Two-stage process produces ...
SEPARATION OF
TECHNOLOGY
Process originally
developed to use
ethylene extended to
propylene and butene
Wacker Process Can Make Acetone, MEK
A new production route to either ace-
tone or methyl ethyl ketone (MEK)
by direct oxidation of propylene or
butene has been opened up by extend-
ing the Wacker process for oxidizing
ethylene to acetaldehyde. Reactions
involved are similar to those used in
the ethylene oxidation, but differ in
reaction rates and by-product type
and amount, Dr. Juergen Smidt, di-
rector of Wacker Chemie, told the
Sixth World Petroleum Congress in
Frankfurt.
According to Wacker, the new proc-
esses have several advantages over
current routes:
• Reactions are one-step, produce
crude product (mixed with catalyst
solution) directly from starting ma-
terial.
• Reactions are highly selective,
produce relatively few by-products.
• Yields are h i g h - 9 2 to 94% for
acetone, 85 to 88% for MEK vs. less
than 80% by other routes.
• Energy consumption is relatively
low—about 18 kwh. per 100 lb. of
ketone.
• Feed can be a mixture of olefins
and saturated hydrocarbons.
• Only one main product is formed
and thus there is no by-product mar-
keting problem.
However, Wacker points out, ad-
vantages depend on plant location
and whether or not a new plant is
50 C&EN JULY 8, 1 9 6 3
REACTION
Off gas
Propylene orbutene
Air
being considered. These advantages
may not be so clear-cut in cases where
a company already has an existing
plant.
Wacker isn't giving details at the
moment, but says several firms in the
U.S. and Japan are interested in both
processes. For now, though, there
seems to be little interest in either
process in Germany itself. For one
thing, there is excess capacity for
acetone. For another, MEK doesn't
enjoy such wide use as a solvent as
it does in the U.S.; the Germans favor
esters.
Whether the extended Wacker
process will pick up as fast as the
original ethylene-to-acetaldehyde
route is an open question. Celanese
brought its 100 million-pound-per-
year plant on stream last summer
(C&EN, Aug. 6, 1962, page 2 9 ) ,
with increased capacity to 160 million
pounds by 1964 (C&EN, June 24,
page 2 3 ) . In the next year or two
about 500,000 metric tons annual ca-
pacity of Wacker acetaldehyde will be
on stream throughout the world. It
was only three years ago that Hoechst
started up the first acetaldehyde plants
using the Wacker process.
Direct Oxidation. In the Wacker
process, olefins react with an aqueous
solution containing palladium (II) and
copper (II) chlorides. Active com-
ponent of the catalyst is the PdCl 2 .
This reacts stoichiometrically with
the olefin to form the corresponding
OXIDATION CRUDE PRODUCT
Off air
Crude product
Stripping
column
Catalyst pump
carbonyl compound, metallic pal-
ladium, and hydrochloric acid. In a
simultaneous and instantaneous step,
CuClo reoxidizes the palladium to the
chloride. Thus only catalytic amounts
of PdCl 2 are needed. The over-all
reaction is thus olefin plus CuCl 2
and water in the presence of PdCl 2 to
form the carbonyl, CuCl, and HC1.
In a separate but continuous step,
CuCl is reoxidized to the cupric form
with oxygen or air and HC1. The
net reaction for the whole system is
thus a direct oxidation of olefin to
the corresponding carbonyl compound
in the presence of the two chlorides.
The reaction between olefin, PdCl 2 ,
and water actually occurs in two
steps; first a PdCl2-olefin-7r-complex is
formed. This complex hydrolyzes to
the carbonyl compound, metallic pal-
ladium, and HC1. The complex for-
mation is an equilibrium reaction but
the hydrolysis is irreversible.
Wacker finds that increasing the
carbon chain length of the olefin shifts
the equilibrium of the complex for-
mation back toward the olefin. It
also lowers the rate of hydrolysis.
