Article No : a19_299

Phenol
MANFRED WEBER, INEOS Phenol GmbH, Gladbeck, Germany
MARKUS WEBER, INEOS Phenol GmbH, Gladbeck, Germany
MICHAEL KLEINE-BOYMANN, INEOS Phenol GmbH, Gladbeck, Germany

1. Introduction. . . . . . . . . . . . . . . . . . ..... . 503 4.4.3. Direct Oxidation of Benzene . . . . . . . . . . . . 513

2. Physical Properties . . . . . . . . . . . . ..... . 503 5. Environmental Protection . . . . . . . . . . . . . 514
3. Chemical Properties . . . . . . . . . . . ..... . 504 6. Quality Specifications. . . . . . . . . . . . . . . . . 515
4. Production . . . . . . . . . . . . . . . . . . . ..... . 505 7. Storage and Transportation. . . . . . . . . . . . 515
4.1. Cumene Oxidation (Hock Process) ..... . 505 8. Uses and Economic Aspects . . . . . . . . . . . . 516
4.2. Toluene Oxidation . . . . . . . . . . . . . ..... . 509 9. Toxicology and Occupational Health . . . . . 516
4.3. Phenol from Coal. . . . . . . . . . . . . . ..... . 511 References . . . . . . . . . . . . . . . . . . . . . . . . . 518
4.4. Other Processes . . . . . . . . . . . . . . . ..... . 512
4.4.1. Sulfonation of Benzene . . . . . . . . . . ..... . 512
4.4.2. Chlorination of Benzene . . . . . . . . . ..... . 512

1. Introduction 2. Physical Properties

Phenol is the specific name for hydroxybenzene, Phenol has a melting point of 40.9  C. At lower
C6H5OH [108-95-2]. It is the generic name for temperatures it crystallizes as a white mass. In
any molecule containing one or more hydroxyl the molten state it is a clear, colorless liquid.
groups attached to an aromatic ring. Phenol was The melting and solidification point of phenol
discovered in 1834 by RUNGE, who isolated it is lowered considerably by traces of water (see
from coal tar and named it carbolic acid. In 1841 Fig. 1).
LAURENT obtained it in crystalline form, deter- At temperatures up to 68.4  C it is partially
mined its composition, and named it phenolic miscibile with water [1] (see Fig. 2).
acid, which was later abbreviated to phenol. Phenol is soluble in most organic solvents, for
Finally KEKULE formulated its molecular struc- example aromatic hydrocarbons, alcohols, ke-
ture in 1858. Till the end of the 1800s all phenol tones, ethers, acids, and halogenated hydrocar-
was recovered from coal. It was mainly used as a bons. It is less soluble in aliphatic hydrocarbons.
disinfectant. In 1897 HOFFMANN was the first to
synthesize acetylsalicylic acid, the active ingre-
dient in Aspirin, from phenol in a pure and stable
form. In the 1900s demand for phenol grew with
the commercialization of the phenolic resins
after World War I, bisphenols after World
War II, and polycarbonates during the 1960s.
The first synthetic phenol was produced com-
mercially by the benzenesulfonate process.
Nowadays more than 95 % of phenol, around
7.3
106 t in total in 2003, is produced by the
cumene oxidation process, and the rest is pro-
duced via toluene oxidation or recovered from
coal tar. A direct process for oxidation of ben-
zene to phenol has still not been commercialized. Figure 1. Effect of water on the solidification point of phenol

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a19_299.pub2
504 Phenol Vol. 26
Specific heat (vapor state)
27  C 1.105 kJ kg1 K1
527  C 2.26 kJ kg1 K1
Flash point (DIN 51758) 82  C
Lower explosion limit in air at 1.3 vol% (50 g/m3)
101.3 kPa (corresponds to 73 C
product temperature i.e.,
vapor – liquid equilibrium)
Saturation concentration in air (20 C) 0.77 g/m3
Ignition temperature (DIN 51794) 595  C
Temperature class (VDE, EN) T1 (> 450  C)
Autoignition temperature 715  C
No allocation to a hazard class
according to VbF because of a
Figure 2. Miscibility of phenol and water solidification point > 35  C
Flash point of mixtures with water
Table 1. Azeotropic mixtures with phenol 1–4 % water ca. > 82 C
>4.5 % water >100  C
Phenol in Specific resistance (45  C) >1.8
107 Wcm
Second component Pressure, kPa bp,  C vapor, wt % Mixture with 5% water 4.9
106 Wcm
Vapor pressure
Water 101.3 94.5 9.21
20 C 0.02 kPa
70.8 90.0 8.29
36.1 C 0.1 kPa
39.2 75.0 7.2
48.5 C 0.25 kPa
16.9 56.3 5.5
58.3 C 0.5 kPa
Isopropylbenzene 101.3 149 2
69 C 1 kPa
n-Propylbenzene 101.31 158.5 14
84.8 C 2.5 kPa
a-Methylstyrene 101.3 162 7
98.7 C 5 kPa
114.5 C 10 kPa
137.3 C 25 kPa
Phenol forms azeotropic mixtures with water and 158 C 50 kPa
181.5 C 100 kPa
other substances [2] (see Table 1).
207.5 C 200 kPa
Phenol has the following physical properties 247.7 C 500 kPa
[3–6]: 283 C 1000 kPa

