NITED STATES PATENT OFFICE.

ARTHUR GEORGE GREEN, OF LEEDS, ENGLAND.

ANUFACURE OF PICRIC ACD.

1,299,171. specification of Letters Patent, Patented Apr. 1, 1919,

NoDrawing. Application fled January 29, 1916. Serial No. 75,023,
To all whom it may concern: generated in the mixture from sodium nitrate.
Beit known that I, ARTHUR GEORGE GREEN, The dinitrophenol itself is most conveniently
B.Sc., F. R. S., F. I. C., subject of the King produced by chlorinating benzene to mono
of Great Britain and Ireland, residing in the chlorobenzene, nitrating the latter with a
University of Leeds, Leeds, in the county of mixture of nitric acid and surfuric acid to 60
York, England, professor of applied chem: dinitrochlorobenzene, and conversion of this
istry, have invented certain new and useful into dinitrophenol by boiling with caustic
Improvements in the Manufacture of Picric alkali. The entire chain of reaetions, start
Acid, of which the following is a specifica ing from benzene, is therefore the follow
0. tion. --- O Ing:- . . . 35
The ordinary method of manufacturing
picric acid from phenol is subject to several
disadvantages. In the first place it is de
CHCHCCNO)Cl.
of Nö),0fc.H.(NO),OH
pendent upon the available supplies of phe As the conditions for carrying out the first
nol, which if much in demand is liable to rise three steps are well known, it is only neces
to a high price. In the second place the ni sy to describe
tration of phenol, as usually carried out,
"only gives, a yield of 70 to 75% of the theo
effecting the last instepdetail
in thetheconversion
best wayi. ofe.
the nitration of dinitrophenol as above men
retical amount, and owing to the fact that tioned. This is effected in presence of con 75
20 the operation has to be performed in presence centrated sulfuric acid employing one molec
of water cannot be effected in iron or lead ular proportion (or slightly more) of strong
lined vessels but necessitates the employment
of earthenware pots. This fact generally nitric acid. The process is carried out for
example in the following manner:-
restricts the size of the charge and as the In a round-bottomed cast-iron pot, pro
25 operation requires about two days for com vided with a cast-iron agitator, 500 lbs. of 80
pletion, the output is correspondingly lim dinitrophenol in powder (containing 8% of
ited. Furthermore the manufacturing opera water) is stirred with 2,000 lbs. of cold con
tion is an unpleasant one, the large quanti centrated sulfuric acid (95% HSO.). Into
ties of nitrous fumes evolved being a danger this mixture is run within a period of about
30 to the health of the workmen and a nuisance five minutes a mixture of 180 lbs. of nitric 85
to the surrounding neighborhood. acid (90% HNO) and 200 lbs. of concen
: I have now invented a process of manufac trated sulfuric acid. The temperature of the
turing picric acid which overcomes these mixture rises rapidly to about 100° C. the
difficulties and has the following advantages: dinitrophenol dissolves, and ultimately pic
ss phenol.
(1) It is independent of the supplies of ric acid separates in the form of small crys 90
The primary raw material, being tals. After standing for about ten minutes
Ene, is much cheaper and subject to very to complete the reaction, the mixture is
little fluctuation in price. . . . . - cooled down to about 40°C. and is then run
(2) The loss in manufacture is very small into a wooden vat containing about 7000 lbs.
40 as the reactions occur nearly theoretically. of cold water or of wash water obtained from 95
(3) The operations can be conducted in a previous batch. The liquor, still warm, is
large charges and in cast-iron nitrating ves run on to a suction filter, the picric acid
sels, thus greatly increasing the output. which remains on the filter being then washed
(4) The evolution of nitrous fumes is very free from sulfuric acid by means of cold or
45 small. warm water, and dried. The yield is nearly 00
(5) The waste sulfuric acid from the ni theoretical (about 110% of the damp di
tration can
contains be readily reconcentrated
no by-products. . . as it, nitrophenol)
quality.
and the product is of standard
The process consists in the nitration under An alternative method of separating the
50 special conditions of dinitrophenol in the picric acid from the waste sulfuric acid 05
presence of sulfuric acid. According to the which permits of the latter being obtained at
invention dinitrophenol is nitrated in pres a higher strength (about 80%. H.S.O.), con
ence of concentrated sulfuric acid with about sists in adding to the mixture after nitration
one molecular equivalent of nitric acid, the and cooling about 20 gallons of cold water.
55 nitric acid being either employed as such or This causes the crystallization of almost all G
 $2 1,299,171
the picric acid, which is then separated from treating same with water, separating and 30
the waste sulfuric acid by filtration through washing the picric acid.
acid resistant material, from which it is sub 4 Aprocess for the manufacture of picric
sequently transferred to water and washed acid, comprising treating about 500 parts of
free from sulfuric acid. dinitrophenol with about 2200 parts of con
Retaining the above proportion of sulfuric centrated sulfuric acid and about a molecu 35
acid, the nitric acid may be replaced if de lar proportion of strong nitric acid, cooling
sired by dry sodium nitrate (one molecular the resulting nitration mixture, diluting
proportion) which is added quickly in pow same with water, separating and washing the
10 der with rapid stirring. In this case how picric acid, substantially as described.
ever the recovery of the waste sulfuric acid 5. A process for the manufacture of picric 40
presents difficulties. acid, comprising treating a mixture of about
What I claim and desire to secure by Let 500 parts of dinitrophenol and about 2000
ters Patent is:- . parts of concentrated sulfuric acid with a
15 1. A process for the manufacture of picric mixture of about 180 parts of strong nitric
acid, comprising nitrating dinitrophenol in acid and about 200 parts of concentrated sul 45
presence of concentrated sulfuric acid with furic acid, cooling the resulting nitration
about one molecular proportion of nitric acid. mixture, adding same to about 7000 parts
2. A process for the manufacture of picric of water, separating from the mixture the
20 acid, comprising nitrating dinitrophenol picric acid formed and washing the same, 50
with about one molecular proportion of ni substantially as described.
tric acid in presence of concentrated sulfuric In witness whereof I have hereunto signed
my name in the presence of two subscribing
acid, to form picric acid, cooling the mixture witnesses.
and separating and washing the picric acid.
3. A process for the manufacture of picric ARTHUR GEORGE GREEN.
acid, comprising nitrating dinitrophenol
with about one molecular proportion of ni Witnesses:
tric acid in presence of concentrated sulfuric HARRY HYMANN,
WILFRID ARMITAGE.
acid, to form picric acid, cooling the mixture,