Patented Nov.

10, 1942
2,301,231

UNITED STATES PATENT OFFICE

2,301,231
NITRATION OF ALCOHOLS
Charles Philip Spaeth, Woodbury, N.J., assignor
to E. I. du Pont de Nemours & Company, Will
nington, Del, a corporation of Delaware
No Birawing. Application May 3, 1940,
Serial No. 333,109
1. Clain. 260-46)
This invention pertains to the nitration of
solid polyhydroxy alcohols. ent' or 'stabilizer,' I may employ sulfuric acid,
The nitration of solid polyhydroxy alcohols acetic acid, phosphoric acid, and the like. Al
presents certain difficulties which prevent the di though the proportions of the water and diluent
rect addition of Said alcohols to a nitrating mix 3. present in the medium employed for dissolution
ture of nitric and sulfuric acids. Thus, prior at of the polyhydroxy alcohol may be varied rather
tempts to effect nitration in this manner have widely, I prefer to restrict the Water content to
invariably baen characterized by inconnplete dis the minimum quantity which is essential for
tribution of the rnass of crystals of the solid facile dissolution of the alcohol to be nitrated
polyhydroxy alcohol throughout the nitrating 0 and yet is sufficient to prevent charring and de
medium, due partly to the fact that the nitrated composition of said alcohol, as well as to inhibit
product separates in a solid phase as soon as raterial chemical reaction thereof.
formed. As a result of this incomplete distribul After the alcohol has been dissolved in such
tion, there is a tendency for localized heating to solution, it may be nitrated readily by reacting
occur, said heating, of course, presenting an ex With a mixed acid composed of nitric and Sull
plosion hazard. Likewise, incomplete distribu may furic acids to yield a crystalline product that
tion of the alcohol is attended by low yields, due be purifled easily.
to incomplete nitration of the material. The following example is cited as a specific 'em
Because of the foregoing difficulties, many ef bodiment of my process in order that it may be
forts have been made to develop a method of ni described more in detail. It is understood, of
tration which would give a high yield of the ni course, that this example is merely illustrative
trated product without entailing hazardous or and is not intended to limit my invention.
Complicated steps in the procedure. Thus, Mar Eacarple
shall in U. S. Patent 1,660,651 discloses a method Twenty-one pounds of mesoerythritol were dis
for the nitration of solid polyhydroxy alcohols 25
which is characterized by the dissolution of the and water, the acid andawater
solved in 42 pounds of mixture of sulfuric acid
representing a sul
solid alcohol in sulfuric acid of 90 to 95 percent
strength, following which the resulting Solution furic acid solution of 70% strength. The result
is added to concentrated nitric acid of 90 to 100 ing solution was run into a stainless steel nitrator,
percent strength, nitration being effected at a 30 wherein was present 276 pounds of a nitrating
temperature between 40 and 60° C. Although acid mixture composed of 27.5 parts of nitric acid
this method, in general, represents an improve and 72.7 parts of sulfuric acid, said mixture being
ment in the art, the yields of nitrated product agitated vigorously. The charge was cooled dur
obtained when operating in accordance there ing the nitration reaction by passing cold Water
with are not entirely satisfactory. through the jacket of the nitrator. After nitra
35 tion was complete, the charge was drowned in
The object of the present invention is a proc
ess for nitrating solid polyhydroxy alcohols, said about 1300 pounds of cold Water and the drowned
process permitting the attainment of yields of charge neutralized by washing with a dilute sodi
the nitrated product appreciably higher than um carbonate solution. The crude erythritol
those obtained by any process known heretofore, tetranitrate was then dissolved in a 50-50 mix
Another object is a process for the nitration of 40 ture of acetone and ethyl alcohol, any occluded
solid polyhydroxy alcohols, which process is acidity being neutralized with aqueous sodium
characterized by safety as well as ease of opera carbonate, and the resulting solution forced
tion. A further object is a process for producing through a spray nozzle having a circular opening
a pure, granulated, solid, nitrated polyhydroxy water,of 0.10 inch in diameter into a vessel containing
alcohol, such as erythritol tetranitrate, for ex interval which was vigorously stirred during the
ample. Still further objects will become appar tetranitrate required for spraying the erythritol
ent as the invention is described more fully here solution. The precipitated erythritol
inafter. tetranitrate was then separated from the liquid
