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Jan. 3, 1933. H.

WALTER ET AL 1,892,742

Filed Feb. 19, 1931 2 Sheets-Sheet >1

Jain. 3, 1933. I H.‘ WALTER ET AL ‘1,892,742

Filed Feb. 19. 1931 2 Sheets-Sheet 2

. IBM. 420
Patented Jane}, 1933 1,892,742




Application ?led Iebruary'm, 1931, Serial No.' 517,014, and in Germany January 26, v1928.
The present invention relates to the pro comparatively high temperatures over car
duction of acetone from acetic acid, acetylene, bonaceous catalysts contained in chambers,
alcohol, acetaldehyde, ethyl acetate or other the walls of which consist of substances,
ketonizable substances‘ or mixtures of the WlllCll, during the process of the reaction, have
same by passing their vapors mixed with no substantial decomposing action on the
steam at elevated temperatures over catalysts, acetone formed. The temperatures are those
disposed in chambers constructed of particu generally employed .in' the manufacture of
lar material. _ acetone, that is, between 400 and 500° 0.
It is already known, for example, tocon Examples of suitable carbonaceous cata
vert acetic acid into acetone by passing its lyspts ' are wood charcoal, animal charcoal,
vapors together with steam over lime, iron, bone charcoal, activated charcoal and the like,
strontium and the like. These processes are, which may, if desired, be covered or impreg
however, attended with the disadvantage nated with catalytically active substances,
> that the’ acetone formed begins to decompose which themselves also have no decomposing
ll even at temperatures at which the conversion action on the acetone, such as oxides, acetates
is not yet quantitative. _ and the like'of iron, calcium, zinc, cerium,
Attempts have also been made to convert thorium, etc.’ '
the vapors of dilute acetic acid into acetone The choice of the catalysts depends on the v
by passing the same over heated coke. Iron nature of the initial material.
contact tubes have been used for this purpose, The hitherto known processes, however, 70
including tubes of abnormally large surface also possess the considerable disadvantage
area. -In this case the catalytic action was that the catalysts employed lose their activity
entirely due to the iron walls, and was at after a relatively short time, thereby giving
tended with the same defects as when em rise to a considerable decline in production.
ploying pure iron for the catalysis. This is avoided by employing catalysts, con
_ These defects have led to the mistaken con sisting of or containing carbonaceous mate'
clusion that the poor yields, hitherto ob rial, as described above. '
tained in the above described rocesses for The following materials, which have no
preparing acetone, are attributa le to the low detrimental e?ect on the process of catal sis,
heat conductivity of the catalysts employed. may be suitably employed for the walls 0 the
For this reason it has alsolbeen proposed to contact apparatus : copper, copper alloys, alu
employ catalysts, prepared by coating metal mmlum, acid-resisting iron alloys, such as
balls with catalytically reacting substances, Krupp’s V2a steel, ceramic masses and the
such as lime, baryta and the like.‘ These like. Any copper alloy is suitable, but espe
combined catalysts were employed for the cially alloys with zinc, tin, silver, nickel.
conversion in contact chambers of steel, cop The so-czilled Krupp’s V-steel (V2a,'V4a etc.)
per, aluminum and the like. The same dis contains as essential constituents besides iron,
advantages were encountered, however, as approximately 18% of chromium together
when employing lime, baryta and the like as with nickel and, if desired, molybdenum or
catalysts. .
According to this invention it has been un copper.
The V2a steel which is a'well known
is a steel containing chromium and
ex tedly found that. the reaction can not
0 y be carried out at relatively high tem nickel. When acetylene, alcohol or other
peratures but that the already formed ace non-acid reacting products are employed as
tone can be prevented from decomposing, if, initial materials, the walls of the contact
in the production of acetone from acetic acid, chamber may consist of iron, since in this case
acetylene, alcohol or other ketonizable sub iron also will have no substantial decompos- _.
stances or mixtures of the same, the process ing action on' the acetone ‘formed, and can,
of catalysis is e?ected by diluting the vapors therefore, be included in the materials, which, '
with steam and passing the diluted vapors at during the course of the reaction have no,
2 1,892,742
substantial decomposing action on the ace tion of the apparatus through the conduit 1.
tone formed. Referring to Figure 2, the actual assembly
In the process of ketonizing acetylene, al shown is especially devised as previously
cohol and the like, by employing catalysts, mentioned for ketonizing very impure and
which essentially contain carbon (active dilute acetic acid, such as wood vinegar, 70
