TECHNOLOGY
Hoechst Reveals Wacker Process Details
Process to convert ethylene to acetaldehyde exhibits
expected cost advantages, works with different raw materials
Now that Farbwerke Hoechst's two
German plants to make acetaldehyde
from ethylene (C&EN, Aug. 24, 1959,
page 39 ) have been on stream for over
a year, the company has lifted the lid
on some of the process details. Op-
erating experience has shown, Hoechst
says, that the Wacker process gives
high yields of acetaldehyde with a
quality comparable to that from the
conventional acetylene hydration proc-
ess, that it will work on raw materials
from a variety of sources, and that the
cost advantages foreseen for it have
been realized.
Germany's organic chemical indus-
try started and developed strongly on
coal-based raw materials. Most of the
acetaldehyde, for example, has been
52 C&EN APRIL 17, 1961
made from carbide acetylene since
WTorld War I (although some in
Europe is made from ethanol). From
the acetaldehyde have come acetate
esters, acetone, and other derivatives.
But during the past few years, the
German organics industry has been
turning to petroleum to supply the
growing quantities of raw materials it
needs. With the doubling of German
oil refining capacity since 1957, chemi-
cal companies are assured of constant
supplies of oil fractions to feed their
organic complexes. Further, petro-
leum ethylene is cheaper than acety-
lene, and handling is easier and safer.
Two factorsethylene is cheaper
than acetylene, and oil supplies from
which to make the ethylene are as-
suredhave been decisive in Hoechst's
plans to go ahead with its Wacker
process plants. In development since
1956, the process was ready for scale-
up at about the time that ethylene
expansions were coming on stream.
Two Variants. The Wacker process
for direct oxidation of ethylene to acet-
aldehyde was developed by Aldehyd
G.m.b.H. of Munich (jointly owned by
Wacker Chemie of Munich and
Hoechst). It has two variantssingle-
stage oxidation with oxygen, and two-
stage oxidation with air.
In both variants, ethylene is oxidized
in an aqueous solution of cupric chlo-
ride and palladium chloride. The cu-
pric chloride is reduced to cuprous
chloride during the oxidation. The
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54 C&EN APRIL 17, 1961
WACKER PROCESS CONSUMES PER H O U R . . .
Single-Stage Variant
Ethylene (at 88 p.s.i.a.)
Oxygen
Cooling Water
Steam (at 190 p.s.i.a.)
Steam (at 51 p.s.i.a.)
Electricity
Two-Stage Variant
Ethylene (at 176 p.s.i.a.)
Cooling Water
Steam (at 190 p.s.i.a.)
Steam (at 51 p.s.i.a.)
Electricity
Based on 66,000 ton-per-year capacity, working for 8000 hr. per year.
cuprous chloride is then oxidized back
to the cupric form by oxygen or air,
thus keeping the process continuous.
Using oxygen, the process goes like
this: Ethylene is fed into a vertical
reactor filled with catalyst solution.
Oxygen and recycle gas are also fed
into the bottom of the reactor. The
reaction takes place at the boiling point
of water-slightly higher than 100 C ,
since the reactor carries a "slight over
pressure." Heat of reaction is ab
sorbed by evaporation of some of the
water; the evaporated water is made
up to keep catalyst solution constant.
The gaseous reaction mixture
(steam, unreacted ethylene, and reac
tion products) goes to a separate wash
ing tower, where the acetaldehyde is
washed out with water. The alde
hyde-free gas is recycled back to the
reactor, with a side stream bled off to
keep the inert content constant. The
side stream is also oxidized to convert
the last bit of ethylene.
To oxidize with air, Hoechst has a
modified process design. Ethylene
flows through the catalyst solution in
nient in auxiliary oxygen facilities.
a single-pass reactor at higher pres
sures and temperatures than in the
single-stage process. The mixed reac
tion products and catalysts are sepa
rated by distillation in a separate unit,
using the heat of reaction to supply the
heat. The catalyst solution flows
from the still to a regeneration unit,
where the cuprous chloride is reoxi-
dized to cupric chloride with air and
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returns to the first reactor for its next
cycle.
Crude acetaldehyde is purified in
both processes by a final distillation to
separate it from water and higher-boil
ing components. Its quality after re
covery is comparable to that from
other processes, according to Hoechst.
Two-Stage Process Is Flexible. Ad
vantage of the two-stage process,
Hoechst points out, is that it can han
dle either a pure ethylene feed or an
ethylene-rich gas, since there is no re
cycle gas stream. The waste air, with
so much of its oxygen removed, can be
used as a blanketing gas. The process
will also work with oxygen in the
catalyst regeneration.
