IMPROVEMENTS IN THE MANUFACTURE OF COLORING MATTERS
Year: 1875

page_text: LETTERS PATENT to Frederick Versmann, of 12, Brecknock Crescent,
Camden Town, in the County of Middlesex, Ph.D., Consulting and
Analytical Chemist, for the Invention of "IMPROVEMENTS IN THE
MANUFACTURE OF COLORING MATTERS.
PROVISIONAL SPECIFICATION left by the said Frederick Versmann at
the Office of the Commissioners of Patents, with his Petition, on
the 20th March 1875.
I, FREDERICK VERSMANN, of 12, Brecknock Crescent, Camden Town,
in the County of Middlesex, Ph.D., Consulting and Analytical Chemist,
do hereby declare the nature of the said Invention for "IMPROVEMENTS IN
THE MANUFACTURE OF COLORING MATTERS," to be as follows:-
In the manufacture of rosaniline or red aniline dye a small proportion
of a yellow dye is always produced which is known under the name of
chrysotoluidine or phosphine.

page_text: The object of my Invention is to separate this yellow dye either from
the crude rosaniline, commonly called the melt, or from any bye product
residue or refuse resulting from the manufacture of rosaniline. This
object I obtain by treating either of the above substances with bisulphide
of carbon or with petroleum, the latter in preference, petroleum spirit of
700 to 720 specific gravity. Both these liquids readily dissolve the
yellow coloring matter together with some impurities, from which the
phosphine may be separated and purified. This treatment with either
bisulphide of carbon or with petroleum I carry out in a suitable apparatus
either cold, or by the aid of heat produced by means of steam pipes
passing through or round the apparatus, or by other convenient
means.
The extraction of phosphine is greatly facilitated by working under
pressure, which is produced by making the apparatus containing the
material and the liquid perfectly air-tight and then heating it, by which
means the vapors of the liquid exert a pressure upon the contents of the
SPECIFICATION in pursuance of the conditions of the Letters Patent, 2
filed by the said Frederick Versmann in the Great Seal Patent
Office on the 20th September 1875.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, FREDERICK
VERSMANN, of 12, Brecknock Crescent, Camden Town, in the County.
of Middlesex, Ph.D., Consulting and Analytical Chemist, send 2
greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Twentieth day of March, in the year
of our Lord One thousand cight hundred and seventy-five, in the
thirty-eighth year of Her reign, did, for Herself, Her heirs and suc- 3
cessors, give and grant unto me, the said Frederick Versmann, Her
special licence, that I, the said Frederick Versmann, my executors,
administrators, and assigns, or such others as I, the said Frederick
Versmann, my executors, administrators, and assigns, should at any

page_text: time agree with, and no others, from time to time and at all times
thereafter during the term therein expressed, should and lawfully
might make, use, exercise, and vend, within the United Kingdom of
Great Britain and Ireland, the Channel Islands, and Isle of Man, an
Invention for "IMPROVEMENTS IN THE MANUFACTURE OF COLORING MATTERS,"
upon the condition (amongst others) that I, the said Frederick
Versmann, my executors or administrators, by an instrument in writing
under my, or their, or one of their hands and scals, should particularly
describe and ascertain the nature of the said Invention, and in what
manner the same was to be performed, and cause the same to be filed
in the Great Scal Patent Office within six calendar months next and
immediately after the date of the said Letters Patent.
NOW KNOW YE, that I, the said Frederick Versmann, do hereby
declare the nature of my said Invention, and in what manner the
same is to be performed, to be particularly described and ascertained
in and by the following statement thereof, that is to say :-
In the manufacture of rosaniline or red aniline dye a small proportion
of a yellow dye is always produced which is known under the name of
chrysaniline, chrysotoluidine, or phosphine.
The object of my Invention is the separation of this yellow dye, cither
from the crude aniline dye, commonly called the melt, or from any byc
product refuse or residue resulting from the manufacture of rosaniline.
This object I attain by treating either of the above-named substances
with bisulphide of carbon or with pretroleum; if I use the latter I
prefer to use petroleum spirit of 700 to 720 specific gravity, and I now
give a detailed description of this operation.
The treatment of the crude melt is most advantageous, and although
the extraction of any of the products or residues from the crude melt
yields sensible quantities of phosphine, I prefer, whenever possible, to
treat the crude melt before any of the coloring matters have been
extracted therefrom.
It is well known that in most cases the coloring matters exist in the
crude melt in the form of salts, i.e., combined with an acid, chiefly
arsenic acid. Now, I find the solvents I employ, bisulphide of carbon
or petroleum, to act much better upon the free base than upon the
phosphine salts, and I therefore prefer to separate all the bases from the

page_text: acids with which they are combined by any of the well-known means.
I then take the mixture of the coloring matters thus separated and place
it in an apparatus to extract the phosphine by means of either of the
two solvents mentioned before.
This apparatus may be made of copper, iron, or any other suitable
material capable of withstanding a pressure of several atmospheres. The
apparatus is provided, a few inches above the bottom, with a perforated
false bottom upon which the material to be extracted is placed, the open
top is then closed perfectly air-tight by means of a lid, and the liquid
introduced by means of a pipe at the bottom of the apparatus; this
pipe leads to a reservoir of the liquid above, and has a stop-cock to
regulate and to cut off the supply of the liquid from the reservoir.
As soon as the apparatus is nearly filled the liquid standing a little
above the dry material, the stop-cock in the supply pipe is turned
off and the apparatus is heated by means of a steam pipe passing
through the inside of the apparatus or through an outer casing sur-
rounding the apparatus, or by other convenient means. After a while
the liquid becomes saturated with phosphine and some soluble
impurities from the melt, when a stop-cock in a second pipe near the
top of the apparatus is turned on, after which the stop-cock in the
bottom pipe is also turned on and more liquid allowed to pass into
the apparatus. The saturated solution is thus replaced by a fresh
quantity of liquid and runs off through the top pipe into a closed
reservoir or still connected with a well cooled condenser. The stop-
cocks at top and bottom are then turned off, steam is turned on again,
and the operation is repeated till the liquid runs off perfectly colorless
from the top pipe, or in other words till all the phosphine has been
dissolved. The solutions collected in the still are then heated by means
of a steam pipe, or otherwise, the liquids are driven off in the form of
vapor, and are condensed to be used over and over again. The concen-
trated solution remaining in the still is brought to dryness, and the
crude phosphine thus obtained may be further purified in the usual
manner.
The exhausted material in the apparatus is frced as much as possible
from any liquid, when it will be found that the process separates only
phosphine and some of the resinous impurities of the melt, but it does
not dissolve any sensible quantities of red coloring matters which have
to be separated from the original material in the usual manner.

page_text: Any of the bye products or residues from the aniline manufacture
may be treated in a similar manner with results more or less satisfactory,
but I wish it distinctly to be understood that I do not claim the con-
struction or the use of any particular apparatus. The above description is
merely given as an illustration of the working of my process, which may
be modified according to circumstances; but what I do claim as my
Invention is, the separation of a yellow dye usually called phosphine
from the crude aniline dye, commonly called the melt, or from any bye
products, residues or refuse resulting from the manufacture of rosaniline,
substantially as described above, namely, by the use of bisulphide of
carbon or of petroleum; if using the latter in preference, petroleum
spirit of 700 to 720 specific gravity, both liquids being used either
under ordinary circumstances or under pressure, with or without the aid
of heat.
In witness whereof. I. the said Frederick Versmann, have here-
FRED. VERSMANN. (L.s.)