Applied Catalysis A: General 280 (2005) 89103

www.elsevier.com/locate/apcata

Industrial catalytic processesphenol production

Robert J. Schmidt*
UOP LLC, 25E Algonquin Rd., Des Plaines, IL 60017-5017, USA
Available online 19 October 2004

Abstract
Significant improvements in the technology for the production of phenol have been made over the past decade. New catalysts and
processes have been commercialized for the production of cumene via alkylation of benzene with propylene. Recent process design
innovations have been commercialized for the cumene hydroperoxide route that remains the process of choice for the production of phenol.
All of this effort has been directed at improving yield, process economics/costs, and process safety for the preparation of phenol as a key
intermediate for the growing bis-phenol A and phenolic resins markets. A review of technology offerings by major licensors of these new
processes is provided as well as a discussion of key process differences and recent advances.
Published by Elsevier B.V.
Keywords: Alkylation; Benzene; Propylene; Cumene; Zeolites; Phenol; Cumene hydroperoxide; a-Methylstyrene

1. Introduction
The history of the phenol market has been examined in
great detail with much discussion regarding product usage,
emerging markets, and process economics over the past
1020 years [1]. With more than 90% of the worlds phenol
production technology currently based on the cumene
hydroperoxide route, it is the focus of this article to review
the latest technology improvements made over the past 10
years for innovations in cumene/phenol processing.
Current state-of-the-art processes for the production of
cumene as a feedstock for phenol involve technology
offerings from UOP, Badger Licensing (formerly ExxonMobil and the Washington Group) and CDTech based on
zeolitic catalysis. For cumene hydroperoxide processing to
phenol technology, offerings by UOP/Sunoco (formerly
Allied-UOP technology), GE/Lummus, and KBR (Kellogg-Brown&Root formerly BP-Hercules technology)
represent the state-of the-art based on the autocatalytic
cumene oxidation and dilute acid cleavage (cumene
hydroperoxide decomposition) processing routes. Much
of the improvement in these technologies falls along the
lines of improved yield and stability for the zeolitic
* Tel.: +1 847 391 2402; fax: +1 847 391 3736.
E-mail address: robert.schmidt@uop.com.
0926-860X/$ see front matter. Published by Elsevier B.V.
doi:10.1016/j.apcata.2004.08.030

cumene technologies and improved yield, safety, and

economy for the phenol technologies. A brief discussion
regarding alternative methods of phenol production such as
the toluene oxidation route and direct oxidation of benzene
to phenol is also presented as shifting economic
considerations in the future may make these processes
more attractive.

2. Cumene production
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. Cumene
processes were originally developed between 1939 and 1945
to meet the demand for high octane aviation gasoline during
World War II [2,3]. In 1989, about 95% of cumene demand
was used as an intermediate for the production of phenol and
acetone. A small percentage is used for the production of amethylstyrene. The demand for cumene has risen at an
average rate of 24% per year from 1970 [4,5] to 2003. This
trend is expected to continue through at least 2010.
Currently, almost all cumene is produced commercially
by using zeolite-based processes. A limited number of

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remaining units consist of the fixed-bed, kieselguhrsupported phosphoric acid (SPA) catalyst process developed
by UOP and the homogeneous AlCl3 and hydrogen chloride
catalyst system developed by Monsanto. Two new processes
using zeolite-based catalyst systems were developed in the
late 1980s. These included Unocals technology based on a
conventional fixed-bed system and CR&Ls catalytic
distillation system based on an extension of the CR&L
MTBE technology [69].
2.1. SPA catalyst
Although SPA remains a viable catalyst for cumene
synthesis, it has several important limitations:
(1) cumene yield is limited to about 95% because of the
oligomerization of propylene and the formation of
heavy alkylate by-products;
(2) the process requires a relatively high benzene/propylene
(B/P) molar feed ratio on the order of 7/1 to maintain
such a cumene yield; and
(3) the catalyst is not regenerable and must be disposed of at
the end of each short catalyst cycle.
Also, in recent years, producers have been given increasing incentives for better cumene product quality to improve the quality of the phenol, acetone, and especially amethylstyrene (e.g., cumene requires a low butylbenzene
content) produced from the downstream phenol units.
For the UOP SPA process, propylene feed, fresh benzene
feed, and recycle benzene are charged upflow to a fixed-bed
reactor, which operates at 34 MPa (400600 psig) and at
200260 8C. The SPA catalyst provides an essentially
complete conversion of propylene on a one-pass basis. A
typical reactor effluent yield contains 94.8 wt.% cumene and
3.1 wt.% diisopropylbenzene (DIPB). The remaining 2.1%
is primarily heavy aromatics. This high yield of cumene is
achieved without transalkylation of DIPB and is unique to
the SPA catalyst process.
The cumene product is 99.9 wt.% pure, and the heavy
aromatics, which have a research octane number (RON) of
109, can either be used as high octane gasoline-blending
components or combined with additional benzene and sent
to a transalkylation section of the plant where DIPB is
converted to cumene. The overall yields of cumene for this
process are typically 9798 wt.% with transalkylation and
9496 wt.% without transalkylation.
2.2. AlCl3 and hydrogen chloride catalyst
Historically, AlCl3 processes have been used more
extensively for the production of ethylbenzene than for
the production of cumene. In 1976, Monsanto developed an
improved cumene process that uses an AlCl3 catalyst, and by
the mid-1980s, the technology had been successfully
commercialized. The overall yields of cumene for this