Mr 94.11
bp (101.3 kPa) 181.75 C 3. Chemical Properties
mp 40.9 C
Relative density
0 C 1.092 The chemical properties of phenol are character-
20 C 1.071 ized by the mutual influence of the hydroxyl
50 C 1.050 group and the aromatic ring upon each other.
Vapor density (air ¼ 1) 3.24
Refractive index
nD41 1.5418 Reactions Involving the O H Bond. In
nD50 1.5372 contrast to aliphatic alcohols phenol is a weak
Dynamic viscosity acid and therefore reacts with strong bases to
20  C 11.41 mPas
form salts which are soluble in water. This effect
50  C 3.42 mPas
100  C 1.5 mPas is used to recover phenol from organic liquids
150  C 0.67 mPas such as coal tar. The pKa value in aqueous
Cubic expansion coefficient (50  C) 8.8
107L g1 K1 solution is 10.0. The phenolate anion is stabilized
Dissociation constant in water (20 C) 1.28
1010
by the aromatic ring system. At room tempera-
Heat of fusion (41  C) 120.6 kJ/kg
Heat of vaporization (182  C) 511 kJ/kg ture phenol can be liberated from the salts even
Heat of formation (20  C) 160 kJ/kg with carbon dioxide. At temperatures near the
Heat of combustion 32 590 kJ/kg boiling point of phenol, it can displace carboxylic
Specific heat
acids such as acetic acid from their salts, whereby
0 C 1.256 kJ kg1 K1
20  C 1.394 kJ kg1 K1 phenolates are formed. The hydoxyl group can
50  C 2.244 kJ kg1 K1 easily be esterified (e.g., to phenyl acetate) and
100  C 2.382 kJ kg1 K1 etherified (e.g., diphenyl ether).
Vol. 26
Reactions of the Aromatic Ring. The acid-
ity of phenol is due to the fact that the unshared
electron pair is delocalized over the aromatic ring
and thus stabilized [7].
The excess of electrons in the aromatic ring
at the ortho and para positions makes phenol
very susceptible to electrophilic substitution.
An example is the reaction with bromine in
aqueous solution to give 2,4,6-tribromophenol
in high yield. Another important reaction is the
coupling of carbon dioxide with sodium phen-
oxide at 125  C to give the sodium salicylate
(Kolbe reaction). At 125  C carbon dioxide is
substituted in the ortho position, whereas at
temperatures above 250  C the para isomer is
favored. Other reactions following electro-
philic substitution are chlorination, sulfona-
tion, and nitration.
Liquid-Phase Oxidation. The oxidation of
organic substances by molecular oxygen leads to
a large number of intermediate products, for
example, cumene hydroperoxide. These process-
es proceed with a complex radical mechanism
[8]. Phenol acts as an inhibitor in such reactions
by reacting with free radicals to form phenoxy
radicals. These are relatively stable radicals
which do not propagate the chain mechanism.
Therefore any unwanted ingress of phenol into
such oxidation processes must be avoided.
4. Production
Today the oxidation of cumene (Hock process) is
by far the dominant synthetic route to phenol
with a production rate of more than 6.7
106 t/a
of phenol and about 4.1
106 t/a of the coprod-
uct acetone. It is the most competitive process,
supported by the demand for acetone. As the
demand for phenol may increase more strongly in
the future, there is still a commercial interest in
finding new, coproduct-free routes to phenol, for
example, the direct oxidation of benzene to
Phenol 505
phenol. The oxidation of toluene with benzoic
acid as intermediate product is used for phenol
production with an annual production of about
300 000
106 t. About 300 000
106 t of
phenol is still recovered from coal tar. Since ca.
1995 the direct oxidation of benzene to phenol
with nitrous oxide has been developed by Solutia
but has still not been commercialized. Classic
synthetic routes such as the benzene sulfonation
process and hydrolysis of chlorobenzene with
caustic soda no longer have any economic
importance.
4.1. Cumene Oxidation (Hock Process)
General Overview. The process consists of
two fundamental chemical reactions: cumene is
at first oxidized with oxygen to cumene hydro-
peroxide (CHP). CHP is then cleaved to phenol
and acetone by using a strong mineral acid as
catalyst. Both reactions are very exothermic with
heats of reaction of 117 kJ/mol for the oxida-
tion of cumene and 252 kJ/mol for the cleavage
of the peroxide.
These reactions were first reported in 1944 by
H. HOCK and S. LANG [9]. The industrial cumene
oxidation process was developed and commer-
cialized after World War II by The Distillers Co.
in Great Britain and the Hercules Powder Com-
pany in the USA [10, 11]. The first plant started
up in 1952 at Shawinigan, Canada, with a capac-
ity of 8000 t/a. Today the biggest producers
of phenol using cumene oxidation are INEOS
Phenol (Europe and USA), Sunoco (USA),
Mitsui (Japan, Singapore), Shell (USA), Poly-
meri Europa (Italy), and Ertisa (Spain). Some
developed their own technology. Others use a
licensed process from, for example, Kellogg
Brown and Root or UOP. Although all use the
principles of the Hock synthesis, there are dif-
ferences in the technical design of the reaction
and fractionation sections. The key item for the
overall process yield is the formation of the
506 Phenol
Figure 3. Production of phenol from cumene
R1, R2 cumene oxidation reactor; X1 – X3 condensers; A1, A2 activated-carbon adsorbers; VC vacuum distillation column;
R3 – R5 cleavage reactors; V1 neutralization drum; C1 acetone column; C2 cumene column; C3 AMS column; C4 phenol
column; R6 hydrogenation reactor; V2 cumene scrubber
byproducts dimethylbenzyl alcohol (DMBA)
and acetophenone (ACP) in the oxidation step.
ACP leaves the process with the high boilers
from distillation. DMBA is dehydrated in the
cleavage stage to a-methylstyrene (AMS), which
partially forms high-boiling dimers and cumyl-
phenols in the acid-catalyzed process step. The
unconverted AMS is hydrogenated back to cu-
mene later in the process.
The flow sheet of the cumene oxidation pro-
cess is shown in Figure 3. The oxidation of
cumene as the first reaction step is usually carried
out in a series of bubble column reactors R1 and
R2. Fresh and recycle cumene are fed to the first
reactor. Oxygen is used in each reactor as oxi-
dant. The bubble columns are operated at pres-
sures 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 [12]. The final CHP concentra-
tion varies typically from 20 to 40 % [13]. The
off-gas from the reactor is purified by two-step
condensation of organic components with cool-
ing water in condensers X1, X2 and chilled water
or other refrigerants in X3. The organic compo-
nents are mainly cumene and methanol besides
some smaller amount of water. The residual
impurities in the off-gas are finally removed in
activated carbon adsorbers A1, A2. Layers of
different types of activated carbon may be used
for better co-adsorption of cumene and methanol
[14]. The condensed cumene is recycled to the
oxidation reactors. The CHP concentration in the
Vol. 26
oxidation product is increased by vacuum distil-
lation in column VC to about 65 – 90 %.
The first part of the cleavage section is a series
of heat exchangers R3, R4 within a circulation
loop. Heat exchangers are used as reactors be-
cause the reaction is very fast and exothermic.
The CHP is spontaneously diluted in the circula-
tion product, which consists of phenol, acetone,
cumene, and several byproducts as well as resid-
ual amounts of CHP. Normally sulfuric acid is
used as the catalyst at a concentration of several
hundred parts per million by weight (wppm). As
the acid is completely dissolved in the reaction
mass this type of process is called homogeneous
cleavage. The temperature is in the range 40 –
80  C at atmospheric pressure. The product from
the first step, so-called cleavage product, is heat-
ed in R5 to temperatures above 100  C. In this
second step residual CHP is cleaved, as is the
intermediate dicumyl peroxide (DCP), which is
formed in the first step by condensation of CHP
and DMBA. Finally residual DMBA is dehy-
drated to AMS and water. The product is cooled
and neutralized with aqueous sodium phenolate
NaPh. An aqueous phase is formed containing
sodium sulfate and salts of organic acids. The
aqueous phase is separated in neutralization
drum V1 and sent to wastewater treatment. The
organic phase, consisting of phenol, acetone,
cumene, AMS, dissolved water, and low- and