Both variants give about 959^ yield
with alrflost no by-products, operate at
low working pressures and tempera
tures, consume little energy, and re
quire relatively low capital investment,
Hoechst adds. A 66,000 ton-per-year,
single-stage plant in Germany will cost
abo^t $2.9 million, a two-stage plant
of about the same capacity will be
sc*nie $3.7 million, but with no invest-
\ Besides the two plants it is building
fcfr itself, Hoechst has licensed the
Wacker process to Celanese, which is
now building it into its new acetyls
plant at Bay City, Tex. (C&EN, Feb.
6, page 3 7 ) . Hoechst admits that sev
eral other companies around the world
are negotiating for licenses, although it
will not name them.
Abbott Pushes Ruthenium Catalyst Work
Ruthenium catalyst process for hydrogenating
pyridine to piperidine to move into pilot plant
Abbott Laboratories is planning to
move its ruthenium catalyst process
for hydrogenating pyridine to piperi-
dine into the pilot plant stage, the
company said last week. If the cata-
lyst works as well in a continuous
process as it does in lab studies, the
company expects to be able to produce
piperidine under much milder condi-
tions than those required by current
higher pressure catalysts. Another
big advantage is that the process works
with pyridine as the sole liquid phase.
The current market for piperidine
is about 300,000 lb. a year, Abbott's
chemical market research department
estimates. The reactive, secondary
amine is an intermediate in synthesiz-
ing dyes, polymers, pharmaceuticals,
and oil and fuel additives.
Lab tests have shown several ad-
vantages for the ruthenium catalyst
HYDROGENATION BOMB. Morris Frei-
felder of Abbott Laboratories loads a
hydrognation bomb. Mr. Freifelder has
been able to hydrogenate pyridine to
piperidine under relatively moderate
conditions using a ruthenium catalyst
ISOTOPES
for Your
Development Work
in hydrogenating pyridine and a num-
ber of its derivatives, Abbott's Morris
Freifelder says (C&EN, April 3, page
57). As the dioxide, or distributed on
a carrier, ruthenium will reduce
pyridine without solvent, at moderate
temperature and pressures, and in
quantitative yield, Mr. Freifelder says.
Infrared analysis of undistilled prod-
uct filtered from the catalyst shows
complete conversion to piperidine, he
notes. This takes place with less than
2% weight ratio of R u 0 2 to pyridine,
is complete in half an hour, and goes
at 95 C. and 70 atm., he says. An-
other factor that makes the process Oak Ridge National Laboratory offers
commercially attractive is that the raw more than 300 radioactive and stable
material need not be the purest grade. isotope products.
Unlike other hydrognation cata- RADIOISOTOPES
lysts, rutheniumas the dioxide or on Processed Solutions 90 processed ra-
a carrierdoesn't appear to be dioisotopes may be obtained, including
many carrier-free and high specific activ-
affected by nitrogen base poisons, Mr.
ity products.
Freifelder points out. Platinum oxide,
Now Available Iridium-192 gamma
for example, will reduce pyridine in sources with specific activity up to 100
a reasonable time. But an equivalent curies per gram, and cobalt-60 radiogra-
of organic or mineral acid has to be phy sources 1/8 and 1/16-inch in diame-
present or pyridine will poison the ter with specific activity greater than
100 curies per gram. At a reduced price,
catalyst. Also, it's difficult to separate carbon-14 barium carbonate is available
the piperidine economically. a t $9.50 per millicurie.
Raney nickel and other commer-
STABLE ISOTOPES
cially available nickel catalysts require
More than 200 stable isotopes available
more drastic conditions. Reports of from 50 elements Chemical processing
reductions with this catalyst generally and target fabrication services also of-
quote pressures of 150 to 300 atm., fered Ultra-high isotopic purity in a
temperatures above 150 C , and far number of isotopes.
longer reaction times, Mr. Freifelder For information or literature, write t o :
Isotopes Division, Oak Ridge National
points out. Rhodium also has been Laboratory, P . O. Box X , Oak Ridge,
mentioned as a possible catalyst. But Tennessee.
Abbott finds it undergoes nitrogen
base poisoning too.
In hydrogenating some 20 other de-
rivatives, Mr. Freifelder found only
one that was difficult. This was 2, 4,
6-trimethylpyridine. It required
higher temperatures and longer reac-
tion times, probably due to steric
effects, he says. Most of the reduc-
OAK RIDGE
tions could be carried out in alcohol NATIONAL LABORATORY
solvents, from which separation is Operated by
relatively simple, he found. Carboxyl UNION CARBIDE CORPORATION
for the
groups aren't affected, except for ni- U.S. ATOMIC ENERGY COMMISSION
cotinic acid, which was decarboxy-
lated. This he prevented by carrying
out the reduction in aqueous sodium
bicarbonate solution. Also, alcohol
substituents aren't hydrogenolyzed,
Mr. Freifelder notes.
APRIL 17, 1 9 6 1 C&EN 55