Patented June 2, 1953

2,640,826

UNITED STATES PATENT OFFICE

PRODUCTION OF HEXAMINE
Alexander F. MacLean, Robstown, and Adin Lee
Stautzenberger, Corpus Christi,Tex., assignors -
to Celanese Corporation of America, New York,
N.Y., a corporation of Delaware. . . . . . . . . . . . . .
No Drawing. Application November 8, 1949,
Serial No. 126,244
3 Claims. (Cl. 260-248.6)
2
The present invention relates to the produc dimensions that the reaction mixture is main
tion of hexamine by reacting formaldehyde and tained therein for about 30 minutes during its
8O2. passage therethrough. The aqueous reaction
An object of this invention is the provision of product is then piped into an evaporator or ther
an improved process for the production of hex 5 moSyphon concentrator maintained under a
S.
amine whereby the formaldehyde-ammonia reac vacuum of 25 inches of mercury where the solu
tion and the concentration and Separation of the tion is concentrated at a temperature of about
hexamine formed thereby may be carried out 50° C. Hexamine continuously precipitates from
in a continuous manner. the concentrated Solution as the Water is vapor
Other objects of this invention will appear O ized and removed. The hexamine slurry thus
hereinafter from the following detailed descrip produced is continuously withdrawn from the
tion. evaporator and fed to a centrifugal filter. The
Hexamine is a reaction product of formalde nother liquor discharged from the centrifugal
hyde and ammonia widely employed in the pro filter is recycled to the concentrator to recover
duction of thermosetting plastic materials. This 15 the hexamine remaining in solution. In order to
product is usually obtained by evaporating a avoid excessive build-up of soluble impurities in
mixture of an aqueous solution of formaldehyde the concentrator, a side stream of the mother
and ammonia, by a batch process. Batch proc liquor is taken off and discharged to the sewer.
esses are quite uneconomical and a Suitable con The Wet hexamine cake is discharged from the
tinuous process wherein satisfactory yields are centrifuge and dried. The hexamine formed by
obtained has long been sought. our novel process is obtained in a yield of 90%
We have found that hexamine may be prepared to 95% of theory, and analyzes about 98% hex
eficiently and economically in a continuous man amine, the remainder being water.
ner by simultaneously introducing formaldehyde It is to be understood that the foregoing de
and ammonia, into a reaction Zone, reacting the 25 tailed description is given merely by way of illus
mixture in said reaction Zone at a temperature of tration and that many variations may be made
20 to 70° C. and for 5 to 30 minutes, while main therein Without departing from the spirit of our
taining the pH of said reaction mixture at from invention.
about 7.0 to 8.0. The aqueous mixture leaving Having described Our invention, what we desire
the reaction zone and containing the hexamine 30 to Secure by Letters Patent is:
formed is then concentrated by evaporation under 1. Process for the production of hexamine,
vacuum, the concentration being advantageously which comprises continuously introducing a mix
effected under a pressure of about 20 inches of ture of formaldehyde and ammonia, into a reac
mercury absolute and a temperature of less than tion Zone, reacting the mixture formed for 5 to 30
700 C. 35 minutes at a temperature of 20 to 70° C. and at
By controlling the pH of the mixture under a pH of 7 to 8, continuously withdrawing the
going reaction as pointed out above, the reaction aqueous Solution of hexamine formed from the
proportions employed may be held to Substan reaction. ZOne, concentrating the hexamine Solu
tially stoichiometric quantities. Thus, for every tion to precipitate hexamine continuously there
six mols of formaldehyde employed only slightly 40 from and separating the precipitated hexamine
more than four mols of ammonia, are neceSSary from the slurry thus formed.
to ensure very high yields, which yields usually 2. Process for the production of hexamine,
approach the theoretical yield based on both re which comprises continuously introducing a mix
actants. ture of formaldehyde and ammonia, into a rea,c-
In order further to illustrate our invention, but 45 tion zone, reacting the mixture formed for 5 to 30
without being limited thereto, the following ex minutes at a temperature of 20 to 70° C. and at
ample is given: a pH of 7 to 8, continuously withdrawing the
Eacomple aqueous Solution of hexamine formed from the
3800 parts by weight per hour of 39.9% aqueous reaction Zone, concentrating the hexamine solu
formaldehyde are mixed with 580 parts by weight 50 tion to precipitate hexamine continuously there
per hour of ammonia, the pH of the mixture ob from, separating the precipitated hexamine from
tained being adjusted to 8 by controlling the the slurry thus formed and recycling and concen
excess of ammonia, present and the mixture trating at least part of the mother liquor to
formed passed into a reactor maintained at a Separate additional hexamine therefrom.
temperature of 50° C. The reactor is of Such 55 3. Process for the production of hexamine,
 2,840,826
3
which comprises continuously introducing a mix
4
ture of formaldehyde and ammonia, into a reac References Cited in the file of this patent
tion zone, reacting the mixture formed for 5 to 30 UNITED STATES PATENTS
minutes at a temperature of 20 to 70° C. and at Number Name Date
a pH of 7 to 8, continuously withdrawing the 5.
1566,820 Carter ------------- Dec. 22, 1925
aqueous solution of hexamine formed from the 1,774,929 Landt et al. -------- Sept. 2, 1930
reaction zone, concentrating the hexamine Solu 2,449,040 Schideler et al. ----- Sept. 7, 1948
tion under vacuum to precipitate hexamine con
tinuously therefrom, separating the precipitated OTHER REFERENCES
hexamine from the slurry thus formed, and re 10 Latapie: Chem. Abstracts, vol. 38 (1944), p.
cycling and concentrating at least part of the 1209.
mother liquor to separate additional hexamine
therefrom.
ALEXANDER. F. MACLEAN.
AON LEESTAUTZENBERGER. 5