Phenol

Phenol is the specific name for hydroxybenzene, C6H5OH. Phenol has a melting point of 40.9 °C. At lower
temperatures it crystallizes as a white mass. In the molten state it is a clear, colorless liquid. The melting and
solidification point of phenol is lowered considerably by traces of water. The predominant uses of phenol are in
bisphenol A, Phenolic resins, caprolactam, aniline, and alkylphenols.

Manufacture:

The cumene oxidation route is the leading commercial process of synthetic phenol production, accounting for
more than 95% of phenol produced in the world.

There are several licensed processes to produce phenol which are based on cumene. All of these processes
consist of two fundamental chemical reactions: cumene is oxidized with air to form cumene hydroperoxide, and
cumene hydroperoxide is cleaved to yield phenol and acetone. In this process, approximately 0.46 kg of acetone
and 0.75 kg of phenol are produced per kg of cumene feedstock.

A typical phenol plant based on the cumene hydroperoxide (CHP) process can be divided into two principal
areas. In the reaction area, cumene, formed by alkylation of benzene and propylene, is oxidized to form cumene
hydroperoxide (CHP). The cumene hydroperoxide is concentrated and cleaved to produce phenol and acetone.
By-products of the oxidation reaction are acetophenone (ACP) and dimethyl benzyl alcohol (DMBA). DMBA
is dehydrated in the cleavage reaction to produce alphamethylstyrene (AMS).

The recovery area of the plant employs fractionation to recover and purify the phenol and acetone products.
Also in this section the alpha-methylstyrene is recovered and may be hydrogenated back to cumene or
recovered as AMS product. The hydrogenated AMS is recycled as feedstock to the reaction area. The overall
yield for the cumene process is 96 mol %.

Production of Cumene

Cumene is produced commercially through the alkylation of benzene with propylene over an acid catalyst. Over
the years, many different catalysts have been proposed for this alkylation reaction, including boron trifluoride,
hydrogen fluoride, aluminum chloride, and phosphoric acid. Among which >80% of the cumene in the world
was produced by the solid phosphoric acid (SPA) process licensed by UOP.

Although SPA is a highly efficient and economical catalyst for cumene synthesis, it has two important
limitations:

1. Cumene yield is limited to about 95 percent, because of the oligomerization of propylene and the formation
of heavy alkylate by-products

2. The catalyst is not regenerable and must be disposed of at the end of each catalyst cycle.
The synthesis of cumene from benzene and propylene is a modified Friedel-Crafts alkylation, which can be
accomplished by many different acid catalysts. The olefin forms a carbonium ion intermediate, which attacks
the benzene ring in an electrophilic substitution. The addition to the olefin double bond is at the middle carbon
of propylene, in accordance with Markovnikov’s rule. The addition of the isopropyl group to the benzene ring
weakly activates the ring toward further alkylation, producing di-isopropyl-benzene (DIPB) and heavier
alkylate by-products.

Transalkylation of DIPB is the acid-catalyzed transfer of one isopropyl group from DIPB to a benzene molecule
to form two molecules of cumene. After recovery of the cumene product by fractionation, the DIPB is reacted
with recycle benzene at optimal conditions for transalkylation to produce additional cumene.

Phenol production:

Oxidation of Cumene to CHP

The oxidation of cumene as the first reaction step is usually carried out in a series of bubble column reactors
Fresh and recycle cumene are fed to the first reactor. Oxygen is used in each reactor as oxidant. The bubble
columns are operated at pressures ranging from atmospheric to about 700 kPa and temperatures in the range 80-
120°C. The temperature is controled by internal or external heat exchangers. The final CHP concentration
varies typically from 20 to 40%. Phenol is a strong inhibitor, so any recycled cumene must be treated to remove
even traces of phenol. Formation of the byproducts DMBA and ACP depends on the CHP concentration.
Depending on temperature, the residence time in the oxidizer train is between 4 and 20 h.