Both factors lower the rate of reaction
of olefin with PdCl 2 . Thus reaction
rate of propylene is about one third
and that of butene-1 about one fourth
that of ethylene. Therefore, reaction
volumes with acetone and MEK must
be correspondingly larger than that
with acetaldehyde, Dr. Smidt says.
By-Products. In the case of ace-
 . . . MEK, which is purified like this ...
CRUDE
DISTILLATION
Crude product Process
water
, . .or acetone, which is purified like this
EXTRACTIVE
DISTILLATION
H20
Crude product Low-boiling
material
tone, by-products consist of 0.5 to
1.5% propionaldehyde, 2 to 4%
chlorinated material, 0.8 to 1.4%
carbon dioxide, and 0.5 to 1.5% other
substances. For MEK, they consist of
4% n-butyraldehyde, 4 to 6% chlo-
rinated material, 0.5 to 1% carbon
dioxide, and 2 to 2.5% other material.
The process can be run in either of
two ways. Olefin and oxygen can be
reacted simultaneously with catalyst
solution in a one-stage system. Or
olefin can be reacted first with catalyst
solution to form the carbonyl com-
pound. Then, after the carbonyl is
separated, the reduced catalyst solu-
tion is treated separately with oxygen
or air in a second stage. The first
system requires very pure feed, Dr.
Smidt says. The two-stage setup re-
quires less concentrated olefin and
would thus generally be favored.
Except that reduction volume is
larger for MEK, production of crude
acetone and MEK are the same. The
LIGHT END CAUSTIC
DISTILLATION HYDROGENATION SCRUBBING
Low-boiling
material NaOH
H2
DRYING
Pure acetone
Off water
processes differ in subsequent puri-
fication, though. In making crude
acetone or MEK with the two-stage
process, olefin is fed to a reactor where
it's treated with catalyst solution.
Saturated hydrocarbons, small
amounts of nitrogen brought in dur-
ing the oxidation step, carbon di-
oxide, and unreacted olefin separate
as off-gas from the reactor. The re-
action mixture in the catalyst solution
goes to a stripping column where
steam strips off crude product. The
catalyst solution is pumped from the
stripper to the oxidation reactor and
treated with air. Oxidized catalyst
solution is recycled to the reaction ves-
sel, where it reacts with more of the
olefin.
Lifetime of the catalyst is "prac-
tically unlimited," Dr. Smidt says.
Those parts of the system contacting
the catalyst must be made of titanium
or must be carbon-lined, since the
catalyst is so corrosive.
FINAL
DRYING DISTILLATION
Back to crude Pure MEK
distillation
Residue
A two-step distillation is used to
purify the crude acetone to a material
meeting ASTM standards. Purifying
MEK is more complex and expensive.
Separating the by-products formed is
harder. Also, MEK forms an azeo-
trope with water.
MEK Purified. In purifying MEK,
a crude distillation separates an MEK-
water mixture from most of the water
and chlorobutanone, chlorobutanone
coming off as a side stream. The
MEK-water mixture is further purified
in a separator. A second distillation
removes by-products boiling lower
than MEK. Among these are
n-butyric aldehyde, propionic alde-
hyde, acetone, and acetaldehyde.
The next step, hydrogenation, con-
verts n-butyraldehyde to butanol.
The latter doesn't deteriorate the
quality of the final product, according
to Dr. Smidt, and is a more economic
and efficient approach than the com-
plete removal of n-butyraldehyde.
The hydrogenation, however, also hy-
drogenates small amounts of chloro
compounds, so the product stream
must be scrubbed with aqueous so-
dium hydroxide to remove hydro-
chloric acid.
After scrubbing, the MEK is dried
by azeotropic removal of water along
with a certain amount of MEK. The
azeotrope is recycled to the crude col-
umn. The MEK bottom product is
distilled again, and the residue, a
small amount of higher-boiling prod-
ducts, is discarded.
JULY 8, 1 9 6 3 C & E N 51