Production from Mineral Oils of Sulphonic Acids and Sulphones, and the Manufacture of a New Product by Treating Gelatinous Matters with Sulphonic Acid.
Year: 1890

page_text: Date of Application, 29th Nov., 1890
Complete Specification Left, 20th Aug., 1891-Accepted. 24th Oct., 1991
PROVISIONAL SPECIFICATION.
Production from Mineral Oils of Sulphonic Acids and Sulphones,
and the Manufacture of a New Product by Treating Gelatinous
Matters with Sulphonic Acid.
I, ALEXANDER MELVILLE CLARK, of the firm of A. M. and Wm. Clark,
of 53, Chancery Lane in the County of Middlesex, Fellow of the Institute of
Patent Agents, do hereby declare the nature of this invention (a communication to
me from abroad by The Gewerkschaft Messel, of Grube Messel, near Darmstadt,
Germany) to be as follows:
:-
It is a well known fact that on purifying mineral oils by means of sulphuric acid
the latter removes basic bodies and those which are known by the general name of
"acid tar;" also that by washing the "acid tar" with water the adhering sul-
phuric acid may be removed and thus a tarry substance obtained which is insoluble
in water.
It has been proved that amongst the tarry substances mentioned, some of which
derive from bodies analogous to pyrrol, there are other compounds which are highly
unsaturated and easily converted into sulphonic acids when strong or fuming
sulphuric acid is made to act more sharply on them. The sulphonic acids thus
obtained are bodies which either of themselves or in the shape of their alkaline salts
are easily soluble in water. It has been further shewn that these sulphonic acids
are obtainable from any mineral oil, whether it be found already formed in the
earth as petroleum or be prepared by dry distillation of bituminous schists or
lignite.
The general occurrence of the unsaturated mother-substances of the aforesaid
sulphonic acids in all mineral oils forms a characteristic difference to the extremely
limited number of oils rich in sulphur-containing upwards of 10% of this element
of which it has long been known that by virtue of this sulphur they yield on
treament with sulphuric acid the sulphonic acid known by the name of "ichthyol."
The mother-substances of the new sulphonic acids do not contain sulphur but are
simple hydrocarbons. Hence the new method of preparing sulphonic acids from
mineral oils, is not dependent on the latter containing sulphur.
The new sulphonic acids, which it is proposed to designate "tumenolsulphonic
acid," possess the following properties. In the undried condition the tumenolsul-
phonic acid forms a syrupy body of a spicy taste drying at 110° C. to a pulverizible
residue. It is easily soluble in water and is precipitated from this solution on the
addition of common salt, hydrochloric acid, or sulphuric acid. The alkaline salts
are likewise soluble and may be salted out the same as the soaps of the fatty acids.
On the other hand their salts with the alkaline earths and the oxides of the heavy
metals, with the exception of those of mercury and antimony, are insoluble in water.
They are further distinguished by their property of precipitating glue or gelatine
from slightly acid solutions with the formation of an elastic caoutchouc-like pre-
cipitate which can be drawn into threads and the production of which constitutes a
feature of the present invention.
In consequence of their unsaturated character, the tumenolsulphonic acids are
easily oxidized their very formation being accompanied by an oxidation and the
evolution of sulphur dioxide consequent on the reduction of the sulphuric acid
employed in sulphonating. Tumenolsulphonic acid precipitates ferri chloride at
the same time reducing the excessive ferric to ferrous salt. Mercuric chloride is
reduced to calomel on boiling with tumenolsulphonic acid and the latter is con-
verted into an insoluble precipitate when boiled with an acidified solution of
bichromate

