United States Patent Office 3,151,150

atented Sept. 28, 1964

1.
2
cussed in Chemical Week (September 27, 1958), pp.
3,554,450 53-54, Chemical Engineering (June 1, 1957), pp. 42-44,
PROCESS FOR THE MANUEFACTURE OF Chemical and Engineering News (December 1, 1958), pp.
ACRYELONTRLE 49 and 98, and by Sennewald and Steil in Chemie-In
onas Karact, New York, N.Y.; Edna Yadven. Kamiet, genieur-Technik, 30, #7, 440-446 (1958).
executrix of said Josias Kanet, deceased, assignor, by It is the purpose of my invention to provide a process
mesne assign eats, to Edia Y. Kaanet, doing business
as The Kainie Laboratories, New York, N.Y. for the manufacture of acrylonitrile from acetaldehyde
No Drawing. Fied Sept. 4, 1959, Ser. No. 839,570 and hydrogen cyanide which does not require reagents
4 Clains. (C. 260-465.9) other than acetaldeyhde and HCN and does not involve
O by-product recovery, which does not require concentra
This invention relates to a process for the manufacture tion and re-constitution of intermediates, and which gives
of acrylonitrile. More particularly, this invention relates yields in excess of 90% of theory.
to a process whereby acrylonitrile may be manufactured, The basis of my invention is the finding that acryloni
in good yields, from cheap and readily available industrial trile may be obtained in excellent yield by the steps of:
intermediates-acetaldehyde and hydrogen cyanide. (a) reacting lactonitrile (made from acetaldehyde and hy
Acrylonitrile has become an extremely important chem drogen cyanide) with pre-formed acrylonitrile, in the
ical article of commerce, widely used in the manufacture, presence of a basic catalyst, to form alpha,beta'-dicyano
of synthetic rubbers, plastics, fibers, films, plasticizers, dye diethyl ether (alpha,beta'-oxydipropionitrile):
stuffs, pharmaceuticals, solvents and other products.
A tremendous technology has developed and several 20 CH-CH-ON
thousand patents have issued on the manufacture of acry CH3CHOEICN -- CII-CEICN - 9
lonitrile by the dehydration of ethylene cyanohydrin CH2CH2CN
(from HCN and ethylene oxide) and by the reaction of
acetylene with HCN. Lactonitrile (which is isomeric with (b) pyrolyzing the alpha,beta'-dicyanodiethyl ether, at ad
ethylene cyanohydrin) made by the reaction of acetalde vanced temperatures, to form (for each mole of said
hyde and hydrogen cyanide, cannot be dehydrated easily ether) two moles of acrylonitrile and one mole of water
to form acrylonitrile and water, since it tends to decom
pose into the original reagents at advanced temperatures. CH-CH-CN
o - 20EF2=CHCN -- HO
To obviate this tendency of lactonitrile to decompose
into acetaldehyde and HCN, it has been proposed to acyl CHCHCN
ate the lactonitrile and then to pyrolyze the resultant One mole of the acrylonitrile thus obtained is recycled
alpha-acyloxypropionic acid to obtain acrylonitrile and
the organic acid. Thus, lactonitrile is reacted with acetic to the first step of the process, for reaction with the lactoni.
anhydride to form the alpha-acetoxypropionic acid, which trile to form the alpha,beta'-dicyanodiethyl ether. The
is then pyrolyzed to form acrylonitrile and acetic acid. other mole of acrylonitrile is the salable end-product of
(Ritchie, Jones and Burns, U.S. Patent 2,183,357 (1939); Said process.
Miller and Groombridge, U.S. Patent 2,452,672 (1948).) Thus, the overall effect of the process is to form acry
This process requires the use of an additional reagent lonitrile from acetaldehyde and hydrogen cyanide as sub
acetic anhydride-and the recovery and recycling of the 40 stantially the sole reagents.
acetic acid formed. Hansiey (in U.S. Patent #2,333,782 issued November
More recently, a process has been developed for the 9, 1943) has shown that lactonitrile may be reacted with
manufacture of acrylonitrile from acetaldehyde and hy acrylonitrile in the presence of an alkaline catalyst, to
drogen cyanide which involves reacting these compounds form the alpha,beta'-dicyanodiethyl ether.
