Patented May 30, 1933

1,911,315

UNITED STATES PATENT OFFICE

CARL HANER, OF MOYLAN, AND EDWARD P. FENIMORE, OF DIREXEL HILL PENNSYL
WANIA, ASSIGNORS
CORPORATION TO PUBLICKER, INC, OF PHILADELPHIA, PENNSYLVANIA, A.
OF DAWARE
PROCEss FOR THE MANUFACTURE OF ACETIC ACID
No Drawing. Application filed August 19, 1931. Serial No. 558,188.
Our invention relates to a process of pre
paring acetic acid from ethyl alcohol or Itbeis oxidized
well knownto that iyi
ethyl alcohol vapor
mixtures of ethyl alcohol and acetaldehyde, can by passin
it together with oxygen over a catalyst EE
and more particularly it relates to a pro as copper or silver. Difficulty has been en
is cess by which acetic acid can be produced countered, however, in continuing the oxi
by means of a single catalyst by the oxida dation of the
tion of ethyl alcohol or mixtures of ethyl these methods,alcohol to acetic acid since in
alcohol and acetaldehyde to acetic acid in amount of acetaldehydeis together
there produced a large
with cer
the presence
10 or as air.
of oxygen, either in pure form tain undesirable by-products such as acetal,
One object of our invention is to provide methane,
a very
ester, and the like, and with but 60
small amount of acetic acid. It has
a process by which substantial yields of not, heretofore,
acetic acid may be obtained by the oxidation stantial yield ofbeen possible to get a sub
acetic acid by the oxida
of ethyl alcohol or mixtures of ethyl alcohol tion of ethyl alcohol in the presence of air
15 and acetaldehyde in the presence of oxy or pure oxygen by continuously passing the 65
gen by passing the alcohol vapor or the mix vapor
ture containing acetaldehyde vapors over sible toover a catalyst; nor has it been pos
pass a mixture of alcohol and acet
a heated catalyst.
A further object of our invention is to aldehyde continuously over a catalyst and
20 provide a process for the production of very amounts. to acetic acid in substantial 70
convert both
good yields of acetic acid from ethyl al
cohol or mixtures or ethyl alcohol and acet essThe for
present invention contemplates a proc
manufacturing acetic acid, result
aldehyde, which process is characterized by ing in very good yields of acid and with but
the use of a catalyst which is reactivated few by-products, by passing ethyl alcohol
25 during the process and which, therefore, can vapor or a mixture of ethyl alcohol and is
be employed in the system for the produc acetaldehyde vapor over a specially pre
tion of acetic acid without removal there pared non-luminous copper oxide catalyst
from for the purposes of reactivation. in the presence of oxygen either in the form
A further object of our invention is to of air or in pure form, the catalyst being
30 furnish a process for the catalytic produc maintained during the process at a tempera
tion of acetic acid from ethyl alcohol and
mixtures thereof with acetaldehyde which, ture to
varying from approximately 300° C.
400°C., and preferably in the neighbor
due to the reactivation of the catalyst dur hood of 320° E. C. The invention
ing the process, may be run continuously,
35 any unoxidized alcohol or aldehyde pass further contemplates a process for the pro
ing through the catalytic chamber being re the duction of acetic acid catalytically in which cy
circulated and hence utilized in the produc out catalyst
tion of acetic acid.
can be used continuously with
independent treatment to reactivate it,
Still another object of our invention is due to the fact that the oxygen during the
40 to provide a novel catalyst for the produc process acts upon it and keeps it in an
tion of acetic acid, and the method of pre active condition.
The catalyst which is employed in the
&C.
paring it, which catalyst is capable of pro present
ducing large yields of acetic acid from ethyl in any invention is activated copper oxide
suitable form such as mill scale,
alcohol or mixtures of ethyl alcohol and copper oxide
45 acetaldehyde in the presence of oxygen, Prior to its usewire, copper oxide gauze, etc.
in the process of the present C
and is capable of
during the process. reactivation by the oxygen invention, it is treated to render its suitably
active
These and other objects will be apparent accomplishedfor the purpose. The activation is .
hereinafter from a consideration of the oxide by treating the heated copper
50 specification and claims. with alcohol vapor preferably in the
absence of air. At first the proportion of
 2 1,911,815.
alcohol changed into acetic acid is very low at the temperature desired by external
but this increases as the passage of a cohol means. The products issuing from the tube
vapor is increased until a maximum propor are for the most part water and acetic acid
tion is obtained, thereafter the proportion vapors containing some acetaldehyde and a
of alcohol converted begins to decrease. condensed little unconverted alcohol. The vapors are
The treatment of the catalyst is stopped at and the alcohol or absorbed by suitable means
or or near that point where the production tilled from the mixture and acetaldehyde are dis
of acetic acid is at the maximum. and utilized in the
In a typical case, 7 pounds 7 ounces of process. If a continuous process is desired.