high-boiling byproducts, is separated in a series
of distillation columns.
More details on several process steps follow.
Vol. 26
Oxidation. The oxidation of cumene with
oxygen in the liquid phase proceeds by a complex
radical mechanism [15]. The reaction is autoca-
talyzed by cumene hydroperoxide. Thus, the
reaction rate to CHP not only depends on the
cumene but also on the CHP concentration.
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 [16,
17]. The activation energy for these side reac-
tions are higher than for the main reaction. Thus,
the oxidation should be run at low temperatures
to suppress the formation of DMBA and ACP.
As the reaction rate depends on the CHP
concentration, backmixed reactors are preferred
for cumene oxidation to give high CHP concen-
trations. Bubble columns, in which the liquid
phase is well backmixed, are therefore suitable
for this process. On the other hand, high CHP
levels cause more DMBA formation. Thus a
series of several bubble columns is the optimal
reactor concept [17].
The oxidation is operated either under over-
pressure at temperatures between 90 and 120  C,
or under atmospheric pressure at temperatures
below 100  C. Depending on temperature, the
residence time in the oxidizer train is between 4
and 20 h [18]. HATTORI et al. [19] investigated the
influence of the partial pressure of oxygen on
the reaction rate to CHP. As a rule of thumb, the
partial pressure of oxygen in the gas phase should
be above 0.1 bar for temperatures around 100  C
to ensure sufficient mass transfer and thus avoid
hindrance of the reaction rate. This is an impor-
tant issue because atmospheric oxygen is con-
sumed from ca. 21 vol % to some residual value
at the top of the bubble column. Thus, depending
on the absolute pressure, the oxygen partial
pressure also decreases but should not fall below
the above-mentioned value. Lower temperatures
than 100  C may require lower partial pressures
of oxygen. The oxidation of cumene with pure
oxygen in stirred vessels has been already de-
scribed [11].
In the early years of the cumene oxidation
process, the oxidation was carried out as a three-
phase reaction [20–22], 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. Phenol-
Phenol 507
chemie, now INEOS Phenol, was the first to
operate the reactors without adding any caustic
soda or sodium carbonate [23], a process known
as dry oxidation.
CHP is a relatively stable organic peroxide.
Nevertheless the thermal decomposition of CHP
is the main source for DMPC formation in the
oxidation process. Especially in large reactors
the exothermic decomposition of CHP has to be
taken into account during a shutdown when the
reactors are not mixed by aeration. The reactor
must be cooled down to below theself-accelerat-
ing decompositon temperature (SADT). Below
the SADT heat removal by heat losses is higher
than heat production by thermal decomposition,
so that the reactor will not heat up [17, 24].
Concentration is performed by one- or
multiple-step vacuum distillation [11]. Cumene
is separated from concentrated CHP at tempera-
tures below 100  C to minimize thermal decom-
position of the organic peroxide. As traces of
organic acids are present in the overheads the
cumene must be washed with aqueous caustic
soda or sodium carbonate before it is recycled to
the oxidation. To minimize any acid-catalyzed
decomposition of CHP in the concentration step,
fresh cumene is taken as reflux [25].
Cleavage. The first stage of homogeneous
cleavage is performed either in a circulation loop
with one or more heat exchangers in series, as
shown in Figure 3 [26–28] or in a backmixed
vessel with internal or external cooling devices
[18, 29] (see Fig. 4).
In the backmixed vessel with internal cooling
the temperature is, for example, maintained
by vaporizing and refluxing acetone (Fig. 4a).
Figure 4. Cleavage of cumene hydroperoxide (CHP) in
backmixed vessels
Removal of heat by vaporizing and refluxing acetone;
Removal of heat by external cooling
508 Phenol
Figure 5. Heterogeneous cleavage of cumene hydroperoxide
(CHP)
Recycle acetone from the distillation is added to
the CHP before the reaction vessel [11]. Another
possibility is to remove the heat from the reaction
vessel with an external heat exchanger in a loop
(Fig. 4b).
In heterogeneous cleavage the first stage is
carried out in a circulation loop of 40 wt %
aqueous sulfuric acid [11, 30, 31] (Fig. 5). The
heat is removed by a series of heat exchangers in
the loop. Cumene hydroperoxide (CHP) from the
concentration step is added to the acid on the
suction side of the circulation pump in a ratio of
1:4. After the last cooler the organic phase is
separated from the aqueous acid, and the acid is
recycled to the pump.
The homogeneous cleavage of CHP to phenol
and acetone is first-order both in CHP and in acid
[32]. Only small amounts of acid are continu-
ously added to the reactor. The acid activity is
considerably dependent on the solvent system
[13]. Especially the amount of dissolved water,
which is formed by dehydration of dimethylben-
zyl alcohol (DMBA), has a major influence on
the acid activity [33]. In the first stage of cleavage
CHP partially condenses with DMBA to form the
intermediate dicumyl peroxide (DCP) and water
[29]. Other byproducts are hydroxyacetone from
the reaction of CHP with acetone, 2-methylben-
zofurane from the reaction of hydroxyacetone
with phenol, diacetone alcohol from the aldol
condensation of acetone, and mesityl oxide from
the dehydration of diacetone alcohol. An over-
view of these reactions is given in [34].
The product from the first cleavage stage
contains residual amounts of CHP and DMBA
as well as the intermediate DCP. The reaction is
completed in a short-residence-time plug-flow
reactor in the second stage of the cleavage (see
Fig. 3). The product is heated to temperatures
above 100  C [27, 29, 35]. DCP and water react
Vol. 26
back to CHP and DMBA, CHP is cleaved spon-
taneously to phenol and acetone, and DMBA is
completely dehydrated to a-methylstyrene and
water.
After cooling, all reactions are stopped by
adding a neutralizing agent such as aqueous
sodium phenolate to the cleavage product
(see Fig. 3). Salts from the neutralization are
extracted with the aqueous phase. It is important
to neutralize the sulfuric acid and the organic
acids to avoid corrosion in the distillation stage.
On the other hand, salts from the neutralization
should be extracted thoroughly with the aqueous
phase to avoid fouling and plugging of the eva-
porators in distillation. Another possibilty is to
neutralize the cleavage product on a caustic-
exchanged sulfonic ion-exchange resin [13, 36].
Distillation. In the first distillation column
C1 (see Fig. 3), acetone is separated as the top
product. This acetone stream contains mostly
water and low boiling aldehydes as impurities.
For high-purity acetone, the top stream must be
separated in an additional reactive distillation
column [37]. Caustic soda is introduced over the
feed position in this reactive distillation column.
The caustic soda catalyzes condensation reac-
tions of the aldehydes to form high boilers. A side
stream above the feed contains pure acetone. The
top stream of this column is recycled back to the
cleavage. Cumene and AMS are taken as over-
heads in column C2. In column C3 the cumene –
AMS fraction is separated into cumene as a top
product and crude AMS as the bottom stream.
This crude AMS can be further purified to obtain
pure AMS. The top product contains mostly
cumene and some AMS. This stream is sent to
the hydrogenation, where AMS is hydrogenated
to cumene. The hydrogenation takes place in
fixed-bed reactor R6. After removal of residual
phenol by extraction with caustic soda (cumene
scrubber V2), the reactor outlet is recycled back
to oxidation. The aqueous sodium phenolate
from the cumene scrubber is used as neutraliza-
tion agent for the cleavage product. Pure phenol
is taken as the overhead from column C4. The
bottom stream of column C4 consists mainly of
acetophenone, AMS dimers, cumylphenols, and
tar and may be disposed of by incineration. In
older processes the tar is treated thermally to
recover cumene, AMS, and phenol [11]. A new
application is the use of the desalted tar for
Vol. 26 Phenol 509