to form lactonitrile, mixing the lactonitrile with phos I have found that this alphabeta'-dicyanodiethyl ether
phoric acid (nitrile-acid ratio about 2:1) and then spray 45
may be pyrolyzed over a very wide range of tempera
ing this reaction mixture under pressure into a reac ture, in the absence of catalysts as well as in the pres
tion chamber, where it encounters pre-heated oxygen-free ence of dehydration catalysts, in the liquid phase and
combustion gases, at a temperature of about 600 C. in the vapor phase and at subatmospheric, atmospheric
Dehydration occurs in about 0.1 to 0.6 second. Reac and Super-atmospheric pressures, to give excellent overall
tion products are cooled, condensed and separated. 50
yields of acrylonitrile. It must be emphasized that, be
The phosphoric acid is recovered in this process as callse of the wide range and variety of operable reaction
a solution of about 30% acid strength, which must then conditions, I do not wish to be limited in the scope of
be concentrated to 80%-85% acid strength before it can this invention to any specific range of temperatures, cata
be recycled to the process. About two-thirds of the lyst or reaction conditions.
lactonitrile is thus dehydrated to acrylonitrile, the remain 55 The lactonitrile for the process of my invention may
der dissociating into acetaldehyde and HCN, which is be made by any of the well-known methods of the prior
recycled in the process. Part of the lactonitrile reacts art. Thus, for instance, liquid hydrogen cyanide is ad
with the phosphoric acid and the water present to form justed to a pH between 6.0 and 8.0 with 20% aqueous
lactic acid and primary ammonium phosphate Soda. Solution. The stoichiometric amount of acetalde
60
hyde is then added with agitation at a temperature be
-NHHPO tWeen 10 C. and 25° C. to form actonitrile.
About 7.5 kgs. of this ammonium phosphate is obtained The Iactonitrile thus obtained may then be reacted
for every 100 kgs. of acrylonitrile formed. This salt with acrylonitrile, in the presence of an alkaline catalyst
accumulates in the recycling phosphoric acid and must (e.g. alkali and alkaline earth metal hydroxides, alco
be periodically separated from the system. This involves 65
holates and cyanides, trialkyl amines, etc.), substantially
a somewhat diminished yield of acrylonitrile, complicates by the process of Hansley (U.S. Patent #2,333,782) to
the phosphoric acid recovery, requires a concentration form the desired alpha,beta'-dicyanodiethyl ether.
and recycle system and involves the consumption of addi It is also entirely feasible to react acetaldehyde, hydro
tional phosphoric acid reagent. The overall yield of acry gen cyanide and acrylonitrile, in the presence of an alka
lontrile by this process is about 90% of theory. This 70 line catalyst, in a single step, to form the alpha,beta'.
process is described in U.S. Patent #2,790,822 (issued dicyanodiethyl ether.
April 30, 1957, to Wolfram, Steil and Agunte) and dis The reaction of the acrylonitrile with the lactonitrile
 3,151,150
s 4.
(or with acetaldehyde and HCN if the reaction is effected active catalyst form and may be used as such for pro
in a single step) is not quantitative. Thus, after the re longed periods of time. The preferred (but by no means
action of the acrylonitrile with the lactonitrile is effected, solely effective) reaction temperature for the pyrolysis
the reaction mixture is fractionated to recover the alpha employing phosphoric acid as a catalyst (or its dehydrated
beta-dicyanodiethyl ether and to recover and recycle the forms-pyrophosphoric and metaphosphoric acid) is 300
various intermediates. Thus, the reaction product may C. to 400 C.
first be fractionated at atmospheric pressure. Acetalde Alternately, the alphabeta'-dicyanodiethyl ether may
hyde and hydrogen cyanide (formed by the dissociation be passed in the vapor state through a catalyst bed, or a
of unreacted lactonitrile) distill over first (B. Pt. acetalde heated reaction zone containing the catalyst, or through
hyde 21 C., hydrogen cyanide 26 C.). The unreacted 0 heated tubes filled with the catalyst. Catalysts suitable
acrylonitrile (B. Pt. 78.5° C.) first distills over as an azeo for this purpose are activated alumina, pumice, dia
trope with the water present in the system. This azeo tomaceous earth, fullers' earth, silica gel, Alundum, thoria,
trope boils at 71° C. and contains 88% of acrylonitrile dehydrating clays, etc. as well as supported catalysts such
and 12% of water. The fractionation of the reaction mix as phosphoric acid or ammonium phosphates on any solid
ture is then continued under reduced pressure, e.g. at carrier, such as activated alumina, pumice, kaolin, clay,
18-20 mm. Hg. The unreacted lactonitrile distills over at firebrick, silica gel, zinc chloride on any solid carrier
90-100° C. at 18-20 mm. Hg, and the alphabeta'-dicy such as the above, etc.