the products issuing
O copper, oxide are placed in a tube making chamber or tube are condensed at a tem
from the catalytic
a column of catalyst thirty-eight inches perature below the boiling point of acetic
long. Alcohol vapor is passed through the
column of catalyst which is maintained at acid and above the boiling point of the ethyl
alcohol and acetaldehyde, in which case sub 80
300° C. to 340°C. at the rate of 70 grams stantially
15 of 95% alcohol per hour. In this case, it is in the firstall of the acetic acid is retained
found that the formation of acetic acid is aldehyde forcondenser while the alcohol and
at its peak'when 262 grams of 95% alcohol condensed or absorbed inpart
the most pass on and are
subsequent appara
have been passed through the column. It tus and are continuously added to the
will be understood that the rate of passage hol delivered to the catalytic chamberalco or 85
20 of alcohol, the amount of alcohol necessary tube. Obviously, if acetaldehyde is desired
and the temperature of the catalyst may all as a by-product, ethyl alcohol alone and the
be varied to suit the particular conditions air or pure oxygen are passed through the
existing.
In carrying out the process for the manu catalyst,
w
and the acetic acid and acetalde 90
25 facture of the acetic acid, the catalyst is hyde formed are recovered as finished
placed in a catalytic chamber which is main products.
tained between 300° C. and 400° C. and In a typical case, 7 pounds 7 ounces of
preferably in the neighborhood of 320° C.- copper are
oxide activated as herein described
placed in a tube, making a column of 95
340° C. The ethyl alcohol vapor, or the catalyst thirty-eight inches long. 109.2 liters
30 mixture of ethyl alcohol vapor and acetal
of air are passed
dehyde, and air or pure oxygen are pref 95% strength at 46 C. at such through ethyl alcohol of
erably preheated to a temperature approx air is approximately saturateda with rate that the
alcohol
imating that of the chamber in order not to vapor. Water vapor substantially equalling 00
chill the catalyst and make it less active, al the alcohol vapor in weight is then
35 though this preheating step is not necessary
to the alcohol vapor-laden air. Thisadded
mix
if the operator deems it inexpedient. The ture is passed through the activated copper
amount of oxygen employed is such that
there will be sufficient present in the catalytic oxide
mately
catalyst maintained at an approxi,
constant temperature in a bath of 05
chamber not only to furnish oxygen for the liquid sodium and potassium nitrate, the
40 oxidation of at least a portion of the alcohol
and acetaldehyde but also for maintaining bath temperature being kept at approxi
the catalyst active. For the purpose of ob mately 325° C. by external means. The rate
taining the best yield, it has been found ad 67.6 grams ofofthe95%mixed
of passage gases is such that
alcohol per hour are O
vantageous to use such a proportion of oxy
45 gen that practically all of it will be utilized passed through the tube. From 47.4 grams
in the catalytic chamber. It has also been grams of 95% alcohol, there are obtained 26.27.
found that the addition of water vapor or acetaldehyde. of acetic acid and 13.57 grams of
the use of alcohol of less strength, than 95% A little unchanged alcohol is
also recovered.
will give substantially higher yields of acetic is desired as a finished The acetaldehyde, unless it 5
50 acid than are obtained when water-free al product, together with
the unconverted alcohol is mixed with the
cohol or 95% alcohol is used.
It has been found advantageous to pass alcohol In a
fed to the catalytic chamber.
typical case where both ethyl alcohol
the air or pure oxygen through the alcohol and acetaldehyde
in a vaporizer maintained at a proper tem 110.4 liters of freeareairfed are
to the catalyst, 20
passed through
55 perature to give the ratio of alcohol of ox
ygen desired. The vaporizer may also con ethyl alcohol of 95% strength containing
tain acetaldehyde in which case the vapor acetaldehyde kept at a temperature of 42
laden air or oxygen contains both alcohol stantially saturateda rate
C.-43° C. at such
with
that the air is sub
alcohol and alde 25
and acetaldehyde. This vapor laden air is hyde vapor. Water vapor substantially
60 then, passed through a tube charged with
equalling the combined
the activated copper oxide catalyst. The cohol and acetaldehyde is then added amount of ethyl al
tube which may be of metal such as iron or vapor-laden air. This mixture is passed to the
copper is maintained at the desired temper through the activated copper oxide catalyst
ature by any suitable means, for example, 30
65 by placing it in a liquid which is maintained arranged in a metal tube so that 7 pounds 7
 1,911,315 3
ounces make a column of catalyst thirty alcohol vapors at an elevated temperature
eight inches long. During the passage of until the production of acetic acid is at or
the vapor-laden air, the catalytic chamber near the maximum, and thereafter condens
or tube is maintained at the desired temper ing the vapors
ature by placing it in a bath of a liquid 2. The processto of obtain the acetic acid.
