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March 20, 1934.

M. MUELLER~-CUNRAD1 ET AL
'l

PRODUCTION OF ACETIC ACID

1,951,789
y

Filed Sept. '10. 1932

L_MTORNEYS.

Patented-Mai. __zo, 1934

l 1,951,739 .

UNITED STATES PATENT OFFICE


l

1,951,189.

APRODUCTION oF AcE'rIo Aon)


Martin Mueller-Cunralli, Kurt Pieroh,> and
Hellmut Giehne,l Ludwigshafen-on-tlre-Rhine,
Germany, assignors to I. G. Farbemndustne

Aktiengesellschaft, Frankfort - on - the - Main,

Germany

Application septembr 1o, 1932, seriqiNo. 632,550


-

In Germany September 16, 1930

' 8 Claims. .(Cl. ZBO-116)

The present invention relates to the production Within the apparatus. Since such explosions may
`
'
V
occur quite suddenly at any time, working accord
It has already been proposed to prepare acetic ing to either of the said processes is rather danger
acid by oxidizing acetaldehyde byv means of oxy ous and objectionable..
gen, the reaction being carried out in a vertical
Wev have now found that the continuous oxida- Q0
tubular vessel containing solid filler bodies which tion of acetaldehyde to acetic acid by means of-

of aceticl acid.

act as diluents'and are intended to prevent ex

plosions of the mixtureoi oxygen with the alde


hyde vapours since the'oxygen is contacted with
10 the aldehyde only in the spaces left free between
the said solid ller bodies. ln order to maintain
the desired reaction temperature a suitable pro~

portion of acetic acid containing, if desired, one

an oxygen containing gas, such as oxygen or air,

in the presence of acetic acid, which, preferably


carries a catalyst, can be elected in avery ad
vantageous manner while avoiding any >risk of 05

explosion'a'nd lpractically any loss of aldehyde


while continuously supplying acetic acid to the
reaction mixture, and drawing on a quantity of
acetic acid corresponding to that formed from
the aldehyde, if the oxidation is carried out in. a 70
vertical, coherent column of acetic acid, While in

of the catalysts kno-Wn for the reaction is fed into


the cooled upper part of the apparatus, whereas
the acetaldehyde is preferably introduced into the
middle part vof the vessel where it is contacted troducing the oxygen containing gas and acetal
with a current of oxygenntroduced from the dehyde both into the lowest region of said co
bottom of the vessel. The lower part of the vessel herent column. The said coherent column of
is preferably heated so that unaltered aldehyde, acetic acid preferably comprises more than one 75
eventually present in the mixture of acetic acid zone, the uppermost Zone being continuously sup
introduced and formed,v distills oli into the reac plied from its highest region with a. stream of cold
4 tion space, Whereas any peracetic acid formed is

acetic acid free from acetaldehyde and carrying '

decomposed, acetic acid free from aldehyde being the catalyst, if such is employed, whereas the

thus drawn off from the bottom of the vessel.


liquid from the lowest zone of said coherent 3o>
Another continuous process for the production column, preferably moves upwards together with Of acetic acid bythe oxidation of acetaldehyde the oxygen containing gas and the acetaldehyde,
by _means of anoxygen containing gas consists in so that any gaseous materials must ow upwards

conducting the reaction in a medium of acetic and 'pass throughout through a Whole liquid col~

acid containing a soluble catalyst, which medium umn in which there may exist no gas spaces 85
is supplied to a tower provided with iiller bodies other than ,the bubbles formed by the rising gases
and allowed to flow in countercurrent to a stream or vapours introduced into the lowest zone.,
of acetaldehyde vapour and oxygen containing
The catalysts which may be employed accord
gas, the-acetic acid being continuously withdrawn ing to the present process can be chosen from
at the bottom of the tower and then continuously any of those hitherto employed for the reaction- 90
separated into. pure acid and an acid containing such as active carbon or one or more metals, such
the catalyst, which is continuously returned into > as'manganese, copper, cobalt, nickel, chromium,
- the process.` The amount ofv pure acetic- acid iron, vanadium, platmum and other metals of
separated is preferably equal to that produced by the platinum group. The metals may be 'em
the oxidation, so that the solution of the catalyst ployed in the form of their salts soluble in acetic 95
in- the acid is maintained at its original concen acid, especially in the form of their salts with
tration. If desired, the reaction may be per fatty acids, such as formic, acetic, tartaric, pro
formed under pressure. In order to localize the picnic, butyric and like acids, or of their salts
` oxidation in the middle section of the tower, dif with inorganic acids, such as hydrochloric, sul
ferent sections thereof 'may be maintained at phuric or nitric acids, if desired in conjunction 100
various predetermined temperaturesand a part .with the corresponding salts of alkaline earth
of the liquid may be withdrawn from the central metals, that is barium, strontium, and calcium,

