CHEMICALS FROM BENZENE

(NYLON & PHENOL)

Oxidation
HYDROGENATION OF BENZENE
(PRODUCTION OF CYCLOHEXANE)
PRODUCTION OF CYCLOHEXANE

 The hydrogenation of benzene produces cyclohexane.

 Many catalyst systems, such as Ni/alumina and Ni/Pd, are
used for the reaction.
 General reaction conditions are 160–220°C and 25–30
atmospheres.
 Higher temperatures and pressures may also be used with
sulfided catalysts:

Benzene Cyclohexane
 PRODUCTION OF CYCLOHEXANE
 Older methods use a liquid phase process (Figure 10-11).
 New gas phase processes operate at higher temperatures
with noble metal catalysts.
 Using high temperatures accelerates the reaction (faster
rate). The hydrogenation of benzene to cyclohexane is
characterized by a highly exothermic reaction.
 Equilibrium conditions are therefore strongly affected by
temperature and pressure.
PRODUCTION OF CYCLOHEXANE (OLD
METHOD - LIQUID PHASE)
Properties and Uses of Cyclohexane
 Cyclohexane is a colorless liquid, insoluble in water but soluble
in hydrocarbon solvents, alcohol, and acetone.
 As a cyclic paraffin, it can be easily dehydrogenated to
benzene.
 Cyclohexane is also a precursor for adipic acid. Oxidizing
cyclohexane in the liquid-phase at lower temperatures and for
longer residence times) with a cobalt acetate catalyst
produces adipic acid:
 These are monomers for making nylon 6 and nylon 66.
ADIPIC ACID

(CH2)4(COOH)2
INTRODUCTION TO ADIPIC ACID
 Dicarboxylic acids are organic compounds that are
substituted with two carboxylic acid functional groups. In
molecular formular for dicarboxylic acids, these groups are
often written as HOOC-R-COOH, where R is usually an alkyl,
akenyl, or akynyl group. Dicarboxylic acids can be used to
prepare copolymers such as polyamides (nylon) and
polyesters.

 From the industrial perspective, ADIPIC ACID is the most

important dicarboxylic acids
USES OF ADIPIC ACID

a) The main use of adipic acid is as monomer for

the production of nylon.
b) Monomer for production of Polyurethane.
c) Reactant to form plasticizers and lubricant
components.
d) Food Ingredient as a flavorant and gelling aid.
DETAIL ON THE ADIPIC ACID
PRODUCTION PROCESS

Oxidation of Cyclohexane to produce

i. Cyclohexanone-Cyclohexanol (KA Oil)
ii. Adipic Acid
 Cyclohexane is oxidized in a liquid-phase
process to a mixture of cyclohexanone and
cyclohexanol (KA oil- Ketone Alcohol Oil).
 The reaction conditions are 95–120°C at
approximately 10 atmospheres in the presence
of a cobalt acetate and orthoboric acid catalyst
system.
 About 95% yield can be obtained:

cyclohexanol cyclohexanone
Cyclohexane

KA oil
 KA oil is used to produce caprolactam, the monomer for
nylon 6.
 Caprolactam is also produced from toluene through the
intermediate formation of cyclohexane carboxylic acid.
 Cyclohexane is also a precursor for adipic acid.
Oxidizing cyclohexane in the liquid-phase at lower
temperatures and for longer residence times (than for
KA oil) with a cobalt acetate catalyst produces adipic
acid:

Cyclohexane Adipic acid

 Adipic acid and its esters are used to make nylon 6/6.
PRODUCTION PROCESS
OF ADIPIC ACID
PRODUCTION PROCESS OF ADIPIC
ACID
 Historically, adipic acid was prepared from various
fats using oxidation.
 Current commercial adipic acid is produced from
cyclohexane by two oxidation steps.

Step 1:
Cyclohexane + O2 → cyclohexanol and cyclohexanone
(KA Oil) + byproducts

Step 2:
KA Oil + nitric acid + air → adipic acid + nitrous oxide
ALTERNATIVE PRODUCTION PROCESS
OF ADIPIC ACID
 Other patented processes include those using phenol as
feedstock. For example, phenol can be hydrogenated to KA
oil, which is further processed to give adipic acid.

 Utilizing principles of green chemistry, a new method of

synthesis has been developed, which involves oxidizing
cyclohexene with hydrogen peroxide via a tungsten catalyst
and a phase transfer catalyst to produce adipic acid. The
waste product is water.
PROCESS EMISSIONS FROM CURRENT
ADIPIC ACID PRODUCTION PROCESS
 Process emissions from the production of adipic acid vary
depending upon the technologies and level of emissions
controls employed by a facility.