acetic acid 70
mixture of sodium and potassium nitrates catalytically which preparing
heated externally to a temperature of 325 vapor, containing essentially as passing
comprises
an
a
active
C-327°C. The rate of passage of the mixed ingredient a compound capable of catalytic
O gases is such that a total of 60 to 70 grams oxidation to form acetic acid, and oxygen
of alcohol and acetaldehyde are passed
through the tube per hour. From 31.6 grams athrough a catalytic chamber maintained at 75
of 95% alcohol and 15 grams of acetalde in contact withbetween
temperature
a
300° C. and 400° C.
catalyst of non-luminous
hyde, there are obtained 23.36 grams of copper oxide, said catalyst having been acti
acetic acid and 15.33 grams of acetaldehyde vated
5
with a small amount of unchanged alcohol. alcoholbyvapors treating copper oxide with ethyl 80
in the absence of oxygen
The acetaldehyde and alcohol are continu at an elevated temperature until the produc
ously separated from the acetic acid as here tion of acetic acid is at or near the maxi
inbefore described and are continuously add mum, and thereafter condensing the vapors
20
ed to the supply of ethyl alcohol passed to obtain the acetic acid.
through the catalytic tube or chamber. 3. The process of preparing acetic acid 85
In both examples, the catalyst is of such catalytically which comprises passing a
a nature that it is reactivated during the vapor, containing essentially as an active in
process by the oxygen passed through it, gredient a compound capable of catalytie
thus a process is provided in which the oxidation to form acetic acid, and oxygen 90
catalyst can be used continuously without through a catalytic chamber maintained at
the necessity of its removal and reactiva a temperature in the neighborhood of 320
tion by a separate process. The amount of C-340 C. in contact with a catalyst of
air or oxygen to alcohol and aldehyde given non-luminous copper oxide, said catalyst
in the preceding examples may be varied
30
widely, care being taken, however, to avoid havingwith been activated by treating copper. 95
the formation of explosive mixtures. It is oxide ethyl alcohol vapors at an ele
to be noted that herein in both the specifi acetic acid is at or until
vated temperature
near
the production of
the maximum, and
cation and claims the word "oxygen' in thereafter condensing the vapors to obtain
25 cludes both air and oxygen in pure form. the acetic acid.
Furthermore, the strength of the ethyl al 4. The process of preparing acetic acid 100
cohol employed as well as the amount of catalytically which comprises passing a
water vapor added may be varied within vapor, containing essentially as an active in
considerable limits, pure 95% alcohol or pure gredient a compound capable of catalytic
40 95% alcohol and acetaldehyde being em oxidation to form acetic acid, and oxygen
ployed if desired. In most instances, it is
found that some water vapor is desirable, through a catalytic chamber maintained at 105
and it will be obvious that the amount em a temperature between 300° C. and 400° C.
ployed determines the concentration of the in contact with a catalyst of non-luminous
acetic acid solution obtained. The acetalde copper oxide, said catalyst having been acti
hyde and/or water may be added to the al vated alcohol
by treating copper oxide with ethyl O
vapors in the absence of oxygen.
cohol before vaporization and the whole at a temperature in the neighborhood of
mixture vaporized by the air in one process, 300
or the acetaldehyde may be added to the was acetic acid is at or near the
C-340° C. until production of
the maximum. and
50 ter and the mixture vaporized separately and thereafter condensing the vapors to obtain
mixed with the alcohol in air mixture. It 5
will thus be seen that the specific steps em the5. acetic acid. . . '
The process of preparing acetic acid
ployed in the process are capable of wide va catalytically which comprises passing a
riation without departing
features of our invention.
from the essential vapor, containing essentially as an active
We claim: ingredient a compound capable of catalytic
1. The process of preparing acetic acid oxidation to form acetic acid, and oxygen 120
catalytically which comprises passing a through a catalytic chamber maintained at
vapor, containing essentially as an active a temperature in the neighborhood of 320°
C)
ingredient a compound capable of catalytic C-340°C. in contact with a catalyst of non
oxidation to form acetic acid, an oxygen luminous copper oxide, said catalyst having 25
through a catalytic chamber maintained at been activated by treating copper oxide with
a temperature between 300° C. and 400° C. ethyl alcohol vapors in the absence of oxy
in contact with a catalyst of non-luminous gen at a temperature in the neighborhood of
65 copper oxide, said catalyst having been acti 300 C-340° C. until the production of
vated by treating copper oxide with ethyl acetic acid is at or near the maximum, and 30
 4. 1,911,815
thereafter condensing the vapors to obtain vapor, containing essentially as an active in
gredient a compound capable of catalytic
the acetic acid.