oxidation section, acirculated through a cooler and including magesium and aluminium. Although

returned to the tower.

_
any of the said salts, or> mixtures maybe em
Althoughthe described processes each mark a ployed as the catalyst, we- preferto employ the 105
progress as compared with older, similar or other acetates and, more particularly, manganese ace
methods, there is still an important objection tate as the essential constituent which has proved

thereto, namely the risk of explosion which is due to be most efficient. The catalysts'are usually
to the impossibility of preventing the accumula# employed in a quantity oi from about 0.1 to
tion of gaseous mixtures of aldehyde and oxygen about 0.5 per cent by weiglitof the acetic acid lio

1,951,789

employed as the liquid reaction medium, pref


erably in an amount of 0.2 per cent; the quan
tity of saltsof metalsother than manganese is
generally about 10 per cent by weight of the
manganese acetate, if such be employed as the
catalyst and if it is desired to employ mixtures.
Cold acetic acid free from aldehyde which is
supplied as stated above to'the uppermost lone

to 1 or 2per cent, of either of these substances.


The process may be carried out in a tower-shaped,
vertical vessel in which means are arranged which
are capable of restricting the cross-section in
the upper half of said vessel; such means should 80
be arranged .at least near the middle of said
vessel, so that atleast two zones are formed. It

is, however, also possible to form more than two

may be obtained for example by continuouslyy zones, by arranging severaly restricting means,
10 withdrawing, preferably near the highest region preferably in the upper half of the vessel. In Si;
of the lowest zone (in which the oxidation takes

order to introduce the oxygen containing gas and

place), a quantity of acetic acid, corresponding


to the amount of acetaldehyde which is continu
ously introduced into the lowest region of said
zone and -oxidized therein, subjecting the' acid
withdrawn to distillation, preferably until the

20

25

30

40

45

the acetaldehyde, at least two inlet pipes are ar


ranged at or near the bottom of the vessel. An
external cooling device, preferably a thermo
siphon cooler, is connected to about the upper 90
region of the lower zone formed in the said vessel
vapours are free from unaltered aldehyde, and by the said restricting means and to about the
cooling the residual acid which is then free from bottom of said vessel, so that the reaction mix
aldehyde but- still contains the catalyst, if such ture may be quickly circulated upwards through
has beem employed, andsupplying this cold acid the said lower zone and downwards through the 05
cooling device. At about the bottom of the up
to the upper zone of the liquid column.
`
The acid which is supplied to the said upper permost zone an outlet pipe is arranged, through
most zone is cooled to a temperature of from which the acetic acid is led downwards to the
-18 to about 30C., preferably to about 20 C. lower zone to which the said pipe is connected,
Near the lowest region of the uppermost zone the either directly and preferably at about the .bot
temperature of the-acid may be from about 25 tom of the vessel, or indirectly, by means of the
lto about 40 C. owing to the heat developed by upper pipe of the cooling device, in which case
the reaction. This warm acid may be directly the acid coming from the bottom of the upper zone
supplied to the lowest zone of the coherent _liq is mixed with the reaction mixture which is cir
uid column, preferably to a lower region of said culated through the said cooling device. An out 135
zone. As already stated, it is preferable that let pipe is arranged at the top of the vessel, which
pipe is intended for removing gaseous materials;
the lowest zone of the liquid column moves up
wards, that is in the same direction as the if the process is carried out under increased pres
oxygen containing gas and the acetaldehyde, sure, i. e. at a pressure of, say, 3 to 6 atmospheres
which latter is preferably supplied in the liquid above that of the coherent column of acetic acid, 110
state. 'Ihe oxygen containing gas must be n especially `when air is employed as the oxygen
containing gas, the said pipe is provided with a
troduced of course under a pressure at least cor
responding to that ci the whole coherent col pressure-releasing valve. Below the mouth of the
umn of acetic acid; it is also possible to introduce said outlet pipe, an inlet pipe protruding -into
the oxygen-containing gas at a still higher pres the top of the vessel is arranged through which 115
sure for example up to about 6 atmospheres above pipe the cold acetic acid is supplied to the upper
the pressure of the column of , acetic acid. When zone of the vessel. A siphon pipe is further pro
working with pure, or practically pure, oxygen vided at the upper region of the lower zone of the
the lofwest pressure which is necessary is gen vessel the bend of which siphon pipe is slightly
erally employed, whereas a corresponding partial below the mouth of said inlet pipe protruding into 19.0
pressure of oxygen, and, accordingly, a higher the top of the vessel. If the process is carried out
total pressure, is used when air, or air enriched under the said increased pressure vthe air pipe of
in oxygen, containing, say, 40 per cent of oxygen, the siphon pipe is led into the head part of the
is employed.