process can be as high as 99 wt.% based on benzene and

98 wt.% based on propylene [10]. Detailed process flow
information is widely published in the literature for this
technology [11]. Dry benzene, fresh and recycle, and
propylene are mixed in the alkylation reaction zone with the
AlCl3 and hydrogen chloride catalyst at a temperature of less
than 135 8C and a pressure of less than 0.4 MPa (50 psig)
[11]. The effluent from the alkylation zone is combined with
recycle polyisopropylbenzene and fed to the transalkylation
zone, where polyisopropylbenzenes are transalkylated to
cumene. The strongly acidic catalyst is separated from the
organic phase by washing the reactor effluent with water and
caustic. The distillation section is designed to recover a
high-purity cumene product. The unconverted benzene and
polyisopropylbenzenes are separated and recycled to the
reaction system. Propane in the propylene feed is recovered
as liquid petroleum gas (LPG).
2.3. Zeolite catalysts
Unocal introduced a fixed-bed liquid-phase reactor
system based on a Y-type zeolite catalyst [12] in the early
1980s. The selectivity to cumene is generally between 70
and 90 wt.%. The remaining components are primarily
polyisopropylbenzenes, which are transalkylated to cumene
in a separate reaction zone to give an overall yield of cumene
of about 99 wt.%. The distillation requirements involve the
separation of propane for LPG use, the recycle of excess
benzene to the reaction zones, the separation of polyisopropylbenzene for transalkylation to cumene, and the
production of a purified cumene product.
With the introduction of zeolites, UOP began searching
for a new cumene catalyst that would overcome the
limitations of SPA. UOPs objective was to develop a
regenerable catalyst that would increase the yield of cumene
and lower the cost of production. More that 100 different
catalyst materials were screened, including mordenites,
MFIs, Y-zeolites, amorphous silicaaluminas, and b-zeolite.
The most promising materials were modified to improve
their selectivity and then subjected to more rigorous testing.
By 1992, UOP had selected the most promising catalyst,
based on b-zeolite, for cumene production and then began to
optimize the process design around this new catalyst. The
result of this work is the UOP Q-MaxTM process and the QZ2000TM/QZ-2001TM catalyst systems.
The Q-MaxTM process flow scheme is shown in Fig. 1.
The alkylation reactor is divided into four catalyst beds
contained in a single reactor shell. The fresh benzene feed is
routed through the upper-mid section of the depropanizer
column to remove excess water and then sent to the
alkylation reactor via a sidedraw. The recycle benzene to the
alkylation and transalkylation reactors is a sidedraw from the
benzene column. This mixture of fresh and recycle benzene
is charged downflow through the alkylation reactor. The
fresh propylene feed is split between the catalyst beds and is
completely consumed in each bed. An excess of benzene is

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Fig. 1. Q-MaxTM process flow diagram.

used to avoid polyalkylation and to help minimize olefin

oligomerization. Because the reaction is exothermic, the
temperature rise in the alkylation reactor is controlled by
recycling a portion of the reactor effluent to the reactor inlet
to act as a heat sink. In addition, the inlet temperature of each
downstream bed is reduced to the same temperature as the
first bed inlet by injecting a portion of cooled reactor effluent
between beds.
Effluent from the alkylation reactor flows to the
depropanizer column which removes the propane that
entered with the propylene feed along with excess water.
The bottoms stream of the depropanizer column goes to the
benzene column where excess benzene is collected overhead
and recycled. The benzene column bottoms stream goes to
the cumene column where the cumene product is recovered
overhead. The cumene column bottoms stream, predominantly diisopropylbenzene (DIPB), goes to the DIPB
column. If the propylene feed contains excessive butylenes,
or if the benzene feed contains excessive toluene,
butylbenzenes and/or cymenes are distilled out and purged
from the overhead section of the DIPB column. The DIPB
stream leaves the column by way of the sidecut and is
recycled to the transalkylation reactor. The DIPB column
bottoms consist of heavy aromatic by-products, which are
normally blended into fuel oil. Steam or hot oil provides the
heat for the product fractionation section.
The recycle DIPB from the overhead of the DIPB column
combines with a portion of the recycle benzene and is
charged downflow through the transalkylation reactor. In the
transalkylation reactor, DIPB and benzene are converted to
additional cumene. The effluent from the transalkylation
reactor is then sent to the benzene column.
The new QZ-2001 catalyst is utilized in the alkylation
reactor while the original QZ-2000 catalyst remains in the
transalkylation reactor. Expected catalyst cycle length is 24
years, and the catalyst should last for at least three cycles
with proper care. At the end of each cycle, the catalyst is
typically regenerated ex situ via a simple carbon burn by a
certified regeneration contractor. However, the unit can also
be designed for in situ regeneration. Mild operating

conditions and a corrosion-free process environment permit

the use of carbon-steel construction and conventional
process equipment.
An alternative zeolite process was developed by CR&L
and is based on the concept of catalytic distillation [69],
which is a combination of catalytic reaction and distillation
in a single column. The basic principle is to use the heat of
reaction directly to supply heat for fractionation. This
concept has been applied commercially for the production of
MTBE and cumene.
2.4. Current state-of-the-art cumene technology
Current processes for cumene production are similar to
ethylbenzene and consist of liquid-phase technologies
offered by UOP and Badger Licensing (ExxonMobil
technology) based on b-zeolite and MCM-22TM [13]
catalysts, respectively. Over the past decade, great progress
has been made in improving and optimizing catalyst
formulations for use in both the EB and cumene alkylation
applications. For example, the ability to synthesize b-zeolite
in a wide range of Si/Al2 ratios has given catalyst designers
the ability to tailor the zeolite into a form that optimizes
activity and selectivity. A parametric study on the effects of
Si/Al2 ratio on activity and selectivity was published by
Bellussi et al. [14]. In this work, it was found that as the
silica to alumina ratio was increased from 28 to 70, there was
a decrease in both activity and selectivity toward IPBs.
Additionally, the less active catalysts had a greater tendency
toward oligomerization and were more prone toward coking.
An analogous trend was observed for ethylene, as well.
This study parallels work performed at UOP, where,
through the use of non-conventional synthesis techniques,
samples have also been prepared with Si/Al2 ratios down to
10. Through this work it has been found that with a Si/Al2
ratio of 25, the catalyst maintains sufficient activity to
achieve polyalkylate equilibrium (e.g., diisopropylbenzene
equilibrium) and, at the same time, minimizes formation of
heavier diphenyl compounds (and hence maximizes yield) in
cumene service.

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Perhaps the most critical understanding was developed

with regard to the need to minimize the Lewis acidity of the
catalyst and at the same time maintain high Brnsted acidity.
Studies at UOP demonstrated that olefin oligomerization
was directly related to the Lewis acid function of the
catalyst. Olefin oligomerization reactions can lead to the
formation of heavy compounds (coke type precursors),
which have a negative effect on catalyst stability. Thus,
minimization of the Lewis character of the b-zeolite leads to
a catalyst with high stability. Generally, Lewis acidity in bzeolite has been attributed to the existence of nonframework aluminum atoms. The most common mechanism
for the formation of non-framework alumina is through
steam dealumination during the catalyst calcination step of
the manufacturing process. By careful control of the
temperature, time and steam levels during the manufacturing
process, it is possible to produce a catalyst that is extremely
stable at typical alkylation conditions.
From a commercial standpoint this knowledge had the
additional benefit of developing a regeneration protocol that
is extremely robust. It has been demonstrated in commercial
in situ and ex situ procedures that the b-zeolite catalyst can
be regenerated with excellent results providing complete
restoration of fresh catalyst performance. The feature of
complete regenerability is another attribute that distinguishes b-zeolite catalysts from other commercially
practiced technology, where selectivity can be lost upon
regeneration [15]. The ability to regenerate catalyst is
essential in a commercial environment to provide additional
flexibility to cope with a wide range of feedstock sources,
feedstock contaminants, and potential operational upsets.
The historical development of b-zeolite showed that
early versions of b catalyst demonstrated less than optimum
performance when compared to todays state-of-the-art
formulation. Fig. 2 is a plot of the relative stability of bzeolite as a function of the Si/Al2 ratio of the b-zeolite
structure in which the dominating influence of this
parameter is evident. UOP has learned to stabilize the
zeolitic structure through careful process and chemical
means. This has resulted in a catalyst system that is

Fig. 2. Relative stability of b-zeolite as a function of the Si/Al2 ratio.

