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Two-stage process produces ...

SEPARATION OF
REACTION OXIDATION CRUDE PRODUCT

TECHNOLOGY Off gas Off air

Crude product
Process originally

developed to use Stripping


column

ethylene extended to Propylene orbutene

Catalyst pump
propylene and butene Air

Wacker Process Can Make Acetone, MEK


A new production route to either ace- being considered. These advantages carbonyl compound, metallic pal-
tone or methyl ethyl ketone (MEK) may not be so clear-cut in cases where ladium, and hydrochloric acid. In a
by direct oxidation of propylene or a company already has an existing simultaneous and instantaneous step,
butene has been opened up by extend- plant. CuClo reoxidizes the palladium to the
ing the Wacker process for oxidizing Wacker isn't giving details at the chloride. Thus only catalytic amounts
ethylene to acetaldehyde. Reactions moment, but says several firms in the of PdCl 2 are needed. The over-all
involved are similar to those used in U.S. and Japan are interested in both reaction is thus olefin plus CuCl 2
the ethylene oxidation, but differ in processes. For now, though, there and water in the presence of PdCl 2 to
reaction rates and by-product type seems to be little interest in either form the carbonyl, CuCl, and HC1.
and amount, Dr. Juergen Smidt, di- process in Germany itself. For one In a separate but continuous step,
rector of Wacker Chemie, told the thing, there is excess capacity for CuCl is reoxidized to the cupric form
Sixth World Petroleum Congress in acetone. For another, MEK doesn't with oxygen or air and HC1. The
Frankfurt. enjoy such wide use as a solvent as net reaction for the whole system is
According to Wacker, the new proc- it does in the U.S.; the Germans favor thus a direct oxidation of olefin to
esses have several advantages over esters. the corresponding carbonyl compound
current routes: Whether the extended Wacker in the presence of the two chlorides.
• Reactions are one-step, produce process will pick up as fast as the The reaction between olefin, PdCl 2 ,
crude product (mixed with catalyst original ethylene-to-acetaldehyde and water actually occurs in two
solution) directly from starting ma- route is an open question. Celanese steps; first a PdCl2-olefin-7r-complex is
terial. brought its 100 million-pound-per- formed. This complex hydrolyzes to
year plant on stream last summer the carbonyl compound, metallic pal-
• Reactions are highly selective,
(C&EN, Aug. 6, 1962, page 2 9 ) , ladium, and HC1. The complex for-
produce relatively few by-products.
with increased capacity to 160 million mation is an equilibrium reaction but
• Yields are h i g h - 9 2 to 94% for pounds by 1964 (C&EN, June 24, the hydrolysis is irreversible.
acetone, 85 to 88% for MEK vs. less page 2 3 ) . In the next year or two Wacker finds that increasing the
than 80% by other routes. about 500,000 metric tons annual ca- carbon chain length of the olefin shifts
• Energy consumption is relatively pacity of Wacker acetaldehyde will be the equilibrium of the complex for-
low—about 18 kwh. per 100 lb. of on stream throughout the world. It mation back toward the olefin. It
ketone. was only three years ago that Hoechst also lowers the rate of hydrolysis.
• Feed can be a mixture of olefins started up the first acetaldehyde plants Both factors lower the rate of reaction
and saturated hydrocarbons. using the Wacker process. of olefin with PdCl 2 . Thus reaction
Direct Oxidation. In the Wacker rate of propylene is about one third
• Only one main product is formed
process, olefins react with an aqueous and that of butene-1 about one fourth
and thus there is no by-product mar-
solution containing palladium (II) and that of ethylene. Therefore, reaction
keting problem.
copper (II) chlorides. Active com- volumes with acetone and MEK must
However, Wacker points out, ad- ponent of the catalyst is the PdCl 2 . be correspondingly larger than that
vantages depend on plant location This reacts stoichiometrically with with acetaldehyde, Dr. Smidt says.
and whether or not a new plant is the olefin to form the corresponding By-Products. In the case of ace-

50 C&EN JULY 8, 1 9 6 3
. . . MEK, which is purified like this ...
CRUDE LIGHT END CAUSTIC FINAL
DISTILLATION DISTILLATION HYDROGENATION SCRUBBING DRYING DISTILLATION

Low-boiling Back to crude Pure MEK


material NaOH distillation

H2

Crude product Process


water Residue

, . .or acetone, which is purified like this


EXTRACTIVE
DISTILLATION DRYING
A two-step distillation is used to
purify the crude acetone to a material
meeting ASTM standards. Purifying
H20 MEK is more complex and expensive.
Crude product Low-boiling Separating the by-products formed is
Pure acetone
material 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
Off water
coming off as a side stream. The
MEK-water mixture is further purified
in a separator. A second distillation
tone, by-products consist of 0.5 to processes differ in subsequent puri- removes by-products boiling lower
1.5% propionaldehyde, 2 to 4% fication, though. In making crude than MEK. Among these are
chlorinated material, 0.8 to 1.4% acetone or MEK with the two-stage n-butyric aldehyde, propionic alde-
carbon dioxide, and 0.5 to 1.5% other process, olefin is fed to a reactor where hyde, acetone, and acetaldehyde.
substances. For MEK, they consist of it's treated with catalyst solution. The next step, hydrogenation, con-
4% n-butyraldehyde, 4 to 6% chlo- Saturated hydrocarbons, small verts n-butyraldehyde to butanol.
rinated material, 0.5 to 1% carbon amounts of nitrogen brought in dur- The latter doesn't deteriorate the
dioxide, and 2 to 2.5% other material. ing the oxidation step, carbon di- quality of the final product, according
The process can be run in either of oxide, and unreacted olefin separate to Dr. Smidt, and is a more economic
two ways. Olefin and oxygen can be as off-gas from the reactor. The re- and efficient approach than the com-
reacted simultaneously with catalyst action mixture in the catalyst solution plete removal of n-butyraldehyde.
solution in a one-stage system. Or goes to a stripping column where The hydrogenation, however, also hy-
olefin can be reacted first with catalyst steam strips off crude product. The drogenates small amounts of chloro
solution to form the carbonyl com- catalyst solution is pumped from the compounds, so the product stream
pound. Then, after the carbonyl is stripper to the oxidation reactor and must be scrubbed with aqueous so-
separated, the reduced catalyst solu- treated with air. Oxidized catalyst dium hydroxide to remove hydro-
tion is treated separately with oxygen solution is recycled to the reaction ves- chloric acid.
or air in a second stage. The first sel, where it reacts with more of the After scrubbing, the MEK is dried
system requires very pure feed, Dr. olefin. by azeotropic removal of water along
Smidt says. The two-stage setup re- Lifetime of the catalyst is "prac- with a certain amount of MEK. The
quires less concentrated olefin and tically unlimited," Dr. Smidt says. azeotrope is recycled to the crude col-
would thus generally be favored. Those parts of the system contacting umn. The MEK bottom product is
Except that reduction volume is the catalyst must be made of titanium distilled again, and the residue, a
larger for MEK, production of crude or must be carbon-lined, since the small amount of higher-boiling prod-
acetone and MEK are the same. The catalyst is so corrosive. ducts, is discarded.

JULY 8, 1 9 6 3 C & E N 51