Patented July 23, 1940

2,208,934

UNITED STATES PATENT OFFICE

2,208,934
MANUEFACTURE OF TEMETHYLENE TE
NETRAMRE (EEX60GEN)
Josef Meissner, Coogae-sayerCatha, Gersey
No Drawirag. Application August 9, 1939, Serial
No. 289,27. Era Geransay (?ay 23, 1938
3 Cairns. (CA, 28-348)
This invention relates to improvements in the 15-20% HNO3, but it is sufficient for the practi
manufacture
ogen). of trimethylene trinitramine (hex cally complete precipitation of the hexogCn to
The commercial application of hexogen dilute the spent acid only to 40-60% HNO3.
This spent acid contains about the Same quan
NO tity of hexogen dissolved as the 20% spent acid.
N-CH According to a further feature of the inven
of, YNo. tion by immediate introdutcion of the 40-60%
spent acid into sulphuric acid of not too low
O
-C concentration, for example into an acid of
to, 80-95% HaSO4, the hexogen is completely de O
which is generally recognised at the present time stroyed and by this means an acid stable to stor
as an explosive, is still rendered difficult by the ing produced which on account of the high
HNO3 content is immediately capable of denitra
uneconomical use of acid in its manufacture. tion or concentration.
Normally in the nitrations a batch ratio of 1. In the process of mixing it is possible to pro 5
part hexamethylene tetramine to 10 parts of ceed in such a manner that either the waste acid
nitric acid is employed. Such a batch ratio ren is gradually introduced into sulphuric acid, or
ders it necessary to work up the residual acids the waste acid so combined with sulphuric acid
since otherwise the economy of the process is that
20 rendered questionable. This specified batch tions the two liquids in corresponding propor
by weight are continuously allowed to flow
ratio of i:10 must be maintained in all circum together. In this operation the temperature of 20
stances in the direct nitration of hexamethylene the sulphuric acid or of the mixture is main
tetramine in order to obtain a good yield and it
is not possible by reduction of the batch ratio tained between 30 and 80 C.
25 to arrive at a more favourable economy of acid. is The proportion of waste acid to sulphuric acid
on the one hand determined by the require
In the nitration the hexogen remains com ment of the complete decomposition of the heXO 25
pletely dissolved in the spent acid and this must,
gen, on the other hand by the requirement of the
in order that all hexogen is precipitated, be economic working up of the acid. It has been
treated with Water. Hitherto the acid had to
30 be diluted to such an extent with Water that a found that proportions which lie between 1:1.5 to
residual acid of about 20% HNO3 remained 1:7 claim:correspond best to these two requirements.
30
which still contained a few percent of hexogen 1. Process for the working up of the nitration
in Solution. This strong dilution was necessary mixture produced in the manufacture of tri
because a stronger cncentration of the spent acid methylene trinitramine (hexogen), wherein from
35 excluded the possibility of storing the same since the concentrated nitric acid used for the reac
otherwise after a short time the hexogen de tion, by dilution with water to a content of 35
composed. The Working up of this 20% waste 40-60% HNO3 the hexogen is precipitated and
acid produced Was On the one hand not economic the separated residual acid immediately brought
and on the other hand incapable of execution. together with 1-7 times the quantity of concen
40 In fact the dissolved hexogen could not be con trated sulphuric acid, temperatures between 30
pletely precipitated even by still further dilution and 80° C. being maintained.
and thus formed in the denitration column a con
siderable source of danger. 2. Process as claimed in claim 1 in which the
acid mixture is subsequently denitrated.
According to the present invention the nitra 3. Process, as claimed in claim 1 in which the
tion mixture (spent acid with dissolved hexogen) acid mixture is subsequently concentrated.
should not as hitherto customary be diluted to OSEE MESSNER 45