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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
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
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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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Fig. 4. Main reactions for phenol and acetone production via cumene.
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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
References
[1] M. Bentham, R. Schulz, Process improvements for a changing phenol
market, in: Proceedings of the DeWitt Petrochemical Review Conference, Houston, TX, March 1921, 1991.
[2] G. Stefanidakis, J.E. Gwyn, in: J.J. McKetta, W.A. Cunningham
(Eds.), Encyclopedia of Chemical Processing and Design, vol. 2,
Marcel Dekker, New York, 1977, p. 357.
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