anodiethyl ether may be recovered at 145° to 155 C. at Alternately, the vaporized alpha,beta'-dicyanodiethyl
18-20 mm. Hg. However, in the practical application of ether may be passed, at advanced temperatures, through a
this process, it is only necessary to recover the acetalde 20 turbulent bed of any of the catalysts above enumerated,
hyde, hydrogen cyanide, acrylonitrile and lactonitrile frac in very finely divided form, by any of the technics now
tions. The residue in the still, consisting of the alpha used in fluid bed catalyzed reactions, and well known to
beta'-dicyanodiethyl ether, may be submitted directly to the art.
pyrolysis for the formation of acrylonitrile, without prior The preferred temperature ranges when employing such
fractionation or purification. The recovered acetaldehyde, 25 solid catalysts, with the alpha,beta-dicyanodiethyl ether
hydrogen cyanide, acrylonitrile and lactonitrile fractions in the vapor state, is from 250° C. to 450° C., but this is
are recycled to the process for the preparation of the by no means the solely operable or effective range. In
alpha,beta'-dicyanodiethyl ether. The conversion of the the presence of catalysts, the pyrolysis may be effected at
actonitrile and the acrylonitrile to the alphabeta'-dicy temperatures as high as 750° C. The use of a catalyst
anodiethyl ether varies from 40% to 65% per cycle, but 30 is not essentiai, but may be preferred since it usually
the overall yield of the alpha,beta'-dicyanodiethyl ether, gives a higher conversion to acrylonitrile per pass and
based on the actual consumption of acetaldehyde, hydro somewhat better overal yields, as does the use of higher
gen cyanide and acrylonitrile is 95% to 97% of theory. temperatures or temperatures within the indicated pre
The pyrolysis of the alpha,beta'-dicyanodiethyl ether ferred range.
to form the acrylonitrile may be effected over a very wide The products of the pyrolysis of the alpha,beta'-dicy
range of temperatures, in the absence of catalysts or in anodiethyl ether, in each case, will consist of minor.
the presence of dehydration catalysts, and at Subatmos amounts of acetaldehyde (B. Pt. 21 C.), hydrogen cyanide
pheric, atmospheric or superatmospheric pressures. (B. Pt. 26° C.), water (B. Pt. 100° C.) and lactonitrile
In the absence of catalysts, the preferred (but by no (B. Pt. 90-100° C. at 18-20 mm. Hg), and substantial
means the only effective) temperature range for the pyrol 40 amounts of the acrylonitrile (B. Pt. 78.5° C.) formed and
ysis of the alphabeta'-dicyanodiethyl ether to acryloni unreacted alphabeta'-dicyanodiethyl ether (B. Pt. 145
trile is 300° C. to 500 C. 155 C. at 18-20 mm. Hg). It will be noted that these
The pyrolysis may be effected, in the absence of cata products are the very same (although differing in relative
lysts, by dropping the alphabeta'-dicyanodiethyl ether in amounts) as those obtained in the fractionation of the
the liquid state on a heated surface, or by passing it in the 45
product obtained in the condensation of lactonitrile with
vapor phase over a heated surface, or through a heated the acrylonitrile in the preparation of the alpha,beta'-di
reaction zone or pyrolysis tube. The effluent gases are cyanodiethyl ether (above described) which is the feed
cooled, condensed and fractionated to recover the end for the pyrolysis reaction.
products of the pyrolysis, including the acrylonitrile. Thus, the end-product gases of the pyrolysis step, in
Alternately, a dehydration catalyst may be used. An each case, may be cooled and condensed and then frac
extremely wide range of such catalysts may be used in 50 tionated into its components. Alternately, the cooled,
the process of this invention. condensed reaction products may be mixed with the re
Thus, the alphabeta'-dicyanodiethyl ether may be action products from the condensation of lactonitrile
dropped onto the surface of a heated catalyst (at 250 C. and acrylonitrile, and these combined products frac
to 750° C.) and thus pyrolyzed to acrylonitrile. The tionated together. This will permit a considerable econ
catalyst may be solid or molten at the temperature of the ony in equipment and processing costs.