production of carbon black [38]. Several minor
impurities which are formed in cleavage, such as
hydroxyacetone and mesityl oxide, can not be
easily separated from phenol by simple distilla-
tion. For ultrahigh-purity phenol some subse-
quent purification steps are needed. The phenol
from the top stream of column C4 can be treated
with an acidic ion exchange resin in a fixed-bed
reactor in the fluid phase. This catalyzes reactions
of ketones and aldehydes. These reactions gen-
erate low and high boilers, so that further distil-
lation columns are needed to finally obtain pure
phenol [39]. As an alternative the phenol can be
separated from impurities by extractive distilla-
tion [40, 41]. Polyalkylene glycol, alkanediols,
and ethanolamines are used as extractive agents.
The extractive agent is introduced in a first
column above the feed. The interaction between
the phenol and the extractive agent results in their
being in the bottom stream. The impurities leave
the column over the top stream. A second column
is used to separate the extractive agent from the
pure phenol. Water can also be added to enhance
the separation of minor impurities [42]. Another
possibility for the purification of the phenol
stream is to add amines [43]. The amine reacts
in a first step with the ketones and in a second step
with aldehydes to high boilers that can be easily
separated from phenol by distillation.
4.2. Toluene Oxidation
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 [46–48].
Atmospheric oxygen is used. A cobalt
naphthenate is used as a soluble catalyst at con-
centrations between 0.1 and 0.3 %. The oxidation
of toluene to benzoic acid has a complex radical
chain mechanism. Benzyl alcohol and benzalde-
hyde are intermediates in the successive oxida-
tion 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 [46, 47].
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 [46–48]. Benzoic
acid reacts with atmospheric oxygen, steam, and
soluble copper(II) benzoate as catalyst [46, 49].
Magnesium salts may be added to act as a promotor
[50]. The formation of phenol is the net result of
several reactions which occur simultaneously in the
system. Copper(II) benzoate thermally decomposes
to copper(I) benzoate and benzoylsalicylic acid:

General Overview. In the 1950s it appeared

that toluene would be available in large quantities
and it would be a cheaper source for the aromatic
ring than benzene. One suggestion was to use
toluene for the production of phenol. This pro-
cess was developed by the California Research
Corp. [44] and Dow Chemical [45]. The two-
steps of the process are first the oxidation of
toluene to benzoic acid, which was already well The copper(I) benzoate from the first reaction
known, and second the oxidation of benzoic acid step is regenerated with atmospheric oxygen:
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.
510 Phenol
In the presence of water or steam, benzoylsa-
licylic acid is hydrolyzed to benzoic acid and
salicylic acid:
The salicylic acid is decarboxylated rapidly to
give phenol and carbon dioxide:
Thus, the net reaction for the oxidation of
benzoic acid is:
Byproducts include benzene and diphenyl
ether.
Figure 6. Production of phenol from toluene
R1 toluene oxidation reactor; A1 adsorption unit; C1 toluene column; C2 benzoic acid column; R2 benzoic acid oxidation
reactor; A2 adsorption unit; C3 crude phenol column; C4 benzene column; C5 pure phenol column; V1 tar extraction unit
Vol. 26
Dow Process. The first commercial plant
based on the Dow process was started up in the
early 1960s at Landar, British Columbia, operat-
ed by Dow-Canada (shut down), and the second
at Kalama, Washington, operated by Dow Chem-
ical Company (capacity in 2002 ca. 32 000 t/a
phenol). The third plant was built at Rosenburg,
Netherlands, operated by DSM (capacity in 2002
ca. 110 000 t/a phenol). In 1991 a new plant was
brought on line in Japan by Nippon Phenol
(capacity in 2002 ca. 120 000 t/a phenol).
Simplified process flow diagrams of the Dow
process are given in [46–48], [51, 52]. Figure 6
gives an overview of the process. 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
as shown in Figure 6. 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 waste-
water treatment. The noncondensable gas, princi-
pally nitrogen, is treated in activated-carbon ad-
sorption unit A1 to remove traces of toluene and
other organic components. The liquid phase from
the reactor is at first fractionated in column C1.
Vol. 26
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 conver-
sion 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 remain-
ing 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.
Lummus Process. In 1978 The Lummus
Company announced a new process for the oxi-
dation of benzoic acid [53]. The oxidation is
conducted in the vapor phase over a copper-
containing catalyst [54]. Instead of using a gas –
liquid reactor (R2 in Figure 6), the reaction is
conducted in a vapor-phase reactor on a hetero-
geneous catalyst; this is the main difference from
the Dow process. Lummus announced that there
is no formation of tars or nonvolatile residues.
This is probably due to the fact that phenol is
rapidly removed from the reaction zone. It is
Phenol 511
believed that the residues in the gas – liquid
process are derived from phenol. As there is no
need for tar treatment and incineration Lummus
claims that the fixed investment is significantly
lower for their process [53]. However, the pro-
cess has not yet been commercialized.
4.3. Phenol from Coal
The recovery of ‘‘natural’’ phenol from coal is the
oldest commercial process for producing phenol
and it is still practiced. Nowadays, this process is
only of little importance as a source of phenol.
Phenol, as well as many other aromatic com-
pounds, is recovered from the vapors of coal
carbonization (Fig. 7). Coal is heated to above
900  C with the exclusion of air in a coke oven.
Condensable hydrocarbons and gases are removed
as vapors leaving coke as the solid residue. The
vapors are condensed to form coal tar. The gas may
be washed with aqueous sulfuric acid or phospho-
ric acid to recover ammonia. It can also be washed
with a wash oil to further remove benzene. The
remaining gas, which consists of hydrogen and
methane, is used as a fuel on site [55].
The fractionation of coal tar is described in
detail in [56] (see also ! Tar and Pitch, Section
3.4.4.). The simplied process diagram shown Fig-
ure 7 is based on information about the R€utgers
Process given in [57]. The coal tar is further
processed by continuous distillation. In a first
column C1 light oil, which contains benzene,
toluene, and xylenes, is separated together with
water. In the second column C2 carbolic oil, con-
taining phenol and phenolic compounds, is taken as
the overhead and naphthalene oil as a side cut. The
bottom product from C2 is further fractionated in
columns C4 – C6 to give wash oil for benzene
recovery from the off-gas, methylnaphthalene oil,
anthracene oil, and pitch. Plate columns or columns
with random packings are used with high reflux
ratios and a high degree of thermal integration.
The carbolic oil, which constitutes ca. 2 – 3 %
of the coal tar, contains about 30 – 35% of
phenolic compounds such as phenol and cresols.
Other components are non-phenolic benzene
derivatives and pyridine bases. The carbolic oil
is treated with 8 – 9 % caustic soda in extraction
unit E1. Phenol and cresols, which are known as
tar acids, are extracted as salts into the aqueous
phase, which is called phenolate lye. The organic
512 Phenol
Figure 7. Production of phenol from coal
R1 coke oven; C1 light oil/water column; C2 carbolic oil column; C3 naphthalene oil column; C4 anthracene oil column; E1
extraction unit; C5 hydrocarbon removal column; C6 precipitation column; C7 fractionation column
phase is further treated to recover naphthalene by
crystallization. The crude phenolate lye is treated
by steam distillation in column C5 to separate
residual hydrocarbons and pyridine bases. The
phenolate lye is then treated with carbon dioxide
to liberate the acid tars from their salts in column
C6. The aqueous phase containing sodium car-
bonate is further treated to remove dissolved
phenol. The organic phase is fractionated into
pure phenol (bp 181.8  C), o-cresole (bp
191.0  C), a mixture of m- and p-cresoles (bp
202.0 – 203.0  C), and a xylenol fraction (bp up
to 210  C) by batch distillation.
4.4. Other Processes
4.4.1. Sulfonation of Benzene
The production of phenol via sulfonation of
benzene is the oldest process to produce synthetic
phenol. It is based on research by WURTZ and
KEKULE in 1867, who found that heating sodium
benzenesulfonate in molten sodium hydroxide
gives sodium phenolate:
Sodium benzenesulfonate is produced by reac-
tion of benzene with concentrated sulfuric acid to
Vol. 26
give benzenesulfonic acid and subsequent neutral-
ization with sodium sulfite or sodium carbonate.
Phenol is liberated from the sodium phenolate by
treating the aqueous solution with carbon dioxide.
Phenol is no longer produced by this process,
details of which can be found in [50, 51, 58].
4.4.2. Chlorination of Benzene
Alkaline Hydrolysis. DURANT and BARDY
discovered in 1872 that the treatment of chloro-
benzene with aqueous caustic soda affords sodi-
um phenolate and sodium chloride.
Chlorobenzene is produced from benzene and
chlorine. Typically the process was combined
with chlor-alkali electrolysis to recover chlorine
