SEEKING THE BEST ROUTE FOR

MALEIC ANHYDRIDE
ollowing several years of production upheavals associated with
an industry-wide changover from
benzene to n-butane as the primary
feedstock, all is still not quiet on the
maleic anhydride front. Recently, the
commercialization of new routes for
both the production and the recovery of
MA has challenged existing prdesses
and has led to contentious debate
among producers.
The product is made in a two-step
process. "he feedstock is catalytically
oxidized, and the resulting MA is captured and purified from the dilute reactor offgas. In both production and recovery, industry is split over the
relative merits of competing technologies -the traditional fixed-bed reactor vs. newer fluid-bed designs, and
conventional aqueous recovery vs. the
newer solvent-based route.

Ushering out the old

Today, n-butane reigns as the feedstock of choice, thanks to its lower unit
cost (roughly 8 d l b compared to 1301
Ib), and its improved environmentaland
health acceptability relative to benzene,
a known carcinogen. In the U.S.,the
conversion to butane was completed in
the late 1980s. Such a conversionis still
going on in Europe.
Enichem (Milan), Huls AG (Marl),
Akzo AG (Frankfurt), Bayer AG (Leverkusen) and Atochem (Paris) have all
closed down benzene-based production
in Europe, leaving Alusuisse Italia (Milan), Polioli (Mantova), Cray Valley (a
subsidiary of Paris-basedTotal Chimie)
and Cepsa (Madrid) as the major benzenebased producers there.
Austria's Chimie Linz (Linz) and Sisa8 (Milan) produce MA from butane.
Next month, Cepsa -Spain's only MA
producer -will complete the conversion from benzene to butane a t its Alge
ciras facility.
Because of a longer residence time
required with butane, capacity of the

Debate rages
over fixed- vs.
fluid-bed
production, and
aqueousvs.
solvent recovery

I
I
I

Cepsa plant will fall by about 20%, to

4,000 m.t./yr, says Joaquin Solis, refining technology manager. Producers
agree that such yield tradeoffs, typical
for butane, are more than offset by the
lower feedstock costs.
While most producers still depend on
the standard fixed-bed production
route, several limitations have brought
industrv's attention to the newer fluidbed deGgns. The exothermic nature of
butane conversion makes fixed-bed,
shell-and-tube reactors SusceDtible to
localized hot spots and thermk gradients during operation, which can lead

BARBARA BERASI

Since 1989, recession has dampened the demand for fiberglass-reinforced thermoset
resins, and has depresseddemand for key feedstock MA. Global demand is expectedto
strengthen, however, with 3%/yr growth rates predicted for 1992 through 1997,
according to SRI International
CHEMICAL ENGINEERING/DECEMBER 1993
7

61

CHEMICALS

to catalyst overheating and increases

the risk of explosion,partkularly for an
explosive feedstock. In fact, temperatures inside the tubes can rise by as
much as 50Cover a distance as short as
200 mm, says Randy Schumaker, catalySt and licensing manager for BP
Chemicals, Inc. (Cleveland, Ohio).
Butane concentration greater than
1.5 mol% in air forms a potentially explosive mixture, says Schumaker. This
calls for special precautions to prevent
fires, and limits the feed compositionto
a fixed-bed reactor, which ultimately
limits yield.
By comparison, fluid-bed reactors do
not experience hot spots. The suspension of fine catalyst particlev in air,
combined with the use of steah coils to
remove the heat of reaction, promotes
isothermal operation, which allows a
butane-to-ak ratio twice that of a fixedbed unit, says Joachim Portela, technology marketing manager for ABB Lummus Crest, Inc. (Bloomfield, NJ.).
In addition to increased yield, higher
butane input means lower air requirements. Reduced throughput lowers the
size and capital cost of air compressors
and downstream incinerators -reductions that can translate into 2040%savings in capital expenditures, says Roger Johnson, director of the chemical
business group for Lummus Crest.
Despite some advantages, yield tradeoffs associated with fluid-bed systems remain a key disadvantage, says
Monsantos Joe Burnett, technical director for MA. He notes that in general,
a fluid-bed system consumes 20-25%
more butane than a fixed-bed plant for
a given capacity.
Having taken the right safety steps,
Monsanto notes that it has operated
fixed-bed reactors with higher-than-average inlet butane concentrations of 2
mol% for more than 20 years. To further boost MA yield, the firm is also
working on a new fixed-bed catalyst in
the lab that will allow 3 mol% butane
feed concentrationsto the reactor, says
Bill Merman, director of manufacturing of process chemicals, who adds that
for a given reactor size, the jump from
2 to 3 mol% butane feed can increase
MA output by 50%. The firm is working
with D m GmbH (Deggendorf) to d e
velop a reactor to commercialize the
process.