50

vessel, above the mouth of the inlet pipe protrud

. The temperature of the lowest zone is generally ing into the top of said vessel and below the mouth 19,5'

maintained between about 30 and about 100 C., of the outlet pipe provided with the said pressure
preferably between about 50 and about '70 C. releasing'I valve. The said Siphon pipe serves to
Since the reaction develops a good deal of heat, the withdraw acetic acid from the said lower zone and
desired temperature must be regulated by cooling. is connected with a vaporizer the bottom of which
55 Ihis cooling may be effected by means of ex
is connected to a cooler. The top of the vaporizer
tern'al cooling jackets or coils arranged round the is connected to a distillation column or tower,
said zone, or also of cooling devices, such as coils, for example to about the middle thereof, a de
arranged within the said zone. We prefer, how phlegmator being arranged at the top of said
ever, to regulate the temperature in the said zone tower. The reaction mixture with-drawn from
60 by continuously withdrawing a considerable por
the lower zone of the reaction vessel by means of
tion of the liquid reaction mixture from the up said Siphon pipe is led into the said vaporizer
per region of the said lowest zone, externally cool-ing said portion, preferably by a thermosiphon where part of the acid and the whole of the alde
cooler or similar cooling system, and returning hyde are vaporized, the vapours being led into
the cooled liquid into the' lower region of the said said distillation tower, at the bottom of which
zone. This arrangement has the further advan the acetic acid is withdrawn through a cooler,
tage that the reaction mixture is circulated in whereas the aldehyde vapours escape through the
the same direction as the oxygen containing gas dephlegmator and are returned, after cooling
and the aldehyde whereby a very efficient mixing and condensation, into the lower zone of the re
is obtained. It is very advantageous to eifect as action vessel. Acetic acid free from aldehyde but
quickly as possible this circulation of the reaction still containing the whole of the catalyst, if such
be employed, is withdrawn from the said va
mixture.
The oxygen and the aldehyde are usually em porizer, cooled in the cooler at the bottom of said
-ployed in about equimolecular proportions; it is, vaporizer, and lifted by means of a circulating
however, possible'to take a slight excess, say up pump or a similar lifting device, into the said

vo

13!

Mr,

I4@

15

1,951,789.