from the sodium chloride.
Raschig-Hooker Process. The reaction of
chlorobenzene with steam to give phenol and
hydrochloric acid was discovered by MEYER and
BERGIUS in 1914. It was commercialized as the
Raschig – Hooker process at BASF.
Chlorobenzene is produced via oxychlorina-
tion of benzene with hydrochloric acid and oxy-
gen. Thus the hydrochloric acid is recycled and
Vol. 26
the process is therefore also called the regenera-
tive Raschig process.
Details about these processes, in which phenol
is made from the intermediate chlorobenzene, are
given in [50, 51, 58]. They are no longer used for
commercial production of phenol.
4.4.3. Direct Oxidation of Benzene
General. The direct oxidation of benzene
would be the simplest process to produce phenol.
For example, benzene can easily be oxidized by
air, but the phenol which is formed is further
oxidized much more easily than benzene. It
reacts very fast with oxygen or any other oxidiz-
ing agent in successive reactions that finally form
carbon dioxide and water. Therefore, the conver-
sion of benzene must be limited to only a few per
cent. Direct oxidation of benzene has not yet been
used for commercial production of phenol. How-
ever several attempts were made since the mid-
1990s to use nitrous oxide as the oxidzing agent
in a heterogeneous gas-phase process.
Direct Oxidation with Oxygen or Hydro-
gen Peroxide. In [58] a survey is given on the
first patents, granted in the 1920s and 1930s. For
example, benzene can be oxidized to phenol with
air in the gas phase at 600 – 800  C without any
catalyst. A commercial plant of Solvay Process
Company using this process was operated between
1940 and 1947. In [59–61] an overview is given on
the use of oxygen or hydrogen peroxide on dif-
ferent heterogeneous catalysts. With oxygen the
selectivity of phenol formation with respect to
benzene can reach more than 90 %, but only if
the benzene conversion is limited to a few per cent.
When hydrogen peroxide is used the conversion
may reach more than 30 % with a selectivity of
more than 95 %. Titanium silicalites (TS-1) are
typically used as a catalysts for this. However,
because of the high price of hydrogen peroxide, it is
not economic to produce phenol in this way.
Direct Oxidation with Nitrous Oxide. The
direct oxidation of benzene with nitrous oxide
Phenol 513
N2O was mainly developed by Solutia, formerly
Monsanto, in cooperation with the Boreskov
Institute of Catalysis in Russia [62].
N2O is a major component in the off-gas from
adipic acid production plants. Solutia produces
400 000 t/a of adipic acid from cyclohexane
[63], which is associated with the formation of
about 200 000 t/a of nitrous oxide [59]. Nitrous
oxide is a greenhouse gas and must be decom-
posed to avoid emission [64]. The use of nitrous
oxide for the direct oxidation of benzene would
therefore be ideally suited to any adipic acid
producer.
The oxidation is carried out in the gas phase
with zeolites of the ZSM-5 type as the heteroge-
neous catalyst. The heat evolved is 286 kJ/mol
[61]. The reaction temperature is in the range
between 300 and 450  C at atmospheric pressure.
The reaction time is 1 – 2 s. The conversion is up
to 40 % with selectivities of benzene to phenol of
more than 95 %. The space – time yield is
0.24 – 0.64 g phenol per gram catalyst per hour.
Byproducts are carbon dioxide and water from
total oxidation, as well as higher boiling phenol
derivates such as hydroquinone. Many patents
deal with the preparation of the zeolite; a survey
is given in [61]. Coking deactivates the catalyst
after several hours. The catalyst can be regener-
ated by passing an oxygen-containing gas
through the catalyst bed at elevated temperatures
[62].
Based on the literature and patents a simplified
process flow diagram was evaluated (Fig. 8).
Reactor R2 is in operation while reactor R1 is
regenerated. Fresh and recycle benzene is evap-
orated in heat exchanger X3. After adding nitrous
oxide the gas is heated to 300  C. An adiabatic
process would limit the benzene conversion to
about 10 %. Therefore, the reactors may have
cooling devices, for example, external interbed
exchangers. The off-gas is cooled to condense
benzene, water, phenol, and higher boiling by-
products. The off-gas, consisting mainly of ni-
trogen and carbon dioxide, is purged. In the first
column C1 benzene is separated and recycled.
Phenol is taken as the overhead from the second
column C2.
514 Phenol
Figure 8. Production of phenol by direct oxidation of benzene with nitrous oxide
R1, R2 reactors; X1, X2 gas heaters; X3 benzene vaporizer; C1 benzene column; C2 phenol column
Solutia has operated a pilot plant at their site in
Pensacola, Florida, first in 1996 [62]. It is not
clear whether they used pure nitrous oxide or
nitrous oxide from adipic acid off-gas. Neverthe-
less, there may be some problems with commer-
cialization of the process. The construction of a
new plant for 136 000 t/a of phenol was delayed
to post 2002 [65].
5. Environmental Protection
Wastewater Purification. Because of its
toxicity phenol must be removed from waste-
water. Phenol is classified in the water-hazard
class 2 (hazardous to water). For example, the
wastewater from neutralization in the cumene
oxidation process contains about 1 – 2 % phe-
nol. The extraction of phenol from water with an
aromatic solvent is well known. In [66] the
performance of cumene, acetophenone, and
mesityl oxide is compared. Other suitable sol-
vents are a mixture of cumene and a-methyl-
styrene or a mixture of acetophenone and di-
methylphenylcarbinol [67]. For example, the
partition coefficient of phenol for cumene
against water is about 1.5. For effective extrac-
tion a countercurrent process is used, such as a
multistep mixer – settler system or an extrac-
tion column [68]. For nearly complete phenol
Vol. 26
removal the pH of the wastewater should be
below 7 to release all phenol from sodium
phenolate. In this way the phenol content in the
wastewater can be reduced to some 10 ppm by
weight. The remaining phenol is removed in the
subsequent biological wastewater treatment.
Other solvents used for the extraction of phenol
from wastewater are butyl acetate, methyl iso-
butyl ketone, and diisopropyl ether, which are
typically used in the recovery of phenol from
gas condensates in gas production (Phenosolvan
process ! Gas Production, 4. Handling of
Byproducts, Section 2.2.). The removal of phe-
nol from wastewater can also be carried out by
adsorption on, for example, activated carbon.
Waste-Gas Purification. According to TA
Luft phenol is classified in emissions class I
[emission must be limited to a mass stream of
0.1 kg/h or a mass concentration of 20 mg/m3
(STP)]. Phenol in gas streams can be removed by
absorption. Aqueous caustic soda is used as the
scrubbing agent. The absorption columns have
several layers of random packings to improve
mass transfer. Adsorption on activated carbon is
another possibility for removing phenol from gas
streams. Phenol, as well as other organic com-
ponents, can be completely incinerated. Com-
bustion devices for this treatment are thermal or
catalytic incinerators [69] and flares.
Vol. 26 Phenol 515