In the early years of the cumene oxidation process, the oxidation was carried out as a three phase reaction, so-
called wet oxidation. In addition to cumene and air an aqueous sodium carbonate solution was continuously
added to the reactors to extract and neutralize organic acids, which are formed during oxidation.
Phenolchemie, now INEOS Phenol, was the first to operate the reactors without adding any caustic soda or
sodium carbonate, a process known as dry oxidation.

The off-gas from the reactor is purified by two-step condensation of organic components with cooling water in
condensers and chilled water or other refrigerants in another condenser. The CHP concentration in the oxidation
product is increased by vacuum distillation to about 65 – 90 %.
Phenol from toluene (Dow process)
The two-steps of the process are first the oxidation of toluene to benzoic acid, which was already well known,
and second the oxidation of benzoic acid to phenol. In principle the conversion of toluene to phenol is a
complete oxidation of the methyl group with the byproducts carbon dioxide and water.

The oxidation of toluene as the first step is carried out in the liquid phase at temperatures about 100 – 150 °C
and a gauge pressure of about 2 bar. Atmospheric oxygen is used. A cobalt naphthenate is used as a soluble
catalyst at concentrations between 0.1 and 0.3 %. The oxidation of toluene to benzoic acid has a complex
radical chain mechanism. Benzyl alcohol and benzaldehyde are intermediates in the successive oxidation to
benzoic acid. Byproducts such as benzyl benzoate and biphenyl are formed, as well as formic acid, acetic acid,
and, in smaller amounts, carbon dioxide and carbon monoxide.

For the oxidation of benzoic acid as the second step molten benzoic acid is used as the reactant and solvent
medium. The temperature is about 230 – 240 ◦C at atmospheric pressure. Benzoic acid reacts with atmospheric
oxygen, steam, and soluble copper(II) benzoate as catalyst. Magnesium salts may be added to act as a promotor.
Fresh and recycle toluene as well as air and the cobalt catalyst are charged to gas – liquid reactor R1, which can
be, for example, a bubble column. The reactor has cooling devices to remove the reaction heat, for example, in
an external circulation loop. The toluene conversion is limited to 40 %. The yield of benzoic acid is about 90 %.
The off-gas from the reactor is cooled by passing it through a water-cooled condenser. The condensed toluene is
recycled to the reactor, and the water phase is withdrawn for further wastewater treatment. The noncondensable
gas, principally nitrogen, is treated in activated-carbon adsorption unit A1 to remove traces of toluene and other
organic components. The liquid phase from the reactor is at first fractionated in column C1. Toluene and the
intermediate benzaldehyde are taken overhead for recycle. The crude benzoic acid as the bottom product is
purified in the second column C2. The catalyst containing high boilers (tar) is taken as the bottom product,
which is partially recycled to the reactor. Purified benzoic acid is oxidized in the second reactor R2, which is a
stirred gas – liquid reactor. In the presence of the copper(I/II) catalyst the acid is contacted with air and recycled
vaporized water. In addition steam may be added to the air. Small amounts of magnesium benzoate may be
added as a promoter. The benzoic acid conversion is 70 – 80%with a yield of phenol of about 90 %. Phenol,
benzoic acid, water, and other organic components are vaporized continuously. The vapors are charged to
column C3. Water and hydrocarbons are taken as the overhead fraction and separated into two liquid phases.
The remaining gas phase is purified in adsorption unit A2. The separated water is used to extract benzoic acid
from the tar which has to be removed from reactor R2. This is done in extraction unit V1, which consists of a
series of several mixer – settlers. The aqueous phase from V1 is vaporized and recycled to reactor R1. The tar
contains the copper salts. If it is burned special incineration equipment is required to insure that no heavy metal
emissions occur. The organic phase from the overheads of column C3 contains mainly toluene and benzene.
Benzene is separated from toluene in column C4. Toluene is recycled to the oxidation reactor R1. Crude phenol
is taken as a side cut from column C3. In Column C5 pure phenol is taken as the overhead. Benzoic acid is
withdrawn as the bottom product and recycled to reactor R2. Because of the corrosive character of benzoic acid
apparatus must be constructed from stainless steel 1.4571 or even from Hastelloy.