inlet pipe which protrudes into the top of the acetic acidinto zone 2 and then, if not absorbed
vessel.
by the acetic acidfas is the case with _the aldehyde,
.If desired, iiller bodies, such as Raschig rings, escape through' the outlet 12. The acetic acid
maybe Varranged in the upper zone and/or in the which has reached the bottom of zone 2`is led into
lower zone or zones, but the reaction proceeds zone 1 through the pipe 4 or, while dispensing
quite smoothly without ller bodies.
' with the lowerportion of pipe 4, through the
The reaction vessel and the other parts of the cooler, whereas a quantity of acetic acid corre
apparatus must be constructed with materials sponding to that formed by the oxidation of the
which are not attacked by the warm acetic acid; aldehyde is continuously withdrawn from` zone
10 such materials may be metals, for example tech 1 by means of Siphon-pipe 7. I_f the oxygen-con 85
nically pure aluminium, or special steels, such as taining gas be employed under increased pres
chrome nickel steels, or ceramic materials.
sure the pressure of the acetic acid is released in
The nature of the invention'will be further the pipe 7 before the acid is allowed to enter the
described with reference to the accompanying vaporizer 8. _In this case. the siplion at the top
15 diagrammatical drawing which illustrates an ar of pipe 'I communicates with the top of zone 2,
rangement of apparatus according to this inven above the mouth of pipe 11. The crude acetic
tion but the invention is not restricted to the facid thus withdrawn is led into the vaporizer 8,
particular arrangement shown.
which is heated, for example by the internal heat
A tubular vessel is composed by two superim-` ing coils shown, in such a manner that the level
20 posed parts 1 and 2 the latter of which bears at of the liquid therein is always kept at the same 95
its top and outlet pipe 12. The vessel 1 ybears. height; part of the acid flows down at the bottom
near, or respectively at, its bottom two inlet pipes of said vaporizer through the cooler 9 where it is
13 and 15 and above the inlet 13 a sieve plate 14. cooled to about 20 C and then pumped, by
A'check valve or nozzle plate 3 separates the means of the pump 10, through the pipe 11, into
25 vessel 1 from the vessel 2 so that two zones are the top of lzone 2. This cold acetic acid contains 100
formed. A pipe 4 connects the lowest part of the whole of the catalyst withdrawn with the
" vessel 2 with the lower part of vessel 1. Pipes crude acid. The mixture of acetic acid and al
5 and 5' connect a thermo-Siphon cooler 6 to dehyde vapours which escapes from the vaporizer`
the upper and lower regions of the vessel l. The ' 8 is led into about the middle of the still column
upper region of vessel l is connected through a 1'7 by means of the pipe 16, so that' any unaltered 105
Siphon-pipe I to a vaporizer 8 the bottom of aldehyde escapes in the vapour state through the
which latter is connected to a cooler '9. A cir
dephlegmator 18 and is'then condensed in the
culating pump 10 is connected to said cooler 9 cooler 20, from where it is returned into the re
and by the pipe 11 to the top of vessel 2. The action vessel 1. Pure acetic acid is withdrawn
top of the vaporizer 8 is connected throughthe through the cooler 21 at the bottom of the column.- 110
pipe 16 to the middle portion of a distillation col
What we claim isz
umn 17 which is provided with a dephlegmator
1. In the continuous oxidation of acetaldehyde
18. The dephlegmator 18 is connected through a to acetic acid by reacting an oxygen containing
pipe 19 to a cooler 20 which latter is connected gas with acetaldehyde in the presence of acetic
40 to the inlet pipe 15. The bottom of the column 17 acid while continuously supplying acetic acid car 115
is connected to a cooler 2l from which a pipe 22 rying a. catalyst comprising manganese acetate
may lead to a storage vessel (not shown). The to the reaction mixture, and drawing off a -quan
air pipe of the Siphon-pipe '7 may also protrude tity of acetic acid corresponding to that formed
into the top of zone 2 abovethe place where the from the aldehyde, the step which comprises car
pipe 11 protrudes into the vessel, and pressure rying out the oxidation in a vertical, coherent 120
releasing valves may be arranged in pipe 12 and column of acetic acid while introducing the oxy
in pipe 7 between the bend and vaporizer 8. Pipe gen containing gas and liquid acetaldehyde into>
4 may also be connected to pipe 5.
the lowest region of said coherent column and
On working with the above 4described appara supplying cold> acetic acid free from acetaldehyde
tus,
the
Vessel,
or
zone,
1
is
completely
filled
with
50
and carrying the catalyst to the uppermost re# 125
acetic acid, which may contain about 0.2 per cent gion of said coherent column in a quantity suf
by weight of manganese acetate, and vessel, or iicient to superimpose a column thereof to the
zone, 2 also up to about the dotted line just below aforesaid column.
the mouth of pipe 11. Liquid acetaldehyde is in
2. In the continuous oxidation of acetaldehyde
troduced through pipe 15 or into the pipe 5', to acetic acid by `reacting an oxygen containing 130
whereas about an equivalent quantity of oxygen gas with acetaldehyde in the presence of acetic
or a'corresponding amount of air or of a similar
acid While continuously supplying acetic acid car
mixture containing oxygen, as for example air
enriched in oxygen, is supplied through the pipe , rying a catalyst comprising manganeseacetate