Table 2. Quality specifications for phenol

Pharmacopeia Water content % Color Content, % Nonvolatile impurities, % Solidification point,  C

USP 26/2003  0.5 99.0 – 100 0.05  39.0

Ph. Eur., 4th ed., 2002 colorless, faintly 99.0 – 100 0.05  39.0
pink, or faintly yellow
ASTM D 2439  0.1  40.6

6. Quality Specifications methods of investigation. Factory specifications

The quality specifications of the various phar-
macopeias are generally met by synthetically
produced phenol. These specifications are lim-
ited to identity tests, assays, determinations
of acidically reacting impurities, nonvolatile
impurities, color, water solubility, density,
solidification point and water content. Quality
specifications for phenol and the coproduct
acetone are listed in Tables 2 and 3, respec-
tively. The quality specifications of the various
users of phenol go beyond these criteria to
some extent. Impurities such as hydroxyace-
tone, mesityl oxide, 2-methylbenzofuran, and
other carbonyl compounds can result in dis-
coloration of downstream products in further
processing. The content of lower carboxylic
acids can increase the extent of undesired side
reactions. Metal ions can damage catalysts or
lead to discoloration of reaction products. The
concentrations of these components in phenol
must therefore be limited.
Synthetic phenol is normally colorless. Color
is determined by comparison with calibrated
color scales.
The solidification point of phenol is a sensitive
criterion for impurities. It is, however, strongly
affected by the water content (see Fig. 2). The
effect of water on this method of testing can be
excluded by the addition of gypsum or dry 4A
molecular sieves. ASTM methods (D 2439-96, D
329, D 1363, D 1686-96, etc.) are used as the
of the producer and manufacturers are also used
and are much stricter. Especially when phenol is
used for Bisphenol A production it has less than
100 ppm impurities.
7. Storage and Transportation
Large quantities of phenol are transported as
liquids in ships (with double walls) and road or
rail tank cars, all of which are equipped with
heating coils. Steel is generally used as the
container material. If the phenol is to remain
colorless for as long as possible, the walls of the
containers must be made of stainless steel. Pure
phenol is therefore stored predominantly in stain-
less steel tanks, which are insulated to avoid heat
losses. On storing liquid phenol it must be en-
sured that the temperature remains below 70  C.
The lower explosion limit for phenol – air mix-
tures is reached at a saturation temperature of
73  C, corresponding to a phenol vapor fraction
in the mixture of 1.3 vol %. At storage tempera-
tures below 70  C the tank gas volume is blan-
keted with nitrogen.
Smaller quantities of phenol are transported in
steel drums. If the phenol contains water, steel
drums are not suitable because of the coloration
of the phenol which occurs. In this case drums of
galvanized sheet metal are necessary.
For phenol the following transport regulations
are in force:

Table 3. Quality specifications for acetone

Pharmacopeia Water content, % Density Content, % Nonvolatile Free acid Permanganate

impurities (as acetic acid), % test, t/min

USP 26/2003 0.789  99.0  50 mg/kg 15

Ph. Eur. 4th ed., 2002  0.38 0.790 – 0.793  50 mg/kg 120
ASTM D 329  0.5 0.7910 – 0.793  99.5 5 mg/100 mL 0.002 30
DIN 53247  0.3 0.7900 – 0.792  99.5 1 mg/100 mL
BS 509/1987  0.3 0.7890 – 0.791  99.5 5 mg/100 mL 0.002 180
516 Phenol Vol. 26