pyrolysis. Among suitable catalysts for this purpose are: Thus, a fraction of acetaldehyde and hydrogen cy
phosphoric acid, pyro-phosphoric and meta-phosphoric anide may be recovered first, and recycled to the lacto
acid, the alkali metal and alkaline earth metal oxides, nitrile preparation. Then, the acrylonitrile may be re
hydroxides, carbonates, and borates, the alkali metal and 60
covered (first as the azeotrope with water, and then as
alkaline earth metal salts of the fatty acids, the alkali pure acrylonitrile). Part of this acrylonitrile is recycled
metal and ammonium salts of phosphoric acid, zinc salts, to the preparation of the alpha,beta'-dicyanodiethyl ether
aluminum salts, aluminum oxide, and many others. step, and the remainder represents the salable end-prod
- Phosphoric acid is an excellent catalyst for this purpose. uct of this process. Then, the unreacted lactonitrile is
At 150 C., is becomes anhydrous; at about 200° C., it recovered under reduced pressure, and recycled to the
reverts to pyrophosphoric acid and above 300° C. it is 65 process for reaction with the acrylonitrile to form the
largely present in the form of meta-phosphoric acid. alphabeta'-dicyanodiethyl ether. Finally, the still resi
It must be emphasized that this phosphoric acid, in any due (which may be fractionated but must not necessarily
of its forms and dehydration products, acts as a true be so processed) is the alpha,beta'-dicyanodiethyl ether
catalyst. Unlike the phosphoric acid used in the process which is the feedstock for the pyrolysis step.
of U.S. Patent #2,790,822 (above discussed), it is not 70
volatilized with the reaction mixture, it is not diluted by The following examples are given to define and to il
the water of the reaction products, it does not have to be lustrate this invention, but in no way to limit it to re
concentrated and re-constituted and it does not hydrolyze agents, proportions, catalysts, or reaction conditions de
any of the starting materials or end-products to diammo scribed therein. Obvious modifications will occur to any
nium phosphate. The phosphoric acid remains in its 75 person skilled in the art.
 3,151,150
5 6
Example I Example III
Lactonitrile is prepared by adding 20% aqueous caustic Alpha,beta-dicyanodiethyl ether is vaporized under re
soda solution to 271 grams of liquid hydrogen cyanide duced pressure (e.g. at 250-275 C. at 25-30 mm.) and
(10 moles) to adjust its reaction to pH 7.0. A total of this is passed through a quartz tube (0.50' inside diam
443 gms, of acetaldehyde (10 moles) is now added slowly, eter, 15' long) half filled with activated alumina gran
with good agitation, keeping the temperature of the re ules as a catalyst, maintained at a temperature of 300
action mixture between 10° C. and 25 C. In another 325 C., at the rate of 90 gms. per hour. The gaseous
vessel, 531 grams of acrylonitrile (10 moles) and 5 grams pyrolysis products are conducted off, cooled, condensed
of potassium cyanide (as a catalyst) are heated under and fractionated.
O The conversion to acrylonitrile is 50%-55% per pass,
gentle reflux, while the lactonitrile above formed is added with an overall yield of 95% of theory, based on the
slowly over a period of an hour. The reaction mixture alphabeta'-dicyanodiethyl ether actually consumed.
is kept at 85°-90° C. for another hour, and is then cooled, Similar results are obtained by the use of catalysts such
and adjusted to pH 7 by the addition of 20% sulfuric as pumice, diatomaceous earth, fullers' earth, silica gel,
acid. The product is then fractionated (as described in 5
Alundum, thorium dioxide, dehydrating clays, supported
the specification) first at atmospheric pressure, then at
18-20 mm. Hg pressure to recover acetaldehyde, hydro catalysts such as phosphoric acid or ammonium phos
gen cyanide, acrylonitrile, lactonitrile and the alpha, phate on Solid carriers such as alumina, pumice, kaolin,
beta- dicyanodiethyl ether. The conversion to alpha, clay, firebrick, silica gel, zinc chloride, aluminum chlo
beta'-dicyanodiethyl ether varies from 40% to 65% per 20 ride, etc.