 Adipic acid production also generates emissions of non-

methane volatile organic compounds (NMVOC), carbon
monoxide (CO), and nitrogen oxides (NOx).
Production OF Nylon 66
(Polyhexamethyleneadipate)
POLYAMIDES (Nylon Fibers)
 Polyamides are the second largest group of synthetic fibers
after polyesters.
 However, they were the first synthetic fibers that appeared
in the market in 1940. This was the result of the work of W.
H. Carothers in USA who developed nylon 66.
 At about the same time nylon 6 was also developed in
Germany by I. G. Farben. Both of these nylons still
dominate the market for polyamides.
 However, due to patent restrictions and raw materials
considerations, nylon 66 is most extensively produced in
USA and nylon 6 is most extensively produced in Europe.
 Numbers that follow the word “nylon” denote the number
of carbons present within a repeating unit and whether one
or two monomers are being used in polymer formation.
 For nylons using a single monomer such as nylon 6 or nylon
12, the numbers 6 and 12 denote the number of carbons in
caprolactam and laurolactam, respectively.

caprolactam
 For nylons using two monomers such as nylon 610, the first
number, 6, indicates the number of carbons in the
hexamethylene diamine and the other number, 10, is for
the second monomer sebacic acid.
 Polyamides are produced by the reaction between a
dicarboxylic acid and a diamine (e.g., nylon 66), ring
openings of a cyclic amide, (e.g., nylon 6) or by the
polymerization of amino acids (e.g., nylon 11).
PRODUCTION PROCESS OF
NYLON 66
 Nylon 66 is produced by the reaction of
hexamethylenediamine and adipic acid. This produces
hexamethylenediammonium adipate salt.
 The product is a dilute salt solution concentrated to
approximately 60% and charged with acetic acid to a reactor
where water is continuously removed. The presence of a small
amount of acetic acid limits the degree of polymerization to the
desired level:

adipic acid hexamethylenediamine

(dicarboxylic acid) (diamine)
 The temperature is then increased to 270–300°C and the
pressure to approximately 16 atmospheres, which favors
the formation of the polymer.

 The pressure is finally reduced to atmospheric to permit

further water removal. After a total of three hours, nylon 66
is extruded under nitrogen pressure.
Properties of Nylon
 Nylons are generally characterized by relatively high
melting points due to the presence of the amide linkage.
They are also highly crystalline, and the degree of
crystallinity depends upon factors such as the polymer
structure and the distance between the amide linkages.
 An increase in polymer crystallinity increases its tensile
strength, abrasion resistance, and modulus of elasticity.
 Hydrogen bonding in polyamides is fairly strong and has a
pronounced effect on the physical properties of the
polymer such as the crystallinity, melting point, and water
absorption.
 Nylons, however, are to some extent subject to deterioration
by light.

 Nylons are liable to attack by mineral acids but are resistant

to alkalies.

 They are difficult to ignite and are self-extinguishing.

 In general, most nylons have remarkably similar properties,

and the preference of using one nylon over the other is
usually dictated by economic considerations except for
specialized uses.
 Uses of Nylon
 Nylons have a variety of uses ranging from tire cord to
carpet to hosiery (legwear). The most important
application is cord followed by apparel.
 Nylon staple and filaments are extensively used in the
carpet industry.
 Nylon fiber is also used for a variety of other articles such as
seat belts, monofilament finishes, and knitwear. Because of
its high tenacity and elasticity, it is a valuable fiber for
ropes, parachutes, and underwear.
CUMENE TO PRODUCE PHENOL
INTRODUCTION
Cumene (isopropylbenzene), a liquid, is soluble in many organic
solvents but not in water.

It is present in low concentrations in light refinery streams (such

as reformates) and coal liquids.

It may be obtained by distilling (cumene’s B.P. is 152.7°C) these

fractions.

The main process for producing cumene is a synthetic route

where benzene is alkylated with propylene to
isopropylbenzene.

Either a liquid or a gas-phase process is used for the alkylation

reaction.
LIQUID PHASE CUMENE PRODUCTION PROCESS

 In the liquid-phase process low temperatures and pressures

(approximately 50°C and 5 atm )

 Sulfuric acid as a catalyst.

benzene propylene Cumene (isopropylbenzene),

VAPOR PHASE CUMENE PRODUCTION PROCESS
In the vapor-phase process, the reaction temperature and
pressure are approximately 250°C and 40 atm.

Phosphoric acid on Kieselguhr (SOLID Phosphoric acid) is a

commonly used catalyst.

To limit polyalkylation, a mixture of propene-propane feed is

used. Propylene can be as low as 40% of the feed mixture.

A high benzene/propylene ratio is also used to decrease

polyalkylation.

A selectivity of about 97% based on benzene can be obtained.

UOP CUMENE PROCESS
UOP Process Description
In the UOP process (Figure 10-5), fresh propylene feed is
combined with fresh and recycled benzene, then passed
through heat exchangers and a steam preheater before being
charged to the reactor.

The effluent is separated, and excess benzene recycled.

Cumene is finally clay treated and fractionated.