Fig. 3. Accelerated stability testing of QZ-2000 and QZ-2001 catalyst.

extremely robust, highly regenerable, and tolerant of most

common feedstock impurities. Additional studies of bzeolite have come to similar conclusions. For example,
Enichem [16] finds that b-zeolite is the most effective
catalyst for cumene alkylation among others tested
including Y, mordenite and an isostructural synthesis of
MCM-22TM.
The principles described above also led to the development of the new generation cumene alkylation catalyst, QZ2001 [17]. In Fig. 3, results from accelerated stability testing
of QZ-2000 and QZ-2001 catalyst demonstrate the superior
stability of the latest catalyst system. The new formulation
exhibits as much as two times the stability when compared to
the older formulation. The benefit afforded by the new
catalyst can be utilized by cumene producers in several
ways. It can be taken directly through reduction of the
catalyst charge for a specific run length, or alternatively as a
convenient way to increase run length or throughput through
the cumene unit, by allowing operation at a lower B/P ratio.
Since new high activity b-zeolite catalysts such as QZ2001 catalyst are such strong acids, they can be used at lower
temperatures than SPA catalyst or competing lower activity
zeolites such as MCM-22TM [18,19]. The lower reaction
temperature reduces the rate of competing olefin oligomerization reactions which is particularly high in SPA based
processes. The result is higher selectivity to cumene and
lower production of non-aromatics that distil with cumene
(including olefins, which are analyzed as bromine index, and
saturates) as well as lower heavy by-products production.
For example, although butylbenzene is typically produced
from traces of butylene in the propylene feed, there is always
the potential for butylbenzene formation through the
oligomerization of propylene to nonene, followed by
cracking and alkylation to produce butylbenzenes and
amylbenzenes. As a result of the high activity and low
operating temperature of the b-zeolite catalyst system, the
Q-MaxTM process essentially eliminates oligomerization.

R.J. Schmidt / Applied Catalysis A: General 280 (2005) 89103

This results in almost no butylbenzene formation beyond

that from butylenes in the feed. The cumene product from a
Q-MaxTM process unit processing a butylene-free propylene
feedstock typically contains less than 15 wt. ppm butylbenzenes.
The Q-MaxTM process typically produces near equilibrium levels of cumene (between 85 and 95 mol%) and
DIPB (between 5 and 15 mol%). The DIPB is fractionated
from the cumene and reacted with recycle benzene at
optimal conditions for transalkylation to produce additional
cumene. b-Zeolite catalyst is also an extremely effective
catalyst for the transalkylation of DIPB to produce cumene.
Due to the high activity of b-zeolite, transalkylation in the
Q-MaxTM process can be accomplished at very low
temperature to achieve high conversion and minimum side
products such as heavy aromatics and additional npropylbenzene. As a result of the high activity and
selectivity properties of b-zeolite, the same catalyst (e.g.,
QZ-2000) is specified for both the alkylation and transalkylation sections of the process. With both of these reactors
working together to take full advantage of the QZ-2000
catalyst, the overall yield of cumene is increased to at least
99.7 wt.%.
The improvement in b-zeolite catalyst quality has
progressed to the point that any significant impurities in
the cumene product are governed largely by trace impurities
in the feeds. The selectivity of the catalyst typically reduces
by-products to a level resulting in production of ultra-high
cumene product purities of up to 99.97 wt.%. At this level,
the only significant by-product is n-propylbenzene with the
catalyst producing essentially no ethylbenzene, butylbenzene, or cymene beyond precursors in the feed.

3. Phenol production
The phenol market now expands over three centuries with
many production technologies and products uses having
been developed over time. The 19th century phenol was
derived mainly from coal tar and used in the production of
products such as disinfectants and salicylic acid. In the early
20th century, phenol was produced primarily using benzene
chlorination and sulfonation technologies to support the
growing phenolic resin industry after World War I. From the
mid-1940s through mid-1960s, development of the cumene
peroxidation process began taking hold such that by about
1990, more than 90% of the worlds phenol demand was
being satisfied by the cumene route. Refinement of the
process over the past decade has been driven by several
market forces namely: the growing bis-phenol A market,
driven by the electronics and automotive industries demand
for epoxy and polycarbonate resins and the growing
phenolic resin market, driven by housing and furniture
industries for composite wood resins.
Also, because competition in these areas for product
differentiation and price has become so keen, phenol

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technology suppliers have been driven to improve production yield, process safety and phenol/acetone product quality
to remain competitive. Three main competitors in the area of
phenol production via cumene peroxidation include Sunoco/
UOP, KBR and GE/Lummus. Perceived benefits of these
technologies are highlighted below along with more details
presented in the section-by-section comparison that follows.
3.1. Cumene peroxidation route to phenol production
The Sunoco/UOP Phenol process produces high-purity
phenol and acetone by the cumene peroxidation route, using
oxygen from air. This process features low-pressure
oxidation for improved yield and safety, advanced CHP
cleavage for high product selectivity, an innovative direct
product neutralization process that minimizes product
waste, and an improved, low cost product recovery scheme.
The result is a very low cumene feed consumption ratio of
1.31 wt. cumene/wt. phenol that is achieved without acetone
recycle and without tar cracking. The process also produces
an ultra-high product quality at relatively low capital and
operating costs. Extensive commercial experience has
helped to validate these claims.
The KBR 4th Generation Phenol process [20] also claims
improvements for the cumene peroxidation route for a
process based on high-pressure oxidation technology. These
include improved oxidation yield, an advanced cleavage
system, elimination of tar cracking, and an efficient energy
and waste management system.
Finally, GE/Lummus also claims various improvements
to the cumene peroxidation process [21]. It is similar to KBR
in that it is also based on high-pressure oxidation technology.
Improvements include enhanced oxidation reaction rates, an
advanced cleavage section using a co-catalyst, elimination
of tar cracking, and an improved product recovery scheme.
These improvements are discussed for each of the key
major sections of the process.
3.2. Overall process description/chemistry
The main reactions for phenol and acetone production via
cumene peroxidation are shown in Fig. 4.
Both reactions are highly exothermic. Oxidation of
cumene to cumene hydroperoxide (CHP) proceeds via a
free-radical mechanism that is essentially auto-catalyzed by
CHP. The decomposition reaction is catalyzed by strong
mineral acid and is highly selective to phenol and acetone. In
practice, the many side reactions which take place
simultaneously with the above reactions are minimized by
optimization of process conditions. Dimethylphenylcarbinol
is the main oxidation by-product, and the DMPC/AMS
reactions play a significant role in the plant as shown
in Fig. 5.
The block flow diagram (Fig. 6) using the Sunoco/UOP
Phenol process as an example shows the major processing
steps required to manufacture phenol.

