Fenol

Applied Catalysis A: General 280 (2005) 89–103
www.elsevier.com/locate/apcata

Industrial catalytic processes—phenol 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
processeshave 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 keyintermediate 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 thephenol market has been examined in
great detail with much discussion regarding product usage,
emerging markets, and process economics over the past
10–20 years [1]. With more than 90% of the world’s 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 forinnovations 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-mailaddress: 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 shiftingeconomic
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. Cumeneprocesses 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 2–4% per year from 1970 [4,5] to2003. 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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R.J. Schmidt / Applied Catalysis A: General 280 (2005) 89–103

remaining units consist of the fixed-bed, kieselguhrsupported phosphoric acid (SPA) catalyst process developed
by UOP and the homogeneous AlCl3 and...