By the heat evolved by the reaction the to the reaction mixture, and drawing off a quan
temperature in zone 1 soon rises to from about 50 tity of acetic acid corresponding'to that formed
to about l60" C. A considerable portion of the from the aldehyde, the step which comprises car
acetic acid contained,A and moving upwards, in rying out the oxidation in a vertical, coherent
the vessel 1 is continuously run through the ther column of acetic acid, while introducing the oxy

60 13.

65

las

mo-siphon cooler 6, in order to maintain the gen containing gas and liquid acetaldehyde into' 140
said temperature in the vessel l, the degree of the lowest zone of said coherent column and
cooling depending on the external temperature. supplying to the uppermost >zone of said column,
The top of vthe vessel 2 is continuously supplied in aquantity sufficient to superimpose a column
with acetic acid carrying on the catalyst, so that thereof to the aforesaid column, cold acetic acid
the temperature is about 20 C. at the top and
from about >30 to about 40 C. lat the lower part
of zone 2. Gaseous products, such as nitrogen
and any residual aldehyde and carbon dioxide

free from acetaldehyde, carrying the catal st 145

and obtained by continuously withdrawing, from


the lowest zone ofthe column, a quantity of ace

tic acid corresponding to the amount of aldehyde


contained or formed in zone 1 pass through the which ls continuously introduced, subjecting lthe
75 Anozzle plate 3,` ascend through the down iiowing acid withdrawn to partial distillation until the

ipcryeo ~

vapours are free from aldehyde, and cooling the tion until the vapours are free from aldehyde and
residual acid.
_
y
cooling the residual acid, and supplying acetic
3; In the continuous oxidation of acetaldehyde acid withdrawn from the lowest region oi.' said
to acetic acid by reacting an oxygen containing superimposed column to the 'lowest region of said
gas with acetaldehyde in the presence of acetic
acid while continuously supplying acetic acid
carrying a catalyst comprising manganese' ace
tate to the reaction mixture, and drawing oi
a quantity of acetic vacid corresponding to that
10 formed from the aldehyde, the step which corn
prises carrying out the oxidation in a vertical co
herent column of acetic acid, while introducingr
the oxygen containing gas and liquid acetalde
hyde- into the lowest zone oi said coherent col
15 umn, the temperature of which zone being regu

iated by continuously withdrawing a portion of


the liquid reaction mixture from the upper region
of said zone, externally cooling said portion and
returning it into the lower region of said zone,
20 and supplying cold acetic acid free from acetalde
hyde to >tloe uppermost zone of said colic-rent

80
6. An apparatus for carrying out the continu
ous oxidation ot acetaldehyde to acetic mid, com
prising, in combination,_a tower-shaped reaction
vessel, means capable of restricting the cross-sec
tion in the upper half of said vessel at least near 85,
the middle of said vessel,at least two pipe in~
lets at about the bottom of said vessei, a thermo
Siphon cooler connected to about the upper region
of the lower Zone, formed in said vessel by said
restricting means, and to about the bottom of
lowest zone oi' the wholecolumn.