6. The process of claim 1 in which water through a tocatalytic
oxidation form acetic acid, and oxygen
chamber maintained at
yapor is passed through the catalytic cham
ber with the oxygen and vapor containing a temperature in the neighborhood of 320 70
essentially as an active ingredient a com C-330°C. in contact with a catalyst of
nonluminous copper oxide, said catalyst
Ed capable of oxidation to form acetic having been activated by treating copper
CC.
7. The process of claim 2 in which water oxide with ethyl alcohol vapors in the ab
O vapor is passed through the catalytic cham
sence of oxygen at a temperature in the
ber with the oxygen and vapor containing neighborhood of 300° C-340° C. until the
essentially as an active ingredient a com production of acetic acid is at or near the
Ed capable of oxidation to form acetic maximum, condensing the vapors, separat
ing the acetic acid from the unoxidized com
8CO pounds, and continuously returning said un 80
8. The process of claim 4 in which water oxidized
vapor is passed through the catalytic cham compounds to the system to be re
ber with the oxygen and vapor containing st.prized and re-passed through the cata
essentially as an active ingredient a com y: The process of claim 10 in which
pound capable of oxidation to form acetic water vapor is passed through the catalytic 85
20 acid. chamber with the oxygen and vapor con
9. The process of claim 5 in which water taining essentially as an active ingredient
vapor is passed through the catalytic cham a compound
ber with the oxygen and vapor containing acetic acid. capable of oxidation to form
essentially as an active ingredient a com 14. The process of preparing acetic acid 9)
pound capable of oxidation to form acetic catalytically which comprises passing a va
acid.
10. The process of preparing acetic acid por containing essentially as an active in
catalytically which comprises passing a gredient a compound capable of catalytic
vapor, containing essentially as an active oxidation
through a
tocatalytic
form acetic acidmaintained
chamber
and oxygenat
30 ingredient a compound capable of catalytic
oxidation to form acetic acid, and oxygen aintemperature
contact with
between 300° C. and 400° C.
a catalyst of non-luminous
through a catalytic chamber maintained at
a temperature between 300° C. and 400° C. copper oxide, said catalyst having been acti
in contact with the catalyst of non-luminous vated by treating copper oxide with ethyl
35 copper oxide, said catalyst having been acti alcohol vapors at an elevated temperature
vated by treating copper oxide with ethyl untilnear
the production of acetic acid is at or
the maximum, the amount ofsufficient
oxygen
alcohol vapors at an elevated temperature passed through the system being
until the production of acetic acid is at or in amount to cause oxidation of at least a
near the maximum, condensing the vapors, 105
40 separating the acetic acid from the unoxi portion of the initial ingredients and to
dized compounds, and continuously return maintain the catalyst in an active condition,
ing said unoxidized compounds to the sys to 15. obtain the acetic acid.
The process of preparing acetic acid
tem to be re-vaporized and re-passed through catalytically which comprises passing a
the catalyst. vapor containing essentially as an active 10
11. The process of preparing acetic acid
catalytically, which comprises passing a ingredient a compound capable of catalytic
45
oxidation to form acetic acid and oxygen
vapor, containing essentially as an active in through
gredient a compound capable of catalytic a temperature a catalytic chamber maintained at
oxidation to form acetic acid, and oxygen C-340° C. in incontactthe neighborhood of 320°
with a catalyst of
50 through a catalytic chamber maintained at
a temperature in the neighborhood of 320° non-luminous copper oxide, said catalyst hav
C-340° C. in contact with a catalyst of non ing been activated by treating copper oxide
luminous copper oxide, said catalyst having with ethyl alcohol vapors at an elevated tem
been activated by treating copper oxide with perature until the production of acetic acid is 120
5 ethyl alcohol vapors in the absence of oxy at or near the maximum, the amount of oxygen
gen at an elevated temperature until the passed through the system being sufficient in
production of acetic acid is at or near the amount to cause oxidation of at least a por
maximum, condensing the vapors, separat tion of the initial ingredients and to main
0 ing the acetic acid from the unoxidized com
pounds, and continuously returning said tain the catalyst in an active condition, and
thereafter condensing the vapors to obtain.
unoxidized compounds to the system to be the acetic acid.
re-vaporized and re-passed through the cata 16. The process of claim 14 in which water
lyst. vapor is passed through the catalytic cham
12. The process of preparing acetic acid 30
65 catalytically which comprises passing a ber with the oxygen and vapor containing es
 1,911,815
sentially as an active ingredient a compound
capable of oxidation to form acetic acid.
17. The process of claim 15 in which
5 water vapor is passed through the catalytic
chamber with the oxygen and vapor contain
ing essentially as an active ingredient a
compound capable of oxidation to form ace
tic acid.
O CARL HANER.
EDWARD P. FENIMORE.

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