MOVERS AND SHAKERS

IN MALEIC ANHYDRIDE
For more Information, circle the
appropriate number on the Reader
Service Card
ABB Lummus Crest
Alusuisse ltalia
Amoco Chemical Co.
Ashland Chemical Co.
BP Chemicals
Cepsa
Chimie Linz
Davy Process Technology
DuPont Co.
DWE GmbH
Grupo ldesa Petroquimica
Miles, Inc.
Mitsubishi Kasei Corp.
Monsanto Co.
Nan Ya Plastics Corp.
Shinwha Chemical Co.
Sisas
Tonen Petrochemical Cop.
Total Chimie

571
572
573
574
575
576
577
578
579
580
581
582
583
584
585
586
587
588
589

Catalyst refining
For both fixed- and fluid-bedprocesses,
development efforts continue to boost
catalyst performance. For fixed-bedoperation, improvementsaim to extend the
catalysts life to cut the frequency of
routine changeovers. This is important,
says Gunther Moeschel, commercial
manager a t Sisas, who notes that 25
days of downtime are required every
two years to load new catalyst into the
22,000 reactor tubes at the firms 65,000m.t./yr facility in Belgium.
Butane oxidationis carried out using a
vanadium phosphate catalyst with m e
tallic co-catalysts such as zinc or molybdenum. These catalysts are costly, so
minimizingpotential losses is a primary
goal, says Greg Collingwood, MA product manager for Amoco Chemical Co.
(Chicago, Ill.).
To avoid losses by mechanical attrition, fluid-bed catalysts must resist
abrasion. According to fluid-bed licensors Lummus Crest* and BP Chemicals,
todayk systems use more-rugged catalysts and include filters and cyclones to
capture abraded fines, which are then
continuously fed back into the reactor.
In 1991 Lummus Crests fluid-bed ALMA process ointly
develodd with Alusuisse Italii (Milan), mid an ionof
able mention in CEs biennial Kirkpatrick Award, which
honors outstandingadvances in chemical engineering technology. For details, see CE, December 1991, p. 97.

In Asia and Europe, several commercial-scale MA facilities use fluid-bed

technology. However, in the U.S., an
embrace of fluid-bed technology has
been slow to materialize. Many producers remain skeptical about the stated
advantages of the fluid-bed route. Despite some apparent benefits, all current
U.S. capacity -and all announced expansions -continues to rely on fixedbed production.
Such expansions have recently been
announced by Miles, Inc. (Houston) and
Ashland ChemicalCo. (Columbus,Ohio).
Miles is adding 120 million lbs of fixedbed capacity to its Baytown, Tex., facility, to bring output to 180million lb by the
end of 1994. And, next month, Ashland
will boost frontend capacity a t its Huntington, W.V. plant from 63 to 90 million
lbs. Its back-end capacity will remain a t
73 million lb until further debottlenecking is justified, says Michael Killian,
Ashlands vice-president and general
manager.
Monsantos fixed-bed Pensacola,Fla.,
plant is the largest MA unit in the world,
with nominal capacity a t 220 million lbs.
Last month, citing MA as a non-core
product, Monsanto announced plans to
sell the business to Huntsman Chemical
Co. (Salt Lake City, Utah) by year end.
Under the agreement, Monsanto will
continueto operate its two MA facilities
on Huntsmans behalf, and its developmental work with DWE will continue.

Solvent vs. aqueous recovery

In addition to the ongoing debate over
fixed- vs. fluid-bed technology, producers are debating the merits of two competing methods for product recovery.
The conventionalroute uses large quantities of water, often with a xylene
azeotrope, to scrub reactor offgases.
Distilling this stream is energy intensive, and creates acidic wastewater and
the potential for xylene emissions. BP
Chemicalsnotes that its aqueous system
relies on water alone, so the risk of
xylene emissions is avoided.
Using low-volatilityorganic solvents
to separate MA from the reactor offgas,
todays newer non-aqueoussystems c r e
ate no acidicwastewater. By eliminating
condensation and distillation, energy
needs of the closed-loopsystem can be
roughly one third that of an aqueous
system,says Johnson of Lummus Crest.
CHEMICAL ENGINEERING/DECEMBER 1993

63

* h

VERTICAL CENTRIFUGE
For High Pressures and
Temperatures

CHEMICALS

The SharplesB
Super-D-Canter@
vertical centrifuge
meets the need for
separation equipment that can contain high-pressure
and handle high temperatue applications.It can Gntain up to
150 psi and handle temperatures to

