Patented Nov. 20, 1928.

1,691,954
UNITED STATES PATENT OFFICE.
FRANK H. BERGEIM, OF WOODBURY, NEW JERSEY, ASSIGNOR TO E. I. DU PONT DE
NEMOURS & COMPANY, OF WILMINGTON, DELAWARE, A CORPORATION OF DELA
W.A.R.E.
PRODUCTION OF ERYTHIRTO, TETRANITRATE.
NoDrawing, Application filed April 15, 1927. Serial No. 184,180.
This invention relates to the production of ('arried out (parts by weight):-One part of
erythritol tetranitrate, and more particu crythritol is dissolved in 54 parts of concen
larly relates to the nitration of erythritol, trated sulphuric acid 90-95% strength, using
C.H. (OH), by dissolving the same insul cooling water to prevent the temperature ris
5 phuric acid and adding the solution to nitric ing to such an extent that the erythritol be 60
acid or mixed acid containing a large propol'- comes carbonized, it being advisable not to
tion of nitric acid. Also the invention relates permit the temperature to rise above 40 to
to the stabilization of erythritol tetranitrate. 50 C. When all of the erythritol has dis
The major objects of the invention are to solved this solution is run into 7 parts of
to provide such procedures. strong nitric acid (90-100%) keeping the tem 65
In the literature (Stenhouse Ann. 70,226) perature between 40° and 60° C. Instead of
it is reported that erythritol tetranitrate may strong nitric acid, there may be used with
be prepared by dissolving erythritol in stron equally good results a mixed acid of relatively
nitric acid and precipitating the nitrate low sulphuric acid content, containing for ex
15 product by adding sulphuric acid. However, ample 12% HSO, 80% HNO, and 8% H.O. 70
the product prepared by this method has a The mixture is then agitated for a short time,
poor chemical stability (Naoum, Nitroglyc say 20 to 30 minutes, after the addition of the
erine and Nitroglycerine Sprengstoffe p. sulphuric acid solution has been completed.
218). In addition to the undesirable chemi The erythritol tetranitrate separates as an oil
20 cal stability of the product thus prepared the in the warm waste acid. By cooling slowly 75
process itself is open to serious objection as with rapid agitation the explosive is obtained
being unsafe for commercial manufacture, in in a fine crystalline condition. It may be
that it involves the dissolution of an organic filtered from the waste acid, or the whole mix
body in strong nitric acid forming a mixture ture drowned. In either case, the slightly
25 in itself an explosive. I have provided a acid product is purified and stabilized by dis 80
process, comprised by the present invention, solving in warm alcohol, treating the alcoholic
wherein are embodied new and valuable fea solution with preferably powdered ammon
tures, making the process itself safe as a ium carbonate until neutralized, and cooling
manufacturing operation and producing a to crystallize. Desirably, the neutralized
30 product markedly superior in chemical sta product may be forced out of solution by add 35
bility to that previously prepared. ing water. The explosive thus obtained is a
The safety feature involves, as the first white crystalline product having excellent
step, the dissolving of erythritol in sulphuric stability and a nitrogen content very close to
acid. This liberates considerable heat of re the theoretical (18.53% N).
35 action in forming a non-explosive compound, In the method of stabilization, it is to be 90
thus preventing this heat from being liberated understood that other water soluble solvents
later in the process when erythritol comes in than alcohol may be used. It is not necessary
contact with nitric acid. When the sulphuric to add water to the solvent in order to obtain
acid solution is added to strong nitric acid a satisfactory product but by so doing the
40 or a mixed acid high in nitric acid, so little yield is brought up to very near the theoreti 95
heat is liberated that the nitrator must even cal. It is also to be understood that other
be kept warm with steam. weak alkaliesthan ammonium carbonate, such
Another feature of the present process is as sodium and potassium carbonates or bicar
the stabilization of the nitrated product by bonates may be used; and in the claims refer
45 dissolving it in a water soluble solvent such as ences to 'carbonate' are to be understood as 00
alcohol or acetone, adding a weak alkali such including "bicarbonate', except as otherwise
as sodium or ammonium carbonate, and then evident. Furthermore, while the preferred
forcing the erythritol tetranitrate out of so process of stabilizing comprises dissolving the
lution by adding water. This method of sta crude product in a water soluble solvent, e.g.
50 bilization gives a product of excellent stabil alcohol, and (after neutralizing) forcing the 105
ity superior in this respect to the erythritol product out of solution by adding water, since
tetranitrate described in the literature. water soluble solvents offer the advantage of
Without restricting the invention thereto, dissolving an appreciable amount of carbon
the following is cited as a specific example of ate and also offer the advantage of giving
55 the manner in which the invention may be the opportunity of completely recovering the 0
 2 1691,954.
stabilized product by subsequent mixing with tio. In the same way, the nitric acid or mixed
water, it is to be understood that water solu acid ratios E. be varied widely without de
ble solvents need not necessarily be used. parting from the spirit of the invention.
Thus, solvents such as chloroform, ether and I claim: 25
toluene may be used; but recovery of the sta 1. A process for the nitration of erythritol
bilized product from these solutions is more which comprises dissolving the alcohol insul
difficult and expensive than from water-solu phuric acid, and adding the solution thus pre
ble solvents. Whether water-soluble, or wa pared to nitric acid.
ter-insoluble solvents be used and whether or 2. The process of claim 1 in which the sul 30
O not forcing the product out by the addition of phuric acid is of 90-95% strength.
water be resorted to, a particular feature of 3. The process of claim 1 in which the nitric
the stabilization procedure is, the treatment acid contains sulphuric acid.
of erythritol tetranitrate in solution with 4. The process of claim 1 in which the nitric 35
weak alkali. acid is of about 90% strength.
In regard to the nitration process proper, it 5. The process of claim 1 in which the temper
is not necessary to adhere strictly to the acid ature of the nitrating mixture is maintained
ratios given in order to obtain goods results. at about 40-60° C. until the nitration of the
While I prefer the ratio of 51A, parts of sul alcohol is substantially complete.
phuric acid to one of erythritol, an equally In testimony whereof I affix my signature.
20 good product, though in smaller yield, may be
obtained by increasing or decreasing this ra FRANKH. BERGEIM.