Art of Producing Dyestuffs from Natural Mineral Oils by Sulphonation.
Year: 1893

page_text: Date of Application, 25th May, 1893-Accepted, 8th July, 1893
CUMI LUID DIEUITIVATION.
Art of Producing Dyestuffs from Natural Mineral Oils by
Sulphonation.
I, HANS ALBERT FRASCH, of 962 Willson Avenue, Cleveland, Ohio, United
States of America, Chemical Engineer, do hereby declare the nature of my inven-*
tion and in what manner the same is to be performed to be particularly described
and ascertained in and by the following statement, that is to say :-
This invention relates to the utilization of such hydrocarbons as natural mineral
oil or petroleum or the distillates or derivatives thereof for obtaining dyestuffs or
color bases.
In the manufacture of anilin, artificial alizarin, and kindred dyestuffs, and bases
for dyestuffs and colors coal tar obtained from illuminating gas works has hitherto
been employed. The ordinary process of conversion is by fractional distillation of
the coal tar. The aromatic series of hydrocarbons contained in such coal tar
furnishes the course whence these dyestuffs or colors have been derived. A kindred
or similar series of hydrocarbons exists also in petroleum or natural mineral oil or
the distillates or derivatives, residual or otherwise, thereof, and it is upon this
hydrocarbon of the petroleum series as distinguished from the hydrocarbons of the
coal tar series that I act for obtaining my new dyestuff or color base.
My invention consists in the art or method of treating natural mineral oils,
petroleum, or their derivatives or distillates by transforming or couverting the
same into coloring matter or dyestuff or subjecting them to the action of suitable,
reagents. My invention also consists in the method of obtaining dyestuffs or
color bases. My invention also consists of a dyestuff or color base extracted from
such substances and possessing and having as a distinguishing characteristic the
property of emitting the odour of coal oil when highly heated. My invention also
consists in certain details as hereinafter more particularly set forth and claimed.
In practising my invention, I subject crude petroleum or its distillates or products,
residual or otherwise to the action of sulphuric acid until all the aromatic hydro-
carbons, olefines, naphthenes and unsaturated hydrocarbons in the oil are taken up
in the acid as oxidized and corresponding sulpho products. The proportion of acid
to oil varies greatly according to the quality of the oil being treated. Crude oil
requires about twenty-five per cent., while distillates require from two to ten
per cent., and sludge from nothing to five per cent., according to the quantity of acid
remaining in the substance. In all cases, the treatment proceeds alike, substantially
as follows: The mixture of acid and oil is agitated, mechanically or by a forced
current of air, until a sample from which the acid has been permitted to settle, will
discolor little if any upon the addition thereto of fresh concentrated sulphuric
acid. The mixture of acid and oil is then permitted to rest until the acid is
separated from the oil, when the acid containing the aromatic hydrocarbons and
tarry substances is drawn from the oil. The acid mixture is then heated until the
hydrocarbons contained therein are converted into sulpho combinations and oxidized
products.
Sulphonation may be effected without heat by keeping the mixture agitated for
a long time, say, from four to eight weeks, and even longer, thus permitting the
acid to act upon the hydrocarbons. Fuming or 50-called Nordhausen sulphuric
acid, or a mixture of chromic and sulphuric acids may also be employed for
sulphonation.
The requisite degree or extent of sulphonation is determined when the bulk of
a test sample will dissolve in a hot solution of alkali.
The free sulphuric acid is then removed, and this may be readily accomplished
by neutralisation or repeatedly washing the mixture with cold water or by precipi-
tating the sulpho compound from the acid. After the free acid is removed, the

page_text: residuum is heated with water until the water is saturated with the more soluble
products. The solution is left to settle, whereby the soluble products and the
insoluble and oily matter are separated. The soluble products are then drawn off
and consist of a mixture of different higher or lower sulpho products. To separate
these products, calcium carbonate or hydrate is added, with or without heating,
until precipitation ceases, whereby a soluble and an insoluble calcium salt are
obtained. Any other substance which will form a soluble and an insoluble salt
with the sulpho product may be substituted for the calcium. The soluble and the
insoluble salts are then separated, by filtration or other means.
The dyestuff is precipitated from a solution of this soluble salt by the addition
thereto of chloride of sodium or any other salt in which the dyestuff is insoluble.
The dyestuff may be obtained also by transforming the soluble salt above
mentioned into a salt of sodium, potassium, ammonium, &c., by the addition thereto
of sodium carbonate, potassium carbonate, ammonium carbonate, &c., or any
other base which has the capacity of displacing the base already represented
in the solution. From the solution thus last obtained, the dyestuff may be
precipitated as before, as, for example, by the addition of sodium chloride.
The dyestuff is obtained in the form of a yellow powder, soluble in water,
alcohol and glycerine, and also soluble in most of the aromatic hydrocarbons. Its
solutions have a greenish fluorescence. The dyestuff emits the characteristic odour
of coal oil when highly heated. It dyes wool and silk, in acidulated solution, a
bright yellow. If exposed to the action of nitrous or nitric acid, it produces a
dyestuff of a reddish brown color.
Having now particularly described and ascertained the nature of my said inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is:
1. The improvement in the art of treating natural mineral oils, petroleum or
their derivatives or distillates, which consists in transforming the same into a
coloring matter or dyestuff, substantially as described.
2. A hydrocarbon dyestuff having as its distinguishing characteristic the property
of emitting the odour of coal oil when highly heated, substantially as described.
3. A yellow dyestuff, soluble in water, having a greenish fluorescence and emitting
the odour of coal oil when highly heated, substantially as described.
4. A yellow dyestuff, soluble in water, having a greenish fluorescence, and dyeing
wool and silk, in an acidulated solution, without mordant, a bright yellow,
substantially as described.
Dated this 19th day of April 1893.
HANS ALBERT FRASCH.