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R.J. Schmidt / Applied Catalysis A: General 280 (2005) 89103

Fig. 4. Main reactions for phenol and acetone production via cumene.

Fig. 5. DMPC/AMS reactions.

The major processing steps include: (1) liquid-phase

oxidation of cumene to cumene hydroperoxide [CHP], (2)
concentration of CHP, (3) acid-catalyzed decomposition of
concentrated CHP to phenol and acetone, (4) neutralization
of acidic decomposition product, (5) fractionation of the
neutralized decomposition product for recovery of acetone,

phenol, AMS, and residue, (6) recovery of phenol and the

effluent wastewater via an extraction process to prepare it for
further downstream treatment required to meet effluent
quality specifications, and (7) hydrogenation of AMS back
to cumene for recycling to synthesis; or, optionally, refining
of AMS for sale as a product.

Fig. 6. Sunoco/UOP Phenol process.

R.J. Schmidt / Applied Catalysis A: General 280 (2005) 89103

The details of each of these main processing steps are

discussed as follows highlighting recent technological
advances made by various licensors of phenol technology.

4. Process flow and recent technology advances

4.1. Oxidation section process flow
Using the Sunoco/UOP process as an example, Fig. 7
shows a typical series flow two-oxidation reactor configuration for the low-pressure technology. As many as 56
reactors or more reactors can be used in multiple reaction
trains depending on the capacity of the unit, location,
processing objectives, and to stage the investment over time
as capacity increases are needed.
The fresh cumene feed is pumped from the oxidation day
tank to the combined feed surge drum. Recycle cumene
streams from other sections of the plant are combined and
flow through the feed pre-wash column, where organic acids
are removed by scrubbing with weak caustic and water. The
recycle cumene then joins with the fresh cumene feed in the
combined feed surge drum. The combined feed is then
pumped to oxidizer No. 1.
Cumene is also used for various utility-like purposes
through the plant. Cumene is sent from the day tank to the
phenol recovery section on a batch basis as make-up solvent.
It is also used as pump seal flush in the various sections of the
plant.
The two oxidizers are in series with respect to liquid
flow but in parallel with respect to air flow. The oxygen
requirement for the oxidizers is supplied from atmospheric
air. The air is first filtered and then compressed before
going into the oxidizers through a sparger. The heat of
reaction in the first oxidizer is balanced by adjusting the

95

temperature of the cool cumene feed, so that no other

cooling is required.
For large phenol units, it is economical to recover the heat
of reaction from the second oxidizer by heat integration with
the concentration section. The hot oxidizer circulating liquid
stream is used to supply heating to the pre-flash column
upper vaporizer. The net oxidate from oxidizer No. 2
(effluent from oxidation section) flows directly to the
concentration section.
As shown in the flow diagram (Fig. 8) again for the Sunoco/
UOP process, the spent air streams from both oxidizers are
combined and routed through a water-cooled condenser, a
chilled condenser and an entrainment separator for the
maximum removal of hydrocarbon and cumene. From the
entrainment separator, the air flows to the charcoal absorbers.
Two of the adsorbers are always on line in series flow, while
the third one is being regenerated with steam. The cleaned air
from the charcoal absorbers is vented to safe atmospheric
disposal. A catalytic incinerator is usually not needed to meet
emission limits, but one can be provided if regulations
stipulate incineration as the emission control method. The
cumene collected by the charcoal adsorbers is recovered by
desorption with low-pressure steam followed by condensing
the steam and decanting the cumene and water phases. The
cumene is then recycled to the feed pre-wash column.
4.1.1. Recent advances in oxidation section technology
For the Sunoco/UOP technology, recent improvements to
the oxidation section include: (1) the use of high-efficiency
charcoal adsorption to recover trace products from spent air,
(2) use of an emergency water spray installation and
elimination of oxidizer rupture disks, (3) a reduction in
oxygen content of vent gas thus reducing air compressor
capacity, (4) the elimination of the requirement for caustic
scrubbing of fresh feed from zeolitic cumene unit, (5) use of

Fig. 7. Sunoco/UOP Phenol process: oxidation section.

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R.J. Schmidt / Applied Catalysis A: General 280 (2005) 89103

Fig. 8. Sunoco/UOP Phenol process: cumene recovery.

a dilute caustic wash tower that replaces the feed wash

mixer/settler system, (6) the integration of the decanter with
the concentration section vacuum system and elimination of
the vent gas scrubber, (7) the integration of the feed
coalescer into the combined feed surge drum and (8) the use
of common spares for oxidizer pumps and emergency
coolers. All of these improvements serve to reduce capital
and operating costs of the process making it one of the most
effective phenol processes available.
GE/Lummus claims an improved flowscheme to clean up
acids and other activity depressing components present in
the recycle cumene stream. This results in enhanced cumene
oxidation rates for their high-pressure oxidation technology.
However, the process is more likely to have higher yields of
these components as a result of the higher operating
pressure. This requires greater measures to ensure adequate
clean up compared to a more modern low-pressure system
that provides higher oxidation yields. Also, the highpressure system is more complex and costly and requires
higher air compression costs. With either low-pressure or
high-pressure oxidation, the oxidation air strips light acids
out of the oxidation products. With Sunoco/UOP lowpressure oxidation, the air stripping combined with
partitioning of the acids to the condensate in the spent air
cumene recovery system and the weak-caustic scrubbing of
the recycle cumene is so effective that no other method of
acid removal is required. This does not appear to be the case
for GE/Lummus high-pressure oxidation.
KBR employs a similar high-pressure oxidation
technology for the manufacture of phenol. KBR claim
to have eliminated the sodium carbonate scrubbing system
completely thereby reducing capital and operating costs.
The aqueous effluent rate for the oxidation section is
also said to be reduced by as much as 75% resulting in
off-site treating savings. However, similar to GE/Lummus,