said vessel, a pipe connecting the lower region


of the upper zone, formed in said vessel by said
restricting means, to about the bottom of said

vessel, an inlet pipe protruding into the top of


said vessel, an outlet pipe connected to the tcp 95
of said Vessel and a siphon pipe, which is con
column in a quantity sufficient to superimpose a nected to tbe upper region .of said lower zone
column thereof to the aforesaid column.
and the bend of which is slightly below tbe mouth
4. In the continuous oxidation of acetaldehyde of said inlet pipe protruding into the top of said
'
25 to acetic acid by reacting an oxygen containing vessel.
100
gas with acetaldehydein the presence of acetic
7. in apparatus for carrying out tbe continu
acid while continuously supplying acetic acid car ous oxidation of acetaldehyde to acetic acid, com
rying a catalyst comprising manganese acetate to prising, in combination, a tower-shaped reaction
the reaction mixture, and drawing on? a quantity vessel, means capable of restricting the cross--secn
30 of acetic acid corresponding to that formed from tion in the upper half of said vessel at least near 105
the aldchyde, lthe step which comprises carrying the middle of said vessel, at least two pipe in
out the oxidation in a Vertical coherent column lets et about the bottom of said vessel, a thermo
of acetic acid,` while introducing the oxygen con siplion cooler connected to about the upper re
, taining gas and liquid acetaldehyde into the low gion. of the lower' zone, formed in said vessel by
35 est zone of' said coherent column, the temperature said restricting means, and to about the bottom 110
of which zone being regulated by continuously of said vessel, a pipe connecting the lower region
withdrawing a portion of the liquid reaction mix of tbe upper zone, formed in said vessel by said
ture from the upper region of said zone, 'external

restricting means, to a 'thermo-Siphon cooler, an


1y cooling said portion and Vreturning it into the inlet pipe protruding into the top oi said vessel,
40 lower region of said zone, supplying cold acetic an outlet pipe connected to the top of said vessel 115
acid free from acetaldehyde to the uppermost and e. Siphon pipe, which is connected to thel
zone oi said coherent column in a quantity suf~ upper region of said lower zone and the bend of
iicient to superimpose a column thereof to the which is slightly below tiie mouth of said inlet

aforesaid column, withdrawing acetic acid from pipe protruding into the top of said vessel.
8. An apparatus for carrying out the continuous 120
and supplying it to the lowest region of th oxidation of acetaldeliyde to acetic acid, compris
whole column.
1
'
ing, 'in combination, a tower-shaped reaction
5. In the continuous oxidation of acetaldehyde vessel, means capable of restricting the cross
to acetic acid by reacting an oxygen containing sec'tion in the upper half of said vessel at least
50 ygas with acetaldehyde in the presence of acetic near the middle of said vessel, at least two pipe 125
acid while continuously supplying acetic acid car inlets at about the bottom of said vessel, a thermon
rying a catalyst comprising'manganese acetate Siphon cooler connected to about the upper region
45 >the lowest` region of- said superimposed column

to the reaction mixture, and drawing olii a qu n


tity of acetic acid corresponding to that form .

of the lower zone, formed in said vessel by said


restricting means, and to about the bottom of
55 from the aldeliyde, the step which comprises car said vessel, a pipe connecting the lower region 130
rying out the oxidation in a Vertical coherent of the upper zone, formed in said vessel by said
column of acetic acid, while introducing the oxy restricting means, to said tliermo-siphon cooler,
gen containing gas and liquid acetaldel'iyde into an inlet pipe protruding into the top of said
the lower region of the lowest zone of said col-1 vessel, an outlet pipe connected to the top of said
60 umn, the temperature of said lowest zone being vessel and a siphon pipe, which is connected to 135
regulated by continuously withdrawing a portion the upper region of said lower zone and the bend
of acetic acid from the upper region of said zone, of which is slightly below the mouth of said
externally cooling said.` portion and returningit inlet pipe protruding into the top of said vessel,
into the lower region of said lowest zon'e, supply a> vaporizer connected to said Siphon pipe, a, dis
tillation column connected to the top of said 140
65 ing to the uppermost zone of said coherent col
umn in a quantity suilicient to superimpose a vaporizer, a cooler arranged at the bottom of said
column thereof to the aforesaid column, cold ace vaporizer, and a pipe connecting said cooler with
tic acid. free from- aldehyde and carrying tire said inlet pipe protruding4 into the top of said
catalyst, and obtained by continuously withdraw vessel.
ing from the lowest zone of the column a quan
MARTIN MUELLER-CUNRADI. 145
tity of ~acetic acid corresponding to the amount
KURT PIERQH.
of aldehyde which is continuously introduced,`
HELIMUT GIEHNE.

subjecting the acid withdrawn to partial distilla


75

150