyst: con. HNO3 + con. H2SO4
T : 50 o C
- Con. H2SO4 : 2 functions: + react with HNO3 to form nitronium ion.
+ absorb formed water of reaction accelerate the reaction in
the favorable way.
_ +
HNO3 + H2SO4 2 HSO4 + HO
3 + NO2+
NO2
+
+ NO2+ + H

- Applications: 97 % nitrobenzene is used for making aniline.

*Aniline (C6H5NH2): oily liquid, becoming brown when exposed to light, air, used to
make synthetic pigment.
Synthesis: hydrogenation of nitrobenzene.

NO2 NH2

+ 3H
2
+ 2 H2O

* Reaction condition T : 270 oC

P: >1 atm
Catalyst: Cu/silica
Y: 95 %
V. Oxidation of benzene
- Oxidation of benzene is an old fashion for making maleic anhydride.
- Now, the main route to gain maleic anhydride is butane oxidation.
VII. Hydrogenation of benzene:
- Make cyclohexane
- Catalyst: Ni/alumina, Ni/Pd
- T: 160 - 220 oC
- P: 25 - 30 atm

+ 3 H2

Highly exothermic
Reduced volume
T, P strongly affect to the reaction equilibrium.
- Cyclohexane: colorless liquid, not soluble in water, soluble in organic solvent, alcohol,
acetone.
- Applications:+ Dehydrogenated to form aromatic (catalytic reforming).
+ Oxidated to form cyclohexanone/cyclohexanol, for making
caprolactam, adipic acid for nylon 6/6.
•Oxidation cyclohexane
OH O

2 + O2 + + HO
2

Daàu KA
• KA oil: + Make caprolactam, monomer for nylon 6.
+ Make adipic acid, co-monomer for nylon 6/6.

+ 5/2 O2 HOOC-(CH2)-4COOH + H2O

 NYLON

What is nylon?

Nylon is a generic designation for a family of synthetic polymers, more

specifically aliphatic or semi-aromatic polyamides. They can be melt-processed
into fibers, films or shapes. The first example of nylon (nylon 6,6) was
produced on February 28, 1935, by Wallace Carothers at DuPont's research
facility at the Dupont Experimental Station. Nylon polymers have found
significant commercial applications in fibers (apparel, flooring and rubber
reinforcement), in shapes (molded parts for cars, electrical equipment, etc.), and
in films (mostly for food packaging).
The most common type of Nylon are Cast Nylon (Type 6) and Extruded Nylon (Type
6,6). The largest applications for Nylon are bearings, cams, valve seats, gears and
other bearing and wear applications that require quiet operation, wear resistance and
low coefficients of friction.
Nylon is typically not preferred for wet applications as it absorbs water. With this said
however there are grades and design methods that can make them work for specific
applications.
Nylon offers an excellent combination of mechanical performance and cost making it
the most widely used engineering thermoplastics. Today there are many nylon grades
available, the most common being nylon 6/6 and nylon 6. The properties of both
nylon products are very similar; and typically, they can be used interchangeably. With
this said, there are some advantages and limitations to each material both nylon 6/6
and nylon 6.
Want mouldable and extrude-able general- purpose nylon? Nylon 6/6
(polyhexamethylene adiptimide) has good mechanical properties and wear resistance.
Nylon 6/6 has a much higher melting point than cast nylon 6. Nylon 6/6 also has a
higher intermittent use temperature than cast nylon 6. Nylon 6/6 is limited by its
processing methods. What this means is In extrusion, it nylon 6/6 is limited to
constant cross-section profiles as well as the size constraints of the die geometry.
There are however, a larger number of fillers available for extruded nylon 6/6.
The condensation of two amino acids to form a peptide bond
(red) with expulsion of water (blue)
NYLON 6
§ Nylon 6 or polycaprolactam is a polymer developed by Paul Schlack at IG
Farben to reproduce the properties of nylon 6,6 without violating the patent on its
production. It is a semicrystalline polyamide.
§ Unlike most other nylons, nylon 6 is not a condensation polymer, but instead is
formed by ring-opening polymerization; this makes it a special case in the
comparison between condensation and addition polymers.
§ Its competition with nylon 6,6 and the example it set have also shaped the
economics of the synthetic fiber industry. It is sold under numerous trade names
including Perlon (Germany), Nylatron, Capron, Ultramid, Akulon, Kapron (former
Soviet Union and satellite states), and Durethan.
§ Nylon 6 can be modified using comonomers or stabilizers during polymerization to
introduce new chain end or functional groups, which changes the reactivity and
chemical properties. It’s often done to change its dyeability or flame retardance.
§ Nylon 6 is synthesized by ring-opening polymerization of caprolactam.
Caprolactam has 6 carbons, hence 'Nylon 6'. When caprolactam is heated at about
533 K in an inert atmosphere of nitrogen for about 4-5 hours, the ring breaks and
undergoes polymerization. Then the molten mass is passed through spinnerets to
form fibres of Nylon 6.
§During polymerization, the amide bond within each caprolactam molecule is
broken, with the active groups on each side re-forming two new bonds as the
monomer becomes part of the polymer backbone. Unlike nylon 6,6, in which the
direction of the amide bond reverses at each bond, all nylon 6 amide bonds lie in the
same direction (see figure: note the N to C orientation of each amide bond).