higher reactor/compressor section costs and lower yields

are likely to more than offset these gains compared to
low-pressure technology. More recent KBR designs have
been trending toward lower pressure, dry, and externally
cooled oxidation making the process look very similar to
the original UOP CumoxTM process developed in the
1970s.
4.2. Concentration section process flow
An example of the typical flow for the concentration
section of the process where CHP in the oxidizer reactor
effluent is concentrated to a level of 7585 wt.% prior to
decomposition to phenol and acetone is shown for the
Sunoco/UOP process in Fig. 9.
The oxidate from the last oxidizer flows to the
concentration section to recover unreacted cumene. For
large phenol units, it is economical to use a two-column
concentration system, in which the heat of reaction from
oxidizer No. 2 and very low-pressure steam are used to
vaporize cumene in the first (pre-flash) column, reducing
the size of the main flash column. The pre-flash drum and
flash column operate under vacuum to minimize the
temperature necessary to concentrate the CHP. The
vacuum is typically generated by an ejector system. Under
vacuum in the pre-flash drum, cumene vaporizes in the
upper vaporizer using heat from the second oxidizer cooler.
Additional cumene vaporizes in the lower vaporizer with
heat supplied by very low-pressure steam. Final CHP
concentration is achieved in the flash column vaporizer and
flash column, both of which operate under deeper vacuum
than the pre-flash drum. The pre-flash drum bottoms
stream flows through the flash column vaporizer, where
additional cumene vaporizes using heat from low-pressure
steam.

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Fig. 9. Sunoco/UOP Phenol process: concentration section.

The CHP content of the flash column overheads is

minimized by rectification in the flash column, using either
screen trays or packing, whichever is more economical. The
flash column overheads, consisting of primarily cumene, is
recycled to the oxidation section via the feed pre-wash
column. The concentrated CHP collects in the integral
receiver/cooler at the bottom of the flash column, where it is
cooled to a safe temperature. The CHP concentrate from the
flash column bottoms reservoir is then pumped to the
decomposition section.
A cumene quench tank is also provided in this section for
automatic emergency quenching of various strategic
sections of the concentration section if necessary to maintain
safe operating temperatures in the event of an incipient CHP
decomposition excursion.
4.2.1. Recent advances in concentration section
technology
For the Sunoco/UOP process, recent improvements
include: (1) heat integration with oxidation section, (2) a
two-stage concentration section consisting of pre-flash and
flash column, (3) elimination of overhead receivers, (4) use
of a Packinox style exchanger in the flash column condenser,
and (5) use of power traps instead of level-controlled
pumped condensate pots. All of these improvements are
claimed to reduce capital costs for the process.

low temperature/higher contact time for the main CHP

decomposition step followed by a plug flow dehydration
section at higher temperature/short contact time for
conversion of dicumylperoxide (DCP) to AMS. The process
represents a breakthrough in AMS yield improvement and
with the expiration of the patent in 1999, is currently being
used by all licensors as the process of choice for modern high
yield phenol technology. An example of the most advanced
decomposer technology is the process offered by Sunoco/
UOP shown in Fig. 10. It consists of a very simple but
elegant drum and loop reactor design where concentrated
CHP from the concentration section flows into the
decomposer drum, along with a metered amount of water
to maintain optimal reaction conditions in the decomposer
recycle loop. Sulfuric acid is injected via injection pumps
into the loop to provide the catalyst required for the
decomposition of CHP to phenol and acetone. A circulation
pump is provided to circulate the content of the decomposer.
Sulfuric acid is injected into the circulating stream to such an
extent that the decomposition of CHP and dehydration of
dimethylphenylcarbinol (DMPC), a key by-product of

4.3. Decomposition section flow

The decomposition or cleavage section of the process
involves the catalytic decomposition of concentrated CHP in
the presence of ppm levels of acid to crude phenol and
acetone. The most effective technology for this section is a
unique two-step process described in U.S. Patent 4,358,618
[22] by Sifniades/Allied Corporation patented in 1982. The
process involves the use of a backmixed reactor section at

Fig. 10. Sunoco/UOP Phenol process: decomposition section.

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R.J. Schmidt / Applied Catalysis A: General 280 (2005) 89103

oxidation reaction, are precisely controlled. The level of

unreacted CHP is monitored via calorimeters, to which part
of the acid catalyst flow is routed.
The effluent from the decomposer is pumped to the
dehydrator in which the effluent is heated to a temperature
where remaining DMPC is dehydrated and DCP converted
to AMS at very high yield. This is a unique advantage of the
Sunoco/UOP decomposition technology. The Sunoco/UOP
process produces approximately 90% AMS yield from
DMPC. This also results in higher phenol yield, thus lower
cumene consumption and less residue (e.g., tar) formation.
4.3.1. Recent advances in decomposition section
technology
In addition to very high yields across the decomposer
section, the Sunoco/UOP technology offers the following
recent improvements: (1) the implementation of advanced
process control (APC), (2) a reduction in required recycle
rate from 100:1 to 25:1, (3) the elimination of water injection
tank and pumps, (4) use of acid totes to eliminate the acid
tank dependent on unit size and client preference, and (5)
design of the unit for safe containment in most probable
relief situations and elimination of the catch tank. The major
advantage of these improvements is reduced capital costs
and improved process yields and economics. AMS yields as
high as 8590% across the decomposer section have been
demonstrated making the Sunoco/UOP technology one of
the most selective offerings in the industry today.
Similarly, GE/Lummus claims improvements in the CHP
decomposition technology. The technology employs a cocatalyst CHP cleavage process using a very precise mix of
NH3 and H2SO4 to control acidity at the optimal level for
maximum yield. However, use of such a pre-neutralized acid
mix may greatly reduce reaction rate; resulting in much
higher decomposer residence times (e.g., larger reactor
volume).
The use of ammonium hydroxide between the two main
cleavage stages is covered extensively in two main cleavage
patents by Zakoshansky/GE. The first, U.S. Patent 5,254,751
[23], touts use of ammonia to adjust the acid catalyst activity
in the second stage (similar to Sunoco/UOP dehydrator
section) and results in increased AMS yield according to the
examples provided. However, in the second patent, U.S.
Patent 5,530,166 [24], the ammonium hydroxide neutralization step is moved to downstream of the last cleavage
reactor, or the same position as neutralization in the Sunoco/
UOP design. Quoting from the 5,530,166 patent/column 3
tends to refute the effectiveness of the co-catalyst system:
(4) Precise dosing of small amounts of aqueous ammonia
solutions and H2SO4 to maintain the correct ratio is difficult
and lack of precision leads to AMS dimers and formation of
phenol complexes, in case of low H2SO4 neutralization, or to
incomplete DCP conversion in case of over neutralization of
H2SO4. (5) H2SO4 and NH4HSO4 presence in cleavage
products causes the acidic catalytic properties of these
catalysts to increase by 47 times and their concentration to

