Jan. 29, 1946. D. C.

l-UE 2,393,778
PROCESS AND APPARATUS FOR THE PYROLYSIS OF ORGANIC COMPOUNDS
 Patanted Jan. 29, 1946 2,393,778
UNITED STATES PATENT OFFICE
- . . . . 2?????s .. . . . . .
PRocess AND ArPARATUs ron TEnery
ROEYss OF ORGANIC controUNDs
David C. Bun, Kasport, ena, agaor or by
mesne aalgaetate, to
Corporation, Kingsport, Tenn., a corporation
of Virginia
Application September 29, 1945, serial No. 504,524
2 Claims. (C. 260-SSO)
This invention relates to a process and ap tures of the order of 1000 C. or higher. Fifth,
paratus for the pyrolysis of organic compounds the material must be of such a nature that it will
and more particularly to a process and apparatus have no adverse catalytic effect when in contact
for the pyrolysis of ketenizable organic comi with the materials being processed. Finally, the
pounds such as acetone, acetic acid and the like material must not change in composition or phys
to produce ketene and other valuable products. ical characteristics such as by internal grain
This application is a continuation-in-part of growth with accompanying development of brit
my copending application, Ser. No. 375,051, fled tleness after being in use for some time.
January 8, 1941, which is a division of my ap To the best of my knowledge and belief, in spite
plication, Ser. No. 186,151, now U. S. Patent O of the vast accumulation of knowledge and ex
2,232,705. perience on the part of those skilled in the art
In the pyrolysis of acetone, acetic acid and and the prophetic statements in the patent and
other ketenizable compounds to produce ketene technical literature, no one, until the advent of
and other products, it has heretofore been the the present invention, has ever provided a process
practice in carrying out the pyrolysis operation to 15 for pyrolyzing ketenizable organic compounds
employ pyrolysis chambers or apparatus con wherein the pyrolysis reaction could be carried
structed of carbon, copper, silver, brass, bronze, out at maximum efficiency and without shut
clay, silica and various other materials. Such downs, severe material losses and other undesir
materials have numerous disadvantages which able results directly traceable to failure of the
render their use wholly impractical or impossible 20) material employed in the pyrolysis vessel. In
when carrying out the pyrolysis reaction at tem fact, so vital is the matter of carrying out the
peratures of the order of or in excess of 1000 C., pyrolysis reaction in contact win a material
particularly when low vacuum conditions in the which will withstand the extremely severe condi
apparatus are employed. For example, when it tions met with, that thereon depends the success
has been attempted, in accordance with the teach or failure, or, in other words, the operability or
ings of the prior art, to pyrolyze acetic acid to inoperability, of the process.
ketene in copper coils at temperatures in the This invention has for an object to provide an
vicinity of 1000 C. or higher, it has been found improved process of and apparatus for the py
that after only a few days' operation, the copper O
rolysis of ketenizable organic compounds such
pyrolysis chamber had become so severely de as acetone, acetic acid and the like. A further
teriorated as to be completely unuseable for fur object is to provide a process for the production
ther operation. Silver coills are likewise so easily of ketene by the pyrolysis of ketenizable organic
burned up under high temperature conditions as compounds under extremely severe temperature
to be totally unuseable. Coils or pyrolysis cham and oxidation conditions. A still further object
bers constructed of clay and silica, while able un 35 is to provide a process for the pyrolysis of organic
der certain circumstances to resist the relatively compounds attemperatures of the order of, or in
high temperatures employed, are nevertheless excess of, 1000 C. which may be operated con
wholly unfeasible for use in pyrolysis operations tinuously for long periods of time without burn
because of the fact that they have such poor heat ing out or other deterioration of the equipment
transfer and because they are so porous. 40 and with a minimum decomposition of the re
It will thus be readily understood that the py actants through catalytic or other action. Other
rolysis of ketenizable organic compounds, such as objects will appear hereinafter.