Nylon 6 (above) has a structure similar to Nylon 6,6 (below).

Properties

Nylon 6 fibres are tough, possessing high tensile strength, as well as elasticity and
lustre. They are wrinkleproof and highly resistant to abrasion and chemicals such as
acids and alkalis. The fibres can absorb up to 2.4% of water, although this lowers
tensile strength. The glass transition temperature of Nylon 6 is 47 °C.
As a synthetic fiber, Nylon 6 is generally white but can be dyed to in a solution bath
prior to production for different color results. Its tenacity is between 6 and 8.5
gm/den with a density of 1.14 gm/cc. Its melting point is at 215 C and can protect
heat up to 150 °C on average.
Applications
In 2010 over 4 million tons of polyamide 6 were produced.
60% of 2008 production went to fibre applications, engineering resins took 30% and
films 10%.
Nylon 6 finds application in a broad range of products requiring materials of high
strength.
It is widely used for gears, fittings, and bearings, in automotive industry for
underthehood parts, and as a material for power tools housings.
Nylon 6 is used as thread in bristles for toothbrushes, surgical sutures, and strings
for acoustic and classical musical instruments, including guitars, sitars, violins,
violas, and cellos. It is also used in the manufacture of a large variety of threads,
ropes, filaments, nets, and tire cords, as well as hosiery and knitted garments. It can
also be used in gun frames, such as those used by Glock, which are made with a
composite of Nylon 6 and other polymers. In manufacturing, Nylon 6 is used as
washers. It has the potential to be reused as a technical raw material for the
production of new Nylon 6, by depolymerization to caprolactam.
Biodegradation
Flavobacterium sp. and Pseudomonas sp. degrade oligomers of Nylon 6, but not
polymers. Certain white rot fungal strains can also degrade Nylon 6 through
oxidation.Compared to aliphatic polyesters, Nylon 6 has poor biodegradability.
Strong interchain interactions from hydrogen bonds between molecular nylon
chains is said to be the cause by some sources.
NYLON 6,6
Nylon 66 (aka nylon 6-6, nylon 6/6 or nylon 6,6) is a type of polyamide or
nylon. Nylons come in many types, and the two most common for textile and
plastics industries are nylon 6 and nylon 66. Nylon 66 is made of two
monomers each containing 6 carbon atoms, hexamethylenediamine and adipic
acid, which give nylon 66 its name.
Removing water drives the reaction toward polymerization through the formation
of amide bonds from the acid and amine functions.
Applications
In 2011 worldwide production was 2 million tons. At that time fibres consumed just
over half of production and engineering resins the rest. It is not used in films due to
its inability to be oriented. Fibre markets represented 55% of the 2010 demand with
engineering thermoplastics being the remainder.
Nylon 66 is frequently used when high mechanical strength, rigidity, good stability
under heat and/or chemical resistance are required. It is used in fibers for textiles and
carpets and molded parts.
For textiles, fibers are sold under various brands, for example Nilit brands or the
Cordura brand for luggage, but it is also used in airbags, apparel, and for carpet
fibres under the Ultron brand.
Nylon 66 lends itself well to make 3D structural objects, mostly by injection
molding finding broad use in auto application under the hood such as radiator end
tanks, rocker covers, air intake manifolds, oil pans and numerous other structural
parts such as ball bearing cages, electro-insulating elements, pipes, profiles, various
machine parts, zip ties, conveyor belts, hoses, polymer framed weapons, and the
outer layer of turnout blankets. Nylon 66 is also a popular guitar nut material.
Nylon 11: condensation polymerization of 11-aminoundecanoic acid