Sulpho Acid and the Process of Producing the same.
Year: 1893

page_text: COMPLETE SPECIFICATION.
Sulpho Acid and the Process of Producing the same.
1, HANS ALBERT FRASCII, of 962 Willson Avenue, Cleveland, Ohio, United
States of America, Chemical Engineer, do hereby declare the nature of my
invention and in what manner the same is to he 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 oils
or petroleum for obtaining a body or product which may be employed for obtaining
dyestuffs or color bases. In practising my invention I treat crude oil or its
derivatives or distillates with sulphuric acid until sulphonation is effected, and then
separate the product into what by analogy may be termed alpha and beta acids,
from which colors or dyestuffs may be obtained. The present invention consists in
the method of obtaining the beta acid, and also consists in the acid product.
In carrying out my invention, I subject crude petroleum or its distillates or
products, residual or otherwise, to the action of sulphuric acid until all the aromatic
hydrocarbons, 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 remaining oil may be washed and further
utilized for petroleum products as is ordinary crude oil. The acid mixture taken
from the oil is then heated until the hydrocarbons contained therein are converted
into sulpho combinations and oxidized products, and this treatment is of the essence
of my invention.
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 so-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 neutralization or repeatedly washing the mixture with cold water, or by
precipitating the sulpho compound from the acid.
After the free acid is removed, the residnum is heated with water until the water
is saturated with the more soluble sulpho products. The solution is left to settle,
whereby the soluble products and the insoluble matter 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 carbonate of lime or caustic
lime 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 insoluble salt is then separated from the solution by decantation,
filtration or other means, and is converted into a soluble salt by the addition thereto
of carbonate of sodium or caustic soda, or other substance that will serve to
precipitate the base used in obtaining the soluble and insoluble products above

page_text: described and form a soluble coinbination with the acid. This solution contains,
what, by analogy, may be termed the beta-sulpho acid salt. From the solution the
beta acid may be separated by the addition of hydrochloric acid or any other acid
which will displace it from the solution. The precipitated acid is separated by
filtration or decantation.
A main chemical characteristic of the acid is that its calcium salt is insoluble in
water. The acid, when fresh made, is of a black resinous appearance without
apparently well defined crystalline structure, quite frangible, soluble in water and
glycerine, partly soluble in alcohol, benzol and many of the aromatic hydrocarbons;
in many if not all of its solutions it has a greenish or blueish fluorescence, is of a
brownish color in solution and emits the distinctive odour of coal oil when subjected
to high heat, and melts at about 200° F. It forms soluble salts of a brown color
with soluble alkalis.
The acid also may be separated from its calcium salt by exposing the latter to
the action of hydrochloric acid, or any other acid which has a greater affinity
for calcium than the sulpho acid itself. The acid when reacted upon by nitrous
or nitric acid in weak solution forms azo and nitro bodies, and assumes a reddish
brown color.
One purpose for which the acid berein described is specially serviceable is the
production of dyestuffs, and in a contemporaneous application claim such dyestuff.
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 process of manufacturing from mineral oil or petroleum or derivatives or
distillates thereof, an acid whose calcium salt is insoluble in water, which consists
in sulphonating the substance under treatment, removing the free sulphuric acid,
separating the soluble and the insoluble and oily matters from the remainder,
converting the soluble matter into a soluble and an insoluble salt by, for example,
the addition of carbonate of lime or its described equivalent, separating the insoluble
salt, and rendering it soluble by the addition thereto of a suitable reagent such as
carbonate of sodium, caustic soda or other substance that will displace the base
represented in the solution and precipitating from such solution the sulpho acid by
means of hydrochloric or equivalent acid, substantially as described.
2. The process of manufacturing from mineral oil or petroleum or derivatives or
distillates thereof, an acid whose calcium salt is insoluble in water, which consists
in sulphonating the substance under treatment, removing the free sulphuric acid,
separating the soluble and the insoluble and oily matters from the remainder,
converting the soluble matter into a soluble and an insoluble salt by, for example,
the addition of carbonate of lime or its described equivalent, separating the insoluble
salt, and finally treating it with hydrochloric acid or its described equivalent,
substantially as described.
3. As an article of manufacture, a sulpho acid of dark color, soluble in water,
fluorescent in solution, emitting when highly heated the characteristic odour of
petroleum, and whose calcium salt is insoluble in water, substantially as described.
4. As an article of manufacture, a sulpho acid emitting when highly heated the
characteristic odour of petroleum, and whose calcium salt is insoluble in water,
substantially as described.
Dated this 19th day of April 1893.