cycle, but the overall yield, based on the actual consump Having described my invention, what I claim and de
tion of acetaldehyde, hydrogen cyanide and acrylonitrile sire to protect by Letters Patent is:
is 95% to 97% of theory. 1. The cyclic process for the manufacture of acrylo
The alphabeta'-dicyanodiethyl ether is pyrolyzed by nitrile which comprises the steps of:
adding it dropwise, at the rate of about 200 gms. per 25 (a) reacting lactonitrile with acrylonitrile in the pres
hour, from a dropping funnel, into a 500 cc. flask, the ence of a basic catalyst to form alphabeta'-dicyano
bottom of which is heated at 350° to 375 C. The gas diethyl ether,
eous pyrolysis products are conducted off, cooled, con (b) separating the alphabeta'-dicyanodiethyl ether
densed and fractionated, from unreacted lactonitrile and acrylonitrile,
Alternately, the alphabeta'-dicyanodiethyl ether may 30 (c) pyrolyzing the alpha,beta'-dicyanodiethyl ether to
be pyrolyzed by vaporizing it under reduced pressure form two moles of acrylonitrile and one mole of
(e.g. at 180°-200 C. under 20 mm. Hg. pressure), and Water for each mole of dicyanodiethyl ether con
this is passed through a quartz tube (0.50' inside diam Sumed, said pyrolysis being effected at a temperature
eter, 15' long) at the rate of 75 gms, per hour, the tube between 250° C. and 750° C. and at a pressure at
being maintained by electric heating elements at a tem 35 which the acrylonitrile formed is vaporized,
perature of 375 to 400 C. The gaseous pyrolysis (d) recovering acrylonitrile and unreacted dicyano
products are conducted off, cooled, condensed and frac diethyl ether from the pyrolysis products of step c,
tionated. (e) recycling to step c the unreacted alpha,beta'-dicy
The conversion of alphabeta-dicyanodiethyl ether to anodiethyl ether recovered from step d,
acrylonitrile is from 32% to 70% per pass, and the over 40 (f) recycling to step a the unreacted acrylonitrile
all yield, based on the alpha,beta-dicyanodiethyl ether and lactonitrile from step b together with a portion
actually consumed, is 93% to 96% of theory. of acrylonitrile from step d equal to the amount of
acrylonitrile which had been consumed in step a
Example II and
45 (g) recovering as product from step d an amount of
Fifty grams of phosphoric acid is placed in a reaction acrylonitrile stoichiometrically equivalent to at least
flask and heated to 350-360° C. (which converts it 90% of the lactonitrile consumed in the process.
largely to meta-phosphoric acid). The alphabeta'-dicy 2. The process as defined in claim 1 wherein the py
anodiethyl ether (prepared as described in Example I) rolysis is effected at a temperature of 300° C. to 500°C.
is added dropwise onto the surface of the acid from a 50 3. The process as defined in claim 1 wherein the pyrol
dropping funnel, at the rate of 50 gms. per hour. The re ysis is effected in the presence of a dehydration catalyst.
action products of the pyrolysis are conducted off, cooled 4. The process as defined in claim 3 wherein the pyrol
condensed and fractionated. ysis is effected at a temperature of 250° C. to 450° C.
The conversion to acrylonitrile is from 62% to 80% References Cited in the file of this patent
per cycle, with overall yields of 94% to 95% based on 55 UNITED STATES PATENTS
the alphabeta'-dicyanodiethyl ether consumed. Similar re
Sults are obtainable by the use of alkali metal and alkaline 2,333,782 Hansley --------------- Nov. 9, 1943
earth metal oxides, hydroxides, carbonates and borates, 2,562,583 Schulz et al. ------------ July 31, 1951
the alkali metal and alkaline earth metal salts of the fatty 2,832,798 Rapoport ------------- Apr. 29, 1958
acids, the alkali metal and ammonium salts of phosphoric 60 OTHER REFERENCES
acid, Zinc salts, aluminum salts, aluminum oxide, and Institute of Synthetic Organic Chemical Research C.A.,
many other dehydration catalysts. 44 (1950), page 3515 (B).