and the forecast for 2007 and 2010 [70]. As the

Land transportation ADR/RID (cross-border/inland)
automotive industry is an important consumer of
ADR/RID Class 6.1 (T1)
toxic substances phenol derivatives such as polycarbonates and
UN No. 2312 phenolic resins, the entire phenol demand still
Packaging group II tends to be cyclical and closely tied to this market.
Inland waterway transportation ADN/ADNR
The dominant synthetic route is cumene oxi-
ADN/ADNR Class 6.1
UN No. 2312 dation, which accounts for about 95 % of the total
Packaging group II phenol production. This process will maintain its
Sea transportation IMDG/GGVSee leading position as long as a market exists for the
IMDG/GGVSee Class 6.1
coproduct acetone. Production from toluene oxi-
UN-Number 2312
Packaging group II dation and from coal each amount to about
EMS No. 6.1–02 300 000 t/a. Toluene oxidation is only economi-
cal at a low toluene price relative to that of
benzene. The latest plant based on this technolo-
gy was built in 1991 in Japan. This indicates that
8. Uses and Economic Aspects
the economics of the toluene oxidation process
are not competitive with the cumene oxidation
In 2003 about 7.3
106 t of phenol was pro-
process. As long as coal tar is used as the natural
duced. The total production capacity worldwide is
source for aromatics phenol will be recovered in
more than 9
106 t. Around 37 % of global
this way, too. The classic synthetic routes such as
output, is used for the production of bisphenol A
sulfonation or chlorination of benzene are no
[70] ! Phenol Derivatives, Chap. 4.. Bisphenol
longer used because of the formation of consid-
A is especially used for the production of high-
erable quantities of sodium salts as byproducts.
grade polycarbonates for compact discs, for glaz-
Commercial production of phenol by direct oxi-
ing, and for the automotive industry. Bisphenol A
dation of benzene with byproduct nitrous oxide
is also used for the production of epoxy resins.
does not seem to be viable in the near future.
The second largest consumption of phenol is for
the production of phenolic resins with formalde-
hyde. They are mainly used for underseal appli- 9. Toxicology and Occupational
cations in the automotive industry. Phenol is also
used for the production of caprolactam via cyclo-
Health
hexanol – cyclohexanone ! Cyclohexanol and
Phenol occurs as a metabolic product of animals
Cyclohexanone, Section 3.1.. Many other deriva-
and humans in the blood, urine, and feces in free
tives of phenol are produced ! Phenol Deriva-
form as well as in conjugated form as a glucuro-
tives, such as aniline, alkylphenols, diphenols,
nide and sulfate. Excretion via urine is the main
and salicylic acid. Table 4 shows the distribution
elimination pathway of phenol metabolites. An
of phenol capacity and demand in 2000 and 2003
estimated 100 000 t/a of phenol (metabolites)
are released worldwide in human excrement
Table 4. Worldwide production capacity and demand for phenol (in [71].
1000 t/a) Phenol is harmless in small quantities accord-
ing to present knowledge. Because of its germi-
2000 2003 2007 2010
cidal effect phenol was long used in the 1800s
Production capacity from as a very effective disinfectant (carbolic acid,
Cumene 7641 8490 9879 10079
Toluene 307 307 307 307
Lister spray). However, because of its protein-
Coal tar 291 291 291 291 degenerating effect, it often had a severely
Total 8239 9088 10477 10677 corrosive action on the skin and mucous mem-
Demand for branes. Today phenol has only limited use in
Bisphenol A 2306 2678 3446 3864
Phenolic resins 2236 2419 2564 2709
pharmaceuticals because of its toxicity.
Caprolactam 739 705 724 728
Others 1335 1454 1576 1686 Toxicology. Phenol is toxic in high concen-
Total 6616 7256 8309 8987 trations. It can be absorbed through the skin, by
*
Forecast. inhalation, and by swallowing. The typical main
Vol. 26
absorption route is the skin, through which phe-
nol is absorbed relatively quickly, simultaneous-
ly causing caustic burns on the affected area of
skin. Besides the corrosive effect, phenol can
also cause sensitization of the skin in some cases.
Resorptive poisoning by larger quantities of phe-
nol, which is possible even over small affected
areas of skin, rapidly leads to paralysis of the
CNS with collapse and a severe drop in body
temperature. Skin that is wetted with phenol or
phenolic solutions must therefore be decontami-
nated immediately. After removal of contami-
nated clothing, polyglycols (e.g., lutrol) are par-
ticularly suitable for washing the skin.
On skin contamination local anesthesia sets in
after an initial painful irritation of the affected
area of skin. Hereby the danger exists that possi-
ble resorptive poisoning is underestimated. If
phenol penetrates deep into the tissue, this can
lead to phenol gangrene through damage to
vessels. The effect of phenol on the CNS, name-
ly, sudden collapse and loss of consciousness, is
the same for humans and animals. In animals a
state of cramp precedes these symptoms because
of the effect phenol has on motor activity con-
trolled by the CNS.
Caustic burns on the cornea heal with scarred
defects. Possible results of inhalation of phenol
vapor or mist are dyspnea, coughing, cyanosis,
and lung edema. Swallowing phenol can lead to
caustic burns inn the mouth and esophagus and
stomach pains. Severe, though not fatal, phenol
poisoning can damage inner organs, that is,
kidneys, liver, spleen, lungs, and heart. In addi-
tion, neuropsychiatric disturbances have been
described after survival of acute phenol poison-
ing. Most of the phenol absorbed by the body is
excreted in urine as phenol and/or its metabolites.
Only smaller quantities are excreted with the
feces or exhaled [72].
Acute Toxicity. Signs and symtoms of acute
toxicity for animals and humans are similar
independent of the route of administration. Ab-
sorption is rapid. Phenol can produce symtoms of
toxicity within minutes. In animals the LD50 was
determined for different species and forms of
administration. For oral administration the fol-
lowing values are reported: mouse 500 mg/kg;
dog 500 mg/kg; rabbit 420 mg/kg [73]. Concen-
trations of 200 and 20 ppm phenol in aqueous
solution were administered to rats. The LD50
Phenol 517
values determined were 340 and 620 mg/kg re-
spectively [74]. In the summary and evaluation of
data on the lethal dose for humans, a value of
140 mg/kg was reported as the minimum lethal
oral dose [75].
Subacute to Chronic Toxicity. Repeated
administration of phenol leads to neurotoxic,
immunotoxic, nephrotoxic, and hepatotoxic
effects, as well as changes in hematological
parameters [72].
Carcinogenicity. The published reports on
the carcinogenic and cocarcinogenic investiga-
tions give ambiguous indications [72]. Accord-
ing to EU criteria on carcinogenic potential, there
is neither need for classification and labeling nor
for further investigations.
Mutagenic Effects and Reproductive
Toxicity. According to TRGS 905 (the German
technical regulations for handling hazardous sub-
stances, 10/2002) phenol is classified as a class
3 mutagen. The discussion whether phenol should
be classified as a mutagen or not is still on-going.
Occupational Health. The following limit-
ing values (8 h time-weighed average) were laid
down for work protection (2003):
FI, ES, UK 20 mg/m3
D, B, F, CH 19 mg/m3
USA (NIOSH/OSHA AGGH): 19 mg/m3
NL 8 mg/m3
AU, IR, IT 7.8 mg/m3
S, DK, NO 4 mg/m3
Short-term exposure levels:
FI, UK 38 mg/m3
D, CH 19 mg/m3
S 8 mg/m3
Phenol exposure can be determined from the
phenol concentration in urine. The permitted
BAT value is 300 mg/L.
Classification According to the EU Direc-
tives/Ordinance on Hazardous Materials.
Phenol is classified with the hazard symbols T
(toxic) and C (caustic) and must be labeled with
the R phrases R24/25 (toxic in contact with skin
518 Phenol
and if swallowed) and R 34 (causes burns). Phe-
nol-containing formulations require the following
labeling, depending on the concentration c:
5% < c T, R24/25–34
1 < c < 5% Xn, R21/22–36/38
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Further Reading
L. Pilato (ed.): Phenolic Resins: A Century of Progress,
Springer, Berlin 2010.
Z. Rappoport (ed.): The Chemistry of Phenols, Wiley,
Hoboken, NJ 2003.
G. Sartori, R. Maggi: Advances in Friedel-Crafts Acylation
Reactions, CRC Press, Boca Raton, FL 2010.
J. Wallace: Phenol, ‘‘Kirk Othmer Encyclopedia of Chemical
Technology’’, 5th edition, vol. 18, p. 747–756, John Wiley
& Sons, Hoboken, NJ, 2006, online DOI: 10.1002/
0471238961.1608051423011212.a01.pub2.