increase simultaneously in vessel 8 during acetone

evaporation. Side reactions continue in this vessel and byproduct formation reduces process selectivity. The above
mentioned low dosing of NH4OH aggravates this situation
leading to a loss of 1020 kg of starting cumene feed on the
basis of 1 t of phenol and AMS yield can be reduced to as
low as 60% theoretical. (6) Operating the DCP cleavage
reactor 7 with a very weak acidic catalyst (H2SO4 +
NH4HSO4) requires a high reactor volume, 0.8 m3/t of feed
to the reactor which unfavorably compares with 0.40.5 m3/t
of feed in the process of the present invention.
These claims clearly lead one to conclude that injection
of ammonium hydroxide upstream of the last stage was
found to cause lower yield, leads to control and intrinsic
process shortcomings, and requires unnecessarily large
equipment. The net result is the GE/Lummus patent claims
only about 80% AMS yield from DMPC in the feed
compared to yields as high as 8590% in the Sunoco/UOP
technology.
KBR claims to have an improved cleavage system that is
better optimized resulting in a very high selectivity of phenol
from CHP of approximately 99.5%. The process incorporates a boiling cleavage concept in that the cleavage
reactor is cooled by vaporization of the acetone that is
recycled to the process. This is claimed to provide better
process control with less dependence on external cooling
mechanical reliability. Included in this design is a
proprietary interlock shutdown system that improves safety
in the process.
4.4. Neutralization section process flow/improvements
The acid catalyst that is added in the decomposition
section must be neutralized to prevent yield loss due to side
reactions and protect against corrosion in the fractionation
section. The Sunoco/UOP Phenol process uses a novel
approach for neutralization: the acid catalyst is neutralized
by injecting a stoichiometric amount of a diamine which
does not need to be removed from the process, as shown in
Fig. 11.

Fig. 11. Sunoco/UOP Phenol process: direct diamine neutralization.

R.J. Schmidt / Applied Catalysis A: General 280 (2005) 89103

The diamine salt is soluble through the distillation train

and leaves the unit with the residue stream. The diamine salt
does not contribute significantly (if at all) to SOx or NOx
when the residue is used as boiler fuel. The main advantages
of direct diamine neutralization over conventional systems
are: (1) a new/simplified design that is easy to operate and
reduces capital cost, (2) process uses soluble salts that
reduces reboiler fouling and lowers maintenance costs, and
(3) does not require water addition for neutralization which
in turn lowers wastewater production and reduces distillation utilities. By replacing older ion exchange resin
technology with the new direct neutralization process,
Sunoco/UOP claim that phenolic wastewater production can
be reduced by 45% or more at lower capital cost.
4.5. Acetone refining section process flow/improvements
Acetone is a major by-product of the CHP oxidation
process for the production of phenol. The overall economics
of the process are highly dependent on production of high
quality acetone (e.g., 99.799.9% purity) for sales in the
solvents market and bis-phenol A markets. Fig. 12 shows the
typical flowscheme for the Sunoco/UOP process.
Fractionation feed goes from the fractionation feed tank
to the crude acetone column. Water is injected as necessary
to the bottom of the crude acetone column to increase the
volatility of the acetone and maintain the bottom
temperature. The overhead of the column, consisting of
acetone, water and some cumene flows to the finished
acetone column (FAC).
The key impurities removed in the FAC are aldehydes,
which have been historically analyzed with the permanganate fading test, and water. More recently, as the product
quality demands for acetone have increase, most phenol
producers use gas chromatography (GC) as the definitive
method for determining aldehyde content. The Permanganate Fading test is simply not effective for aldehydes unless

Fig. 12. Sunoco/UOP Phenol process: acetone refining section.

99

the level is in the range of several hundred ppm or more.

Caustic is injected into the FAC column to catalyze the
condensation of trace aldehydes. The heavier condensation
products are less volatile and leave with the FAC bottoms.
High-purity acetone flows by gravity from the FAC side cut
near the top of the column to the acetone product day tank.
The net bottoms stream of the FAC flows to the FAC
bottoms drum where cumene and water are separated. The
water goes to the sewer while the cumene is recycled to the
oxidation section. Recent improvements for the Sunoco/
UOP process include the use of stabbed-in condensers and
elimination of overhead receivers, where appropriate, to
save capital cost.
GE/Lummus appears to use structured packing in the
FAC to reduce cost and debottleneck. Although there may be
process advantages to using high-efficiency distillation in
the FAC, such as slotted-sieve trays; it may be difficult to
justify for economic reasons alone.
4.6. Phenol fractionation and purification process flow
Once the crude phenol has been produced, it must be
further fractionated to prepare a finished product that is of
sufficient purity to meet downstream user specs. An example
of the phenol purification is shown in Fig. 13. It is based on
Sunoco/UOP technology using AMS hydrogenation as a
means of recycling the by-product AMS to maximize phenol
production.
The bottoms material from the crude acetone column
flows to the cumene/AMS column where cumene and AMS
are recovered overhead and sent to the cumene caustic wash
in the phenol recovery section. A chemical agent is injected
into the bottom half of the column for the removal of
carbonyl impurities such as acetol (a-hydroxyacetone) and
mesityl oxide from the phenol. The bottoms from the
column are routed through a chemical treatment reactor
which provides residence time for the chemical treatment
reactions.
The effluent from the chemical treatment reactor flows to
the crude phenol column where the heavy components distill
to the bottoms and then flow into the residue stripper column
for removal as the net residue by-product. This separate
residue stripper column section allows the final stripping of
phenol from the residue to be conducted at higher vacuum,
which allows both the crude phenol column and residue
stripper column to be reboiled with medium-pressure steam.
Thus, no high-pressure steam is required for the phenol
plant! The residue product has flow and combustion
properties similar to No. 6 fuel oil, and is typically charged
to a dedicated burner a boiler furnace.
The crude phenol column has a top pasteurizing section to
remove the small amount of light by-products generated
during distillation. The main product from the column is taken
off as a side cut and flows to IX resin treaters, in which the ion
exchange resin catalyzes conversion of methylbenzofurans
(MBF) and residual AMS to high-boiling components. MBF

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R.J. Schmidt / Applied Catalysis A: General 280 (2005) 89103

Fig. 13. Sunoco/UOP Phenol process: phenol purification scheme.