However, increased complexity and the

need for onsite solvent-storagecapabilities may be a drawback.
An upside of the solvent-basedrecovery system is a yield advantage. During
aqueous recovery, MA in the offgas
reacts with water to form maleic acid,
which isomerizes to fumaric acid. While
commercial-or food-gradefumaric acid
can be recovered, its formation depresses MA yield. In general, 97-98%of
700F
the MA produced in the reactor can be
Possible applications include recovered using a solvent-basedsystem,
processes involving flammable, toxic, while recovery rates of 9295%are typicaxinogenic,or pyrophoric materials . calfor an aqueous system, says Monsanvertical-axis design requires tos Burnett. BPs aqueous system has a
only one seal surface $&ad of three, demonstrated recovery efficiency of 96a@ uses lL3 the floor space of horizon- 98%, says Schumaker.
Despite some drawbacks of the aquetaldecanter.
ous method, many producers, including
Formi ~ , C i & N o . 3 0
BP and Ashland, continue to rely on it,
citingdesign simplicityand easy maintenance as advantages. In 1991, BP acHIGH-SPEED SOLIDS- quired the rights to Brussels-based
EJECTING CENTRIFUGE UCBs aqueous process, demonstrating
its long-standing commitment to this
FOR CPI
The Alfa Laval technology.
CHPX series of The quest for new derivatives
h i g h - s p e e d , Meanwhile, the market for MA continsolids-ejecting ues to expand. Davy Process Technoldisc-type cen- ogy (London)and DuPont Co. (Wilmingtrifuges is specifi- ton, Del.) have recently developed two
caUy designed for competing processes that use MA or
s e v e r e - d u t y maleic acid (instead of acetylene) to
chemical^- produce the widely used chemical intering applications. Standard design fea- mediates 1,4-butanediol(BDO), tetrahytures include: product-wetted parts in drofuran (THF) and gammabutyrolac(GBL). The cost to produce BDO
high-grade stainless steel for tone
using the companys butane-to-MAprounequalled corrosion resistance, cess is 20%lower #an the conventional
replaceable protecton for parts subject route, says Andrew Hiles, Davys BDO
to erosion, and high-mp r ~ - business manager.
cessing. Gas-tight, inert gas purging,
The Davy process has already been
and explosion-protected versions are commercialized in two separate plants.
available, as well as models for high- In 1991, Shinwha Chemical Co. (Seoul,
density p.
This series covers a Korea) started up a 20,000-m.t./yr BDO
facility. Last January, Tonen Petrocapcityrangeliwn2to 175GPM
Corp. (Tokyo) followed suit,
chemical
For mom iformation,Circle No. 31
bringing online a 20,000-m.t./yr facility
Contact the procesS Industries Group in Kawasaki, a 35,000-m.t./yr MA plant
of Alfa Laval Sharpie@, a business came online simultaneouslyto feed that
unit of Alfa Lavd sepalaha Inc., 955 plant. Meanwhile,NanYa Plastics Corp.
Meams Rd., Warminster, PA 18974. (Kaohsiung, Taiwan) recently an(215)443-4ooo. Fax: (215)4434112. nounced plans to build a 20,000-ton/yr
MA-to-BDO plant by the end of 1995.
In the Davy process, refined MA is
esterified with alcohol and hydrogenated to form THF and BDO. Since startup

Alfa Lava1Sharple9

64

CHEMICAL ENGINEERING/DECEMBER 1993

_.._

of the Tonen and Shinwha facilities,

improvements made to the countercurrent esterification step have increased
process selectivity, which has eliminated the need for distillation. This has cut
in half the number of components, reducingcapital costs by44%,says Davys
Hiles. Severalother improvements have
also cut utility consumption by 60%,
making the BDO process competitive
with acetylene-based plants.
DuPonts process differs from the
Davy route, in that it involves the catalytic oxidation of butane to maleic anhydride, which is recovered as aqueous
maleic acid. The maleic acid is then
converted directly to THF using a proprietary catalyst. The process does not
isolate and purify MA along the way,
says Tom Dufour, DuPonts planning
manager for Terathane products.
The DuPont process uses a transporb
bed reactor. Unlike a fluid-bed reactor,
in which the catalyst is kept suspended
inside the reactor, the catalyst in a
transport-bedreactor travels through a
circulation loop (CE,
April 1992, p. 17).
This design is capable of boosting yield,
providing up to 70-75 mol% conversion,
compared with an average 48% for current technologies, says Dufour.
DuPont is building a 100-million-lb/yr
THF plant based on maleic acid in the
Asturias region of Spain. It will support
the firms European production of polytetramethylene ether glycol (PTMEG;
trademarked Terathane),a precursor to
its Lycra spandexfiber and Hytrel copolyester elastomer products. When it
goes online in 1996, this facility will be
the first commercial use of transportbed technology.
Some producers are bullish on the
promise of THF and BDO markets expanding demand for MA. Schumakerof
BP notes that since no grassroots acetylene-based capacity expansions have
been announced,MA will likely be a key

feedstockforBD0,THFandGBLinthe
years to come.
Others are not as optimistic. You
dont plan growth rates for new potential uses, says Marshall Kendrick,
Miles director and general manager of
MA. You plan it for existing markets,
and if new uses come along. so much the
better.
Suzanne Shelley with Ken Fouhy and