I have found that the foregoing objects are at by filtration, following which the material was
tained by effecting distribution of the solid poly 50 dried. The finished product represented a yield
hydroxy alcohol in a medium comprising water which wasa nitrogen 91 per cent of the theoretical and
and a material which will act as a "diluent” or apossessed
melting point
content of 18.50 percent and
of 61.3° C.
'stabilizer' when the aqueous solution of the
polyhydroxy alcohol is nitrated. As such "dilu 55 holThe dissolution of the solid polyhydroxy alco
in the water-diluent mixture offers no par
2 2,301,231
alcohols which may be dissolved in diluents, Such
ticular difficulty, AS stated hereinbefore, a Suf as Sulfuric acid, acetic acid, phosphoric acid, and
ficient volume of water should be present to effect the like. Hence, it is applicable to mannitol,
ready solution of the alcohol. Likewise, the ratio arabitol, xylitol, sorbitol, dulcitol, and the like,
of water to acid is maintained Sufficiently high 5 The term "diluent' or 'stabilizer,' as applied
to prevent decomposition and charring or chemi to the acids disclosed in the foregoing, is in
cal reaction with the alcohol. Thus, I have tended to denote the effect which said acids exert
found that, when sulfuric acid is employed as the when the solution of alcohol is brought into
diluent or stabilizer, it is permissible to employ contact with the mixed nitrating acids. Thus,
an aqueous solution of Sulfuric acid having a 0 their presence renders the aqueous alcohol solu
strength as high as about 80% sulfuric acid. tion compatible with the nitrating medium and
However, I prefer to use a solution ranging from avoids the violent reaction which otherwise would
60 to 70% sulfuric acid, because in this range occur. Likewise, their presence serves as a me
it is certain that substantially no decomposition dium for the absorption of heat evolved during
or carbonation of the alcohol Will occur. Nor the nitration reaction. Consequently, such
does the use of such mixture entail a substantial meaning should be ascribed to these terms
heat evolution, characteristic of sulfation. throughout the present description. .
Once the solid polyhydroxy alcohol has been Although I have described my invention in
dissolved in the water-acid mixture, nitration detail, it will be understood by those skilled in
thereof may be effected readily by means of a the art that variations may be made without
mixed acid. The composition of the mixed acid departing from the spirit or scope thereof. For
may be varied rather widely, say to approxi example, it is not essential that the nitrated
mately equal parts of sulfuric and nitric acid, but alcohol be reprecipitated from a solvent solution
I prefer to use an appreciable preponderance as set forth in the specific example. On the
of sulfuric acid, because it facilitates suitable contrary, it may be desirable to employ the prod
agitation of the charge during the nitration uct after it has been washed with water and
stage. I have found a mixed acid composed of neutralized with the aqueous alkaline solution.
about 70 parts sulfuric acid and 30 parts nitric This is permissible because the nitrated product
acid very desirable. The nitration of the solid crystallizes as it is formed, and the crystals may
polyhydroxy alcohol solution, with the afore be purified by methods deemed standard for the
mentioned conditions obtaining, does not require 3 purification of freshly-nitrated materials, that
an exact temperature control, but instead pro is to say, Washing with water and dilute alkaline
ceeds even though the temperature varies over solutions. I intend, therefore, to be limited only
rather wide limits. Obviously, variations in the
temperature affect the time cycle required for in Iaccordance
claim:
with the following claim.
complete nitration of the alcohol, A method of producing erythritol tetranitrate,
The present process makes available a method which comprises dissolving erythritol in a water
for nitrating solid polyhydroxy alcohols which sulfuric acid medium equivalent to a sulfuric
may be executed readily, which is free from the acid solution not exceeding 80% strength, and
hazards characterizing heretofore known proc 40 treating the resultant erythritol-containing so
esses for the nitration of such materials. In ad lution with a nitric-sulfuric acid mixture corn
dition, my process is characterized by an un posed of from 50 to 80 parts of sulfuric acid and
usually high yield of the finished product. from 50 to 20 parts of nitric acid.
It will be understood that the process is not
limited to the nitration of erythritol, but rather CHARLES PHILIP SPAEIH.
is applicable, in general, to solid polyhydroxy 45