The bottom product is mainly diisopropyl benzene, which is

reacted with benzene in a transalkylation section:
UOP Process Description
A plant based on this process may also include one or more
clay treaters (CT), which remove oligomers (dimerization) by
converting them to heavier material, which can be easily
separated by distillation.
NEW TECHNOLOGY IN CUMENE
PRODUCTION PROCESS
To reduce pollution, Dow developed a new catalyst
system from the mordenite-zeolite group to replace
phosophoric acid or aluminum chloride catalysts.

The new catalysts eliminates the disposal of acid

wastes and handling corrosive materials.
USES OF CUMENE

It is mainly used to produce phenol and acetone.

A small amount of cumene is used to make -

methylstyrene by dehydrogenation.

-Methylstyrene is used as a monomer for

polymer manufacture and as a solvent.
PHENOL
Oxidation
PROCESS SYNTHESIS OF PHENOL
Phenol, C6H5OH (hydroxybenzene), is produced from
cumene by a two-step process.

STEP 1:
In the first step, cumene is oxidized with air to cumene
hydroperoxide. The reaction conditions are
approximately 100–130°C and 2–3 atmospheres in the
presence of a metal salt catalyst:

Oxidization

Cumene cumene hydroperoxide

PROCESS SYNTHESIS OF PHENOL

STEP 2:
In the second step, the hydroperoxide is decomposed in
the presence of an acid to phenol and acetone.

The reaction conditions are approximately 80°C and

slightly below atmospheric:

Decomposition

cumene hydroperoxide phenol acetone

Production Process of Phenol
 Production Process of Phenol

 In this process (Figure 10-6), cumene is oxidized in the

liquid phase. The oxidation product is concentrated to 80%
cumene hydroperoxide by vacuum distillation.

 To avoid decomposition of the hydroperoxide, it is

transferred immediately to the cleavage reactor in the
presence of a small amount of H2SO4.

 The cleavage product is neutralized with alkali before it is

finally purified.
 Production Process of Phenol
 After an initial distillation to split the co products phenol and
acetone, each is purified in separate distillation and treating
trains.

 An acetone finishing column distills product acetone from an

acetone/water/oil mixture.

 The oil, which is mostly un reacted cumene, is sent to

cumene recovery.

 Acidic impurities, such as acetic acid and phenol, are

neutralized by caustic injection.
HAZARDOUS CHARACTERISTICS OF PHENOL
Autoignition temperature is 715°C.

Phenol is a volatile, combustible solid that when heated gives

off flammable vapours and carbon dioxide.

Explosive or violent reactions occur with acetylaldehyde;

aluminium chloride plus nitrobenzene; aluminium chloride-
nitromethane; butadine; calcium hypochlorite;
peroxomonosulphuric acid; etc.

Phenol is sensitive to oxidising agents. Splitting of the hydrogen

atom from the phenolic hydroxyl group is followed by
resonance stabilisation of the resulting phenyloxy radical. The
radical that is formed can be further oxidised. This makes
phenol suitable as an antioxidant.
SAFETY MEASURES IN PHENOL
PRODUCTION PLANT
Vents of oleum, phenol and ammonia storage tanks should
be equipped with water scrubbers

Neutralization with a strong acid. Neutralization with acid

gas or flue gas to partition the phenols into a buoyant oily
phase for further treatment;
IMPACT OF PHENOL TO THE
ENVIRONMENT
Phenol is not likely to persist in air, soil or sewage, sea or
surface water.
It readily reacts photochemically, is rapidly biodegraded
aerobically to mainly carbon dioxide, and anaerobic
biodegradation occurs also at a slower rate.
Low removal rates of phenol in ground water and soil may
occur e.g. following spills, with subsequent inhibition of the
microbial populations.
Phenol is toxic to aquatic organisms: the lowest EC50 for water
organisms is estimated to be 3.1 mg/L.
PROPERTIES AND USES OF PHENOL
Phenol, a white crystalline mass with a distinctive odor,
becomes reddish when subjected to light.

It is highly soluble in water, and the solution is weakly acidic.

Many chemicals and polymers derived from phenol.

Approximately 50% of production goes to phenolic resins.

Phenol and acetone produce bis-phenol A, an important

monomer for epoxy resins and polycarbonates. It is produced by
condensing acetone and phenol in the presence of HCI, or by
using a cation exchange resin.
PROPERTIES AND USES OF PHENOL
Phenol is also used in the preparation of cosmetics including
sunscreens, hair dyes, and skin lightening preparations.
Compounds containing phenol moieties can be used to prevent
ultraviolet light-induced damage to hair and skin due to the UV-
absorbing properties of the aromatic ring of the phenol.
It is also used in cosmetic surgery as an exfoliant, to remove
layers of dead skin.
It is also used in phenolization, a surgical procedure used to
treat an ingrown nail, in which it is applied to the toe to prevent
regrowth of nails.
A class of acid organic compounds used in the manufacture of
epoxy resins.