the production of ketene by the pyrolysis of acetic These objects are accomplished by the follow
acid presents a multiplicity of problems, the solu ing invention which, in its broader aspects, com
tion of which is exceedingly difficult. First, the 45 prises pyrolyzing ketenizable organic compounds
pyrolysis reaction must be carried out in a reac such as acetone, acetic acid, and other ketenizable
tion vessel constructed of a non-porous material. compounds at high temperature in a heat-resist
Second, the material must be able to withstand ant and oxidation-resistant pyrolysis vessel com
heat shock and not burn up under the high tem posed of a catalytically inactive high chromium
perature conditions of the reaction. Third, the steel alloy containing nitrogen and small frac
material must have sufficient strength to with tions of manganese, nickel and carbon, such as
stand high pressure, either from the outside or an alloy containing 18-40% chromium, about .2%
from the inside of the vessel. Fourth, it must be to about 1.5% nitrogen and small amounts, gen
able to stand up under the severe oxidizing and erally not exceeding 1%, of manganese, nickel
reducing action of the heating flame attempera and carbon, the balance being iron. Obviously, as
 2 2.393,778
known to skilled metallurgists, small fractions of shown. The preheated vapors thus pass through
a percent of other elements, such as sulfur and conduit 9 into the pyrolysis chamber in which
silicon, may be present as impurities. they are heated to a temperature of 600 to 900
In extensive research carried out for many C. With an outside temperature of the Order of Or
years on large scale commercial Operations, I in excess of, 1000 C. by means of open flame
have found that pyrolysis of ketenizable organic heater to or other equivalent source of heat. As
compounds to produce ketene and other desired Shown, both the preheater and the pyrolysis ves
products at high temperatures of the order of sel may be enclosed within a chamber construct
1000° C. can be successfully carried out only in ed of any appropriate heat-resistant material
O such as fire brick.
pyrolysis vessels of a relatively extremely limited Provision is made by means
chemical constitution. These materials are of baffle 4 to cause the flame to travel in a more
stee alloys containing a relatively high chronium or less circuitous path before reaching the py
content and a relatively low content of other rolysis chamber or the preheater. Partition 5
materials, as indicated. I have found that the divides the preheating chamber from the pyroly
, alloy manufactured and sold by the Babcock and 15 sis chamber, but leaves an opening for the pas
Wilcox Tube Company of Beaver Falls, Pa, um Sage of the heating medium from the pyrolysis
der the trade name “Crolloy 27” is a particularly chamber to the preheating chamber. Under the
valuable material for this purpose. This is a influence of the extremely high temperature pre
high chrome steel alloy containing 2% chro 20
vailing within the pyrolysis vessel the acetic acid
mium, a maximum of 0.2% carbon, 1%. nickel, or other ketenizable organic compound is cracked
about 2% nitrogen C.12 to .25%) and the bal to ketene which passes, together with any other
ance iron. Other alloys having components products of reaction from the pyrolysis cham
within the limits designated in the previous par ber, by means of conduit to condenser 2
agraph are obtainable upon the open market, where the ketene gas is separated from conden
such for instance as the alloy manufactured and 25 sible components, including by-products and un
sold by National Tube Co., Pittsburgh, Pa., con changed raw materials, which latter are removed
taining 24-26% chromium,.6% manganese, 1.5% by suitable draw-off means as shown. If de
silicon, 2% carbon and 3% nitrogen, each of sired, and as shown, a suitable catalyst neutral
the last-four-mentioned ingredients being a mark 30 izer may be introduced into the vapors passing
imum, and the balance being iron. . through conduit before they reach the con
In the following examples and description I. denser 2. The ketene gas produced may then
have set forth several of the preferred embodi be conducted to any other desired reaction zone
ments of my invention but they are included for conversion to other valuable products such
merely for purposes of illustration and not as a 35 as acetic anhydride by reaction with acetic acid.
limitation thereof. . In operating the process as above described,
The single figure of the accompanying draw the pyrolysis reaction may be conducted at at
ing is a diagrammatic elevational view, in pa InoSpheric or super-atmospheric pressure, al
tial section, and in the nature of a flow sheet ill though in general it is preferable to employ re
ustrating a typical method of pyrolizing keten 40 duced pressure in order to facilitate the reac
izable organic compounds in accordance With the tion. As indicated, the products of the reaction
instant invention. may be disposed of in any desired manner.