and AMS are otherwise difficult to remove by distillation. The

effluent from the IX resin treaters goes to the phenol rectifier,
where the heavy components along with some phenol are
distilled to the bottoms and recycled back to the crude phenol
column. The phenol rectifier also has a top pasteurizing
section for removal of small amounts of light by-products
generated during distillation. Phenol product flows by gravity
from the rectifier side cut to storage.
4.7. Recent improvements in phenol fractionation and
purification section
For the Sunoco/UOP process, improvements in the
phenol fractionation and purification section included: (1)
replacement of the azeotropic phenol stripper with chemical/
resin treating, (2) elimination of the acid neutralizer system,
and (3) use of stabbed-in condensers and elimination of
overhead receivers where appropriate. The main benefit of
these changes has been reduced capital/utilities cost while
maintaining the already very high overall phenol product

quality. Further, equipment sizes and wastewater have been

significantly reduced by implementation of the advance
Sunoco/UOP Phenol recovery technology shown in Fig. 14.
In this section there are two process tanks: a phenolic
wastewater tank containing various phenolic wastewaters
from various sections of the plant, and a sodium phenate
tank containing sodium phenate (from phenol and caustic
reaction) from other sections of the plant. This section
performs several functions: removal of phenol from the
cumene/AMS mixture prior to AMS hydrogenation or AMS
purification; recovery of phenol from sodium phenate by
springing with sulfuric acid; and recovery of phenol from
the phenolic wastewater.
Phenol would inhibit the oxidation reaction if not
removed from the cumene and AMS that will ultimately
be recycled to the oxidation section. Due to the formation of
azeotropes, removal of phenol from cumene/AMS mixture
from the column of the same name to the low levels required
is not possible via distillation. However, the phenol is readily
removed by washing with sodium hydroxide (caustic),

Fig. 14. Sunoco/UOP Phenol process: phenol recovery section.

R.J. Schmidt / Applied Catalysis A: General 280 (2005) 89103

forming sodium phenate, which is soluble in water. This

operation is conducted in the cumene caustic wash column,
which is located in the phenol recovery section. The
resulting sodium phenate flows to the sodium phenate tank.
The organic phase from the cumene caustic wash column (a
cumene/AMS mixture) flows through a sand filter to remove
any entrained caustic, and then to the AMS hydrogenation or
AMS purification section.
The phenol removed from the cumene/AMS column
overheads stream is recovered by mixing the sodium phenate
stream from the sodium phenate tank with sulfuric acid,
which converts the sodium phenate back to phenol. The
phenol then forms a separate organic phase. This operation is
commonly referred to as springing the phenol. The
mixture flows to the phenol recovery unit separator where
the sprung phenol is recovered by decanting the phenol
phase from the top of the vessel and recycling it to the
neutralization section, where it joins the decomposition
section effluent.
The aqueous phase from the phenol recovery unit
combines with phenol-containing water from the phenolic
wastewater tank and then flows to the oil extraction column
for removal of residual phenol. Cumene is used as the
extraction solvent to extract the phenol out of the water in a
counter-current extraction column. The extraction column
bottoms is one of the net wastewater streams from the phenol
unit. The cumene solvent from the top of the extraction
column is then scrubbed of phenol in a counter-current
caustic scrubbing column, similar to the cumene/AMS
caustic wash column. The resulting sodium phenate solution
then flows to the sodium phenate tank. The lean cumene is
recycled to the extraction column.
GE/Lummus use special coalescers to separate out salts.
These are located on the oxidation feed or oxidate water
wash (sodium carbonate) and phenol springer (sodium
sulfate). Sunoco/UOP does not have salts in the fractionation
feed that need separating out. However, Sunoco/UOP does
use a coalescer in the oxidation recycle cumene wash
column. With proper design of the phenol springer unit
(PRU), satisfactory performance without a coalescer can be
obtained.
GE/Lummus also claims the use of catalytic separation of
phenol impurities to help improve the net phenol product
quality. Use of a zeolitic catalyst may be possible here
although the process has yet to be demonstrated commercially and this may turn out to be an expensive means to
convert acetol into more 2-MBF. The Sunoco/UOP process
uses an IX resin catalyst that is better at controlling total
carbonyls and 2-MBF in the phenol. Sunoco/UOP claims
<515 ppm total carbonyls and <1 ppm 2-MBF in their
high-purity phenol product. This is compared to GE/
Lummus claims of <20 ppm total carbonyls and <5 ppm 2MBF, in their respective high-purity phenol product. It is
also believed that GE/Lummus are still using an older waterrefluxed based column technology for MBF removal, which
requires higher utilities and can result in corrosion problems.

101

For the KBR technology, improvements include use of

proprietary equipment designs and improved heat integration that results in very low steam consumption on the order
of 2.4 kg high-pressure steam/kg phenol. As a result of
various process improvements, KBR also claims the ability
to meet polycarbonate grade bis-phenol A phenol purity
requirement, similar to Sunoco/UOP and GE/Lummus, with
total carbonyls as low as 5 ppm.
4.8. AMS hydrogenation section flow
The Sunoco/UOP Phenol process utilizes AMS hydrogenation technology developed by Huels. The Huels
MSHPTM process is a mild hydrogenation process based
on a Pd containing catalyst system that operates at moderate
pressure. The process achieves nearly complete conversion
of AMS with very high selectivity to cumene resulting in a
very low overall process cumene/phenol consumption ratio
of 1.31 w/w. The simple process shown in Fig. 15 has been
demonstrated to operate without significant catalyst deactivation over multiple years of operation.
In this section the AMS in the cumene/AMS stream from
the phenol recovery section is selectively hydrogenated to
cumene by the Huels MSHP process. The fresh cumene/
AMS feed is mixed with reactor effluent recycle and
hydrogen. The combined feed passes through Hydrogenation Reactor No. 1, where the bulk of the AMS is
hydrogenated to cumene. The reaction is highly exothermic.
The reactor effluent recycle is cooled before joining with the
fresh feed. The net flow goes to Hydrogenation Reactor No.
2 as a finishing reactor to complete conversion of AMS to
cumene. Product from the second reactor goes through the
product cooler and then to the product separator. Hydrogen
flow is once through, with only a slight excess over
stoichiometric. The flow rate of feed hydrogen is regulated
based on the flow of excess hydrogen and light gases from
the product separator. Dissolved gases which come out of
solution when the liquid flashes to low pressure are
disengaged in the flash drum. The cumene liquid product
is then recycled to oxidation. Advances in the Sunoco/UOP/
Huels AMS hydrogenation technology include: (1) elimination of the recycle hydrogen compressor, and (2) elimination
of the hydrogen flash drum and pumps. Both of these
improvements save capital cost and utilities.

Fig. 15. Huels MSHP process: AMS hydrogenation.