charcoal) and some zinc oxide or cadmium which ‘contains tarry substances in solution.
oxide, the disadvantage very readily occurs The apparatus represents a multiple three
that, during the reaction, the zinc oxide or stage system. The ?rst stage 1 is operated
cadmium oxide escapes with the reaction va at an excess pressure of, for example one
10 pors, whereby the zinc or cadmium content atmosphere, the second stage 2 at, for exam
is lowered and consequently after a short time ple, normal pressure, and the third stage 3
the activity of the catalysts decreases. This at, for example, about 1/2 an atmosphere.
disadvantage can be readily overcome by de In order to operate each of these stages there
positing'strongly basic substances, such as are required: a wood vinegar vaporizer V,
15 lime, baryta and the like, together with the a super-heater U and a contact chamber K. 80
zinc, or by previously combining the zinc or Preheated Wood vinegar ?ows from a suit
cadmium with the same. able container B ?rst into the vaporizer
An economical and particularly advanta V III (which co-operates with the super
geous modi?cation of the process consists in heater U3, contact chamber K3 and the adja
using inexpensive initial materials, such as cent cooler), in which a. working pressure
wood vinegar (pyroligneous acid). For this of about 1/2 atmosphere is maintained by
purpose a catalyst, such as wood charcoal, is means of a vacuum pump D. Crude acetic
with advantage employed, the regeneration acid is vaporized in V III, the vapors heated
of which need not be taken into consideration, in Us to the temperature required for the 90
owing to the low cost of the material. In catalysis, and thereafter the conversion into
order to carry out the process continuously acetone effected in the contact chamber K,.
and uniformly and in order to maintain the The resulting va or mixture is then con
maximum e?iciency of the ketonizing reac densed in the adJaccnt cooler E, still at a
tion, a contact chamber is employed, into pressure of % an atmosphere.
30 which the fresh contact mass is continuously The gases resulting from the catalysis
fed, and from which the spent catalyst is at (chie?y carbon dioxide) are aspirated by
the same time removed. - the air pump D and freed from the accom
For this purpose a reaction chamber, pro panying acetone in the scrubber S. The
vided with valved chambers or the like, is acetone-containing product of catalysis is 100
' employed, by means of which fresh catalyst, conveyed by means of the pump P3 into the
for example wood charcoal, can be continu rectifying column R and there worked up
ously or semicontinuously introduced during into acetone.
the operation, whilst the spent catalyst (char The non-vaporized portion of wood vin
coal) can be withdraw also continuously or egar and the tar are removed from the lower
40 semicontinuously from the bottom of the con portion of V III by the pump P1 and pumped
tact apparatus. into the vaporizer V II, which operates at
In the drawings : normal atmospheric pressure. Here vapori
Figure 1 is a diagrammatic representation zation takes place in a manner similar to that
of one form of apparatus em loying the described above, after which the resulting 110
45 aforesaid valved chambers and %igure 2 is vapors are superheated in the superheater
a diagrammatic representation of a complete U2 and converted into acetone in the contact
apparatus particularly for ketonizing. very chamber K2. The resulting mixture of ace
impure and dilute acetic acid. tone vapor and water vapor which also con
Referring to- Figure-4A1 the contact appa tains carbon dioxide, is then condensed at
ratus consists substantially of the reaction normal atmospheric pressure in a heating
chamber a, which is ?lled with contact ma coil which is mounted in V III, and thereby
terial, for example granulated wood char effects the above described vaporization in
coal 6. The reaction chamber a is surround V III. After the product of catalysis from
ed by a hot jacket 0. Valves d1 and d2 are system 2 has given off its heat of vaporiza 120
disposed in the upper and lower portions of tion in the vaporizer V III and has con
the reaction chamber respectively. Fresh densed, it is pumped together with the prod
contact material can be introduced periodi uct of the catalysis from system 3 by the
cally or continuously from a hopper-like pump P_,, for example, into the rectifying
storage container'e through the upper valve column B.
60 (11 and spent COIItaIfTDafBI‘lHLbBJSjiZlldI‘ilWll
The residue of wood vinegar and tar re
through the valve (12 situated at the lower maining in V II after vaporization is ?nally
end of the reaction chamber. The acetic acid forced by the pump Pg into the vaporizer
steam vapors are introduced into the appa V I in which vaporization is effected at one
ratus at d, whilst the acetone formed escapes atmosphere excess pressure by means of fresh 130
65 together with the steam from the upper por steam. The vaporization is carried out to
1,892,742 3 .