A clearer understanding of my invention will In order more fully to set forth the distin
be obtained from consideration of a typical proc guishing features of my invention and to illus
ess and the apparatus employed therein in ac 45 trate the very marked and unpredictable increase
cordance with my invention. . in efficiency of the process for pyrolyzing keten
Referring to the drawing: izable organic compounds, by carrying out the
the numeral designates a suitable pipe reaction in a pyrolysis vessel composed of the
through which may be led a ketenizable organic particular high chrome-nitrogen-steel alloy de
compound, such as acetic acid, flow of the Com 50 scribed above, a further discussion of the wide
pound to the vaporizer 2 being controlled by discrepancy between the results obtained in py
vaive 3. rolysis processes carried out in vessels composed
In the vaporizer 2, which may take the form of other alloys and the results to be obtained by
of a coil, still pot, or other vessel equipped With carrying out the process in accordance with my .
a suitable source of heat such as a heating jacket, 55 invention, is desirable.
electrical resistance coils or other means, the Reference has been made to the fact that if
acetic acid is vaporized and then conducted the pyrolysis chamber is constructed of copper,
through conduit 4 to preheating vessel 5, which it is substantially worthless because of the fact
may likewise take the form of a heating coil, that it burns out almost immediately Ender the
metal still pot or other appropriate device, and O temperatures encountered and the severe oxidiz
is there heated to a temperature of approximately ing conditions met with during the reaction. For
600 to 800 C. - example, I have found that after a very short pe
In order to facilitate the ketene reaction a suit riod of useage under such conditions a copper
able catalyst, such as a phosphate compound vessel loses all its strength and completely dis
may be admixed in small quantities with the integrates. In addition even for such short pe
acetic acid vapors passing through conduit , riod, it is necessary to protect the outer side of
the catalyst being conveniently supplied to the the pyrolysis vessel from attack by the flames.
acetic vapors passing through conduit 4 through ordinarily used to heat such vessels. Even when
conduit 6 controlled by valve. protected the pyrolysis vessels fail and the proc-.
. . The numeral 8 designates a pyrolysis vessel 70 ess is brought to a standstill.
It might be supposed that other alloys such as
which may take the form of a heating coil sim
ilar to that of coil 5. This vessel is constructed Nichrome or other alloys having high chronium
of the high chrome-nitrogen steel alloy described and nickel content might be employed. How
above. Pyrolysis vessel 8 is connected with the ever, I have found that although such alloys will
preheating vessel 5 by means of a conduit 9, as 75 resist fairly well the oxidizing atmosphere en
 9,808,778 3
countered, as well as the high temperatures pre Nichrone steels are employed, by the use of the
Valling on the outside of the vesses, these alloys high chrome, nitrogen steels described above,
are absolutely worthless when employed in pyroly yields of the order of 90-95% can be readily ob
sis vessels for the production of ketene because tained. Thus, I have provided a process and ap
their catalytic activities are so great that even paratus which will accomplish to an unusual de
at moderate temperatures almost complete care gree of eficiency, a very important chemical re
bonization of the ketenizable substances fed action with much lower cost of operation than
through the apparatus takes place. possible with alloys usually employed for such
Other steel alloys have been found to be almost purposes.
equally deficient for use in the pyrolysis reaction O What claims:
for one reason or another. For example, a well 1. The process of pyrolyzing ketenizable organic
known stainless steel such as Type-36, when compounds such as acetic acid to produce retene
employed in the pyrolysis vessel has approxi and other products which comprises pyrolyzing
mately ten times the adverse catalytic activity of the ketenizable compound in the vapor phase at
the high chrome, nitrogen steel described above. a temperature of the order of 1000 C. in a pyro
This can readily be determined by measuring the lysis vessel constructed of a non-catalytic high
amount of carbon formed by passing a known chrome, nitrogen steel alloy containing 18-40%
amount of acetic acid over the metal at an ele chromium, about 2 to about 1.5% nitrogen and,
wated temperature and measuring the quantities small amounts of manganese, nickel, and carbon,
of the decomposition gases given up when a known 2C the balance being iron.
amount of the acid is passed over. Furthermore, 2. An apparatus for thermally decomposing
the heat resistance of stainless steel alloys such ketenizable organic compounds to produce Ketene
as Type-316 or Type-304 is such that they are and other products which comprises a pyrolysis
entirely unsuitable for any continued use above vessel constructed essentially of a non-catalytic,
an outside temperature of about 700 C., which is high chrome-nitrogen steel alloy containing
a temperature entirely unsuited for successful 18-40% chromium, about .2-1.5% nitrogen and,
large-scale Operation. small amounts of manganese, nickel and carbon,
In addition to deficiencies of such alloys from and the balance iron, means for introducing
the catalytic standpoint, they present the draw ketenizable organic compounds into the pyrolysis
back that, even under the most favorable cir 0 vessel and means for heating the vessel to pyroly
cumstances, they result in the production of very siis temperatures.
poor yields. For example, whereas yields of the DAV DC, U.
order of only 20 or 30% are obtainable when