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R.J. Schmidt / Applied Catalysis A: General 280 (2005) 89103

KBR also claims a simple, low cost, highly efficient

design for AMS hydrogenation. KBR also finds that catalyst
life is very long when operated under the mild conditions
required for the process.
4.8.1. Tar cracking
Both Sunoco/UOP and KBR claim that tar cracking of
heavy ends produced in the phenol process is no longer
required due to the improvement in process yield achieved
over the last 10 years. KBR claims that phenolic tars have
been reduced by as much as 40%. By eliminating tar
cracking, phenol product purity has improved so that total
organic impurities (including cresols) have been reduced to
50 ppm, according to KBR. Sunoco/UOP, with additional
refinements in cumene and phenol fractionation technology,
have further reduced this level to about 30 ppm.
GE/Lummus may still use tar cracking in certain
instances where high yield is required due to the lower
yields achieved across the synthesis section (oxidation/
decomposition) of their process. GE/Lummus claims to have
commercially demonstrated achieving a 1.31 cumene/
phenol consumption ratio at the GE Mount Vernon phenol
plant using new advanced Lummus technology, but it is
unlikely that this low consumption is achieved without some
level of tar cracking.
4.8.2. Phenol process safety
Safety considerations in the production of phenol and
acetone from cumene include design and operating criteria
for processing the intermediate CHP. CHP decomposes
rapidly to phenol and acetone when exposed to strong acids,
even at low temperatures. This reaction is highly exothermic
and is the second reaction step in the process. At high
temperatures, the rate of CHP decomposition catalyzed by
weak acids would also become significant. In addition, CHP
reacts with cumene to form dimethylphenylcarbinol. This
reaction occurs to some extent under normal conditions in
the oxidation, concentration and decomposition sections, but
the rate becomes significant at higher temperatures. At still
higher temperatures, CHP also decomposes thermally to
form acetophenone and methane. CHP decomposition
catalyzed by weak acids and the thermal CHP reactions
would only become significant from a safety standpoint in
the event that heat cannot be removed. In such a case the
increasing temperature from the heat of reaction would
result in a higher reaction rate, creating the potential for an
uncontrolled reaction.
Thus, the availability of heat exchangers, cooling
medium, and pumps for cooling CHP mixtures is critical
from a safety standpoint. A significant advantage of the
Sunoco/UOP low-pressure oxidation technology in addition
to high yields is the very mild operating temperature (e.g.,
typically 8290 8C) required for the process. The lower
oxidizer operating temperature translates into a much longer
allowable operator response time in the event intervention is
required due to an upset to prevent oxidizer temperatures

that are high enough to promote CHP thermal decomposition. The intervention response time may be as long as 24 h
or more to avoid elevated temperatures and high rates of
CHP decomposition in the oxidizers. For high-pressure
processes such as KBR and GE/Lummus, the response time
is much shorter, on the order of only a few hours, to prevent
accelerated CHP thermal decomposition due to the higher
initial process temperature (e.g., typically 95100 8C or
more).
The Sunoco-UOP Phenol process design and operating
criteria are based on an industry accepted 10,000-year
probability guideline. Safety provisions include emergency
coolers and pumps, reliable power supplies, reliable cooling
water supply, and further backup provisions including
ability to use firewater as once through cooling water, and
the capability to use cool cumene to reduce (quench)
temperature. For all cooling services designated as critical, if
cooling becomes unavailable, it must be possible to reestablish cooling within 20 h with 99.99% certainty.
Analysis has shown that meeting this availability criterion
typically requires a cooling water supply system with a
minimum of three pumps, with two normally operating and
the third in standby; and multiple independent power sources
for the pumps and cooling tower fan. For all pumping
services designated as critical, if pumping becomes
unavailable, it must be possible to re-establish pumping
within 20 h with 99.99% certainty. Meeting this criterion
typically requires multiple sources of power.
Options for multiple independent power sources can
include, but are not necessarily limited to, an emergency
electric power generator, steam-driven turbine, a direct drive
engine, or multiple independent external electric power
supplies. While the first three options are less reliable than
normal electrical power, the combination of multiple power
sources provides a more robust system than a typical single
external electrical power supply. For example, if a dieselpowered emergency electric power generator is utilized, a
probability of 97% is typical. Emergency generators are less
reliable than normal electrical power because of the
probabilities associated with failure to start, failure to
run, and unavailability due to testing and maintenance.
Quantitative risk assessment is typically performed to verify
the reliability of such systems.
4.9. Alternative routes to phenol production
Recently, renewed interest in alternative routes to phenol
production has occurred due to the potential burden of
producing by-products such as acetone. Unlike the cumene
peroxidation route, direct oxidation of benzene with nitrous
oxide or hydrogen peroxide or oxidation of toluene in a twostep process does not produce co-products such as acetone.
Historically, for the toluene-based route, a good example
is the two-step process introduced by Dow Chemical in 1961
as described by Thurman [25] where toluene is oxidized via
fee radical oxidation to benzoic acid, then further converted

R.J. Schmidt / Applied Catalysis A: General 280 (2005) 89103

via decarboxylation using a copper salt catalyst to phenol.

With the more recent advances of the cumene hydroperoxide
process over the past 1020 years, the toluene route has been
phased out to a large extent due primarily to lower yields
(e.g., lower oxidation selectivity) and higher production
costs. A number of process flow variations have been
previously published [25] describing more recent innovations in this technology, although none have succeeded in
overcoming the lower selectivity limitations.
Perhaps the best example of an advanced direct oxidation
process is the AlphoxTM process developed by Solutia based
on nitrous oxide (N2O) oxidation of benzene [26]. Phenol
selectivities as high as 97100% at 100% N2O conversion
are reported using a zeolitic catalyst. However, the process at
present requires frequent regeneration driving up capital
costs. Also, the process economics are strongly dependent
on obtaining a cheap supply of N2O. N2O is a by-product in
the production of adipic acid and is an ideal source of this
material that must otherwise be disposed of as a waste
stream by conversion first, to nitric oxide and then nitric
acid. On-purpose production of N2O as a feedstock for the
process is not, at present, economically feasible [27] and will
require further development and/or breakthrough to commercialize. Thus the application of the technology may be
severely limited to just a few sites where N2O from adipic
acid manufacture can be readily accommodated in the
downstream direct oxidation process.
Since the growth rate for acetone has not kept pace with
phenol, there is some concern that the supply of acetone will
exceed the market demand, as has already happened in some
isolated instances. However, within the past 2 years, new
uses for acetone have been developed to help keep demand
in line with production. This essentially postpones any
serious consideration of alternative direct oxidation technologies or toluene-based feedstock routes. The present
acetone by-product value contributes significantly to the
overall economics of the phenol production.

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