Art of Manufacturing Sulpho Acid from Petroleum.
Year: 1893

page_text: ate of Application, 25th May, 1893-Accepted, 8th July, 1893
COMPLETE SPECIFICATION.
Art of Manufacturing Sulpho Acid from Petroleum.
I, HANS ALBERT FRASCH, 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 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 for obtaining a body or product which may be employed for
producing dyestuffs or color bases.
In practising my invention, I treat the petroleum body with sulphuric acid until
sulphonation is effected and then separate the product into what by analogy may
be termed alpha and beta acids, which are further treated for colors or dyestuff's.
The invention herein consists in the process of obtaining these two acids, also the
process of separating the alpha acid; also the product containing the two acids and
also the alpha acid.
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 requires 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 residuum 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 solution is separated from the precipitate. This
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page_text: solution contains what by analogy, I term the alpha acid, and the sulpho acid is
separated from it by the addition of hydrochloric acid, or any other acid that will
displace the calcium.
Instead of obtaining the acid directly as just described, it may be obtained
indirectly by converting the calcium salt into a salt of potassium, ammonium, &c.,
and then separating the sulpho acid by the addition of hydrochloric acid or
the like.
This alpha sulpho acid is soluble in water, glycerine and alcohol and partly
soluble in most of the aromatic hydrocarbons. All its solutions are of a greenish
yellow, with a distinct greenish fluorescence. Its solution dyes wool, and silk,
without mordant, a greenish yellow. The solid substance is greenish black in pure
state, apparently not crystalline, frangible and melts or runs at about 180 F. Its
calcium salt is soluble in water, as are also all the salts of the alkalies and the
earthly alkalies and most of the metallic oxides. The solution of the salts is of a
bright, clear yellow, dyeing wool and silk without mordant, in acidulated solution,
a bright canary yellow; and these solutions also exhibit the greenish fluorescence.
The acid when exposed to high temperature emits the characteristic odour of
burning coal oil. The acid when reacted upon by nitrous or nitric acid in weak
solution forms azo and nitro bodies.
The colors or dyestuffs derived from this acid form the subjects of contemporaneous
applications for patents.
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 art of manufacturing sulpho acid from petroleum, natural mineral oil or
the distillates or derivatives thereof, which consists in sulphonating the substance
and separating the sulpho acid from the remainder, substantially as described.
2. The art of manufacturing sulpho acids from petroleum, natural mineral oil or
the distillates or derivatives thereof, which consists in sulphonating the substance,
removing the free sulphuric acid, separating the soluble from the insoluble and oily
matters in the remainder, splitting the soluble matter into soluble and insoluble lime
salts, and ultimately converting these salts into distinct sulpho acids substantially as
described.
3. The art of manufacturing sulpho acids from petroleum, natural mineral oil, or
the distillates or derivatives thereof, which consists in sulphonating the substance,
removing the free sulphuric acid, separating the soluble and the insoluble and oily
matters from the remainder, splitting the soluble matter into a soluble and an
insoluble lime salt, and separating the sulpho acid by adding to such soluble lime
salt, hydrochloric acid or other acid that will displace the lime, substantially as
described.
4. As an article of manufacture, a sulpho acid producing with carbonate of lime
or caustic lime a salt soluble in water and another salt insoluble in water, having in
aqueous solution a greenish fluorescence and emitting the characteristic odour of
petroleum or coal oil when highly heated, substantially as described.
5. As an article of manufacture, a sulpho acid of greenish black color when solid
and of greenish yellow to yellow coloration in solution, soluble in water, having a
greenish fluorescence in solution emitting the characteristic odour of coal oil
when highly heated, and whose calcium salt is soluble in water, substantially as
described.
6. As an article of manufacture, a sulpho acid emitting the characteristic odour
of coal oil when highly heated, and whose calcium salt is soluble in water, substan-
tially as described.
Dand this yo
1
HANS ALBERT FRASCH.