such an extent that substantially only liquid‘ 'of oxides and acetates of iron, calcium, zinc,
tar remains behind, which is drawn off at cerium and thorium. 7
the lower end of the still. The vapors are 6. The process set forth in claim 1, where
heated, as described above, by the superheat in the catalyst is periodically fed and the .
er U1 and then converted into acetone in the spent catalyst is periodically removed from 70
contact chamber K1. The resulting Vapor the reaction chamber. _
mixture is condensed at one atmosphere ex 7. The process set forth in claim 1, where
cess pressure in a heating coil, which is in the catalyst is continuosly fed and the
mounted in V II, and thereby gives off its spent catalyst is continuously removed from
10 heat of vaporization to the wood vinegar, the reaction chamber.
which is vaporized at normal pressure in 8. The process set forth in claim 1, where
‘V II as described above. The liquid mixture in the steps are carried out in stages so that
of acetone and water condensed under pres the vaporous product of catalysis of one stage
sure together with the acetone-containing so_ is employed for vaporizing fresh quantities of 80
15 lutions from V III and the ad]acent cooler a material in a later stage.
are aspirated from the system 3 by the pump. 9. The process set forth in claim 1, where
1);, and forced into the rectifying column. in the steps are carried out in stages so that
The non-condensable gases (carbon dioxide) the vaporous product of catalysis of one stage
resulting. from the catalysis are collected by is employed for vaporizing fresh quantities 85
20 means of vdeaerating leads and conveyed to of a material in a later stage, the hot roduct
the cooler E, which is arranged behind the of catalysis of the ?rst stage being irectly
system 3. From this point the gases are as subjected to recti?cation.
pirated by the air pump D and freed iI‘. the10. The process set forth in claim 1, where
scrubber S from accompanying acetone by veyedin the vapors undergoing catalysis are con
25 means of water. into the reaction chamber in a super 90
By means of this apparatus considerable heated condition.
economy in heat can be effected, a feature 11. A process of manufacturing acetone
which is of considerable value in ketonizing from a substance containing acetic acid,
. reactions, which are operated with compara which comprises mixing the vapor of the ini
30 tively large quantities of steam. tial substance with steam, and passing the 95
In order to produce as clearly de?ned and mixture into are-action chamber at a tem
uniform a temperature as possible within the perature between 400 and 500° C. in the pres_
contact chamber the gas or vapor mixtures ence of wood-charcoal, the walls of the re
undergoing catalysis are with advantage preé action chamber consisting of a material se
heated to the reaction temperature before the lected from the group consisting of copper; 100
process of catalysis, this being with advan copper alloys of zinc, tin, silver or nickel;
aluminum; steel alloy containing 18%
tage effected in a super heater, the walls of chromium
which have no chemical action on the vapors. with nickel; ceramic masses.
\Vhat we claim is : 12. A process of manufacturing acetone
40 1. A process of manufacturing acetone mixing from pyroligenous acid, which comprises 105
from a ketonizable compound of the group the vapor of the pyroligenous acid
consisting of acetic acid, acetylene, acetalde with steam, superheating the mixture, and
passing the mixture into a re-action cham
hyde. ethyl acetate, which comprises mixing ber at a temperature between 400 and 500° C.
the vapor of the initial substance with steam,
and passing the mixture into a reaction cham of the presence
in the of wood-charcoal, the walls 110
reaction chamber and of the super
ber at a temperature between 400 and 500° C. heating apparatus consisting of a. substancev
in the presence of a ltetonizing catalyst of selected from the group consisting of copper;
carbonaceous material, the walls of the re copper alloys of zinc, tin, silver or nickel;
action chamber consisting of a substance se aluminum; steel alloy containing 18% 115
lected from the group consisting of copper; chromium with nickel; ceramic masses.
copper alloys of zinc, tin, silver or nickel; 13. The process set forth in claim 11,
aluminum: steel alloy containing 18% wherein the catalyst consists of activated
chrominum with nickel; ceramic masses. . charcoal.
2. The process set forth in claim 1, where 14. The process set forth in claim 12,
in the catalyst consists of porous charcoal. wherein the catalyst consists of activated
3. The process set forth in claim 1, where charcoal.
in the. catalyst consists of a carbonaceous ma In testimony whereof we hereunto ailix our
terial containing zinc oxide. signatures this 5th day of February 1931.
(i1) l. The process set forth in claim 1, where HANS WALTER. 125
in the catalyst consists of porous charcoal HERMANN SCHULZ.
containing zinc oxide. I
The process set forth in claim 1, where
in--the catalyst consists of charcoal containing
one of the substances of the group consisting 130