page_text: The mode of preparation is as follows;-Although the unsaturated bydrocarbons
contained in mineral oils are converted into sulphonated derivates on simply heating
the oils with sulphuric acid of 66° B., a greater yield of sulphonic acid and less of
the intermediate sulphone is obtained when fuming sulphuric acid is employed in
the following manner. 100 pounds of any distillate of mineral oil say of a specific
gravity of 0.830 to 0-870 is freed from creosotes and acids by the aid of caustic
soda lye and from bases and pyrollic bodies by the aid of sulphuric acid of 70%
then heated to 80° C. As soon as this temperature has been reached, 20 pounds of
fuming sulphuric acid testing 10% sulphuric anhydride is rapidly stirred in. There
is a rise of temperature and a considerable evolution of sulphur dioxide. The
liquid is allowed to cool down and settle whereupon the supernatent oily part is
decanted and the remaining sirupy part run into boiling water while vigorously
stirring the latter. So far as the sulphuric acid present does not of itself pre-
cipitate the tumenolsulphonic acid, common salt is added to throw down the
sulphonated products which are now collected on a filter, repeatedly dissolved in
water, and reprecipitated by the addition of common salt until all sulphuric acid is
removed. Finally the syrup is mechanically freed from the adhering brine. It
now presents a mixture of the sulphonic acids with the sulphones. As will be
shewn, this mixture is easily soluble in water. It may be separated into its con-
stituent parts by converting the acid into its soda-salt and extracting the latter
with ether or naphtha. The ether dissolves the sulphones, bodies deriving from the
same unsaturated by hydrocarbons as the sulphonic acids but less highly sulpho-
nated and less highly oxidized. By causing sulphuric acid to act sharply on the
sulphones, they are easily converted into the corresponding sulphonic acids. The
tumenolsulphone forms a thick yellow or brownish fluid soluble in ether, benzene,
naphtha, and spirits of wine. Though insoluble in water it is easily dissolved by
an aqueous solution of tumenolsulphonic acid.
Dated this 29th day of November 1890.
A. MELVILLE CLARK,
By A. M. & Wm. Clark,
53, Chancery Lane, London, Patent Agents.
COMPLETE SPECIFICATION.
Production from Mineral Oils of Sulphonic Acids and Sulphones,
and the Manufacture of a New Product by Treating Gelatinous
Matters with Sulphonic Acid.
I, ALEXANDER MELVILLE CLARK of the firm of A. M. and Wm. Clark of
53, Chancery Lane, in the County of Middlesex, Fellow of the Institute of Patent
Agents, do hereby declare the nature of this invention (a communication to me
from abroad by The Gewerkschaft Messel, by Grube Messel, near Darmstadt,
Germany) and in what manner the same is to be performed, to be particularly
described and ascertained in and by the following statement :-
It is a well known fact that when mineral oils are purified by means of sulphuric
acid the latter removes basic bodies as well as those which are known by the
general name of "acid tar;" also, that by washing the latter with water the
adhering sulphuric acid may be removed and thus a tarry substance obtained which
is insoluble in water.
It has been proved that amongst the tarry substances mentioned some of which
derive from bodies analogous to pyrrol, there are other compounds which are highly
unsaturated and easily converted into sulphonic acids when strong or fuming
sulphuric acid is made to act more energetically on them. These sulphonic acids
are bodies which either in the form in which they are thus obtained or in that of
their alkaline salts are easily soluble in water. It has been further shewn that
these sulphonic acids are easily obtainable from any mineral oil whether it be oil
found already formed in the earth or prepared by dry distillation of bituminous

page_text: schists or lignite; also, that such acids may be prepared in an analogous manner
from rosin oil the product of distillation of rosin.
The general occurrence of the non-saturated mother substances of the aforesaid
sulphonic acids in all mineral oils forms a characteristic difference from the limited
number of oils rich in sulphur containing upwards of 10% of this element which it
has long been known yield on treatment with sulphuric acid the sulphonic acid
known by the name of "ichthyol." The mother substances of our new sulphonic
acids and sulphones, are in fact simple hydrocarbons and their convertibility into
sulphonic acids does not depend on the presence of sulphur of combination.
The new sulphonic acids which it is proposed to call "Tumenolsulphonic acids "
possess the following properties:-In the undried condition the tumenolsulphonic
acids form a syrupy body of a spicy taste drying at 110° C. to a pulverizable
residue. They are easily soluble in water and are precipitated from this solution
on the addition of common salt, hydrochloric or sulphuric acid. The alkaline salts
are likewise soluble and may be salted out in the same way as the soaps of fatty
acids. On the other hand their salts of the alkaline earths and of the oxides of the
heavy metals (with the exception of those of a few such as mercury and antimony)
are insoluble in water. They are further distinguished by their property of pre-
cipitating glue and gelatine from slightly acid solutions with the formation of an
elastic caoutchouc-like precipitate which may be drawn into threads.
In conse-
quence of their unsaturated character the tumenolsulphonic acids are easily oxidized
their very formation being accompanied by an oxidation and the evolution of
sulphur dioxide consequent on the reduction of the sulphuric acid employed in
sulphonating. The addition of an excess of ferric chloride to a solution of tumenol-
sulphonic acid causes the formation of a precipitate and the simultaneous reduction
of ferric to ferrous chloride. Mercuric chloride is reduced to calomel on boiling
with tumenol-sulphonic acid and boiling with bichromate causes the formation of
an insoluble precipitate.
Preparation. Although the unsaturated hydrocarbons contained in mineral oils
need but heating with concentrated sulphuric acid to be sulphonated, more of
sulphonic acid and less of sulphones are obtained when fuming sulphuric acid is
employed as follows; 100 lbs. of any distillate of mineral oils say of specific gravity
of 0.860 to 0.890 are freed from creosotes and acids, by the aid of caustic soda-lye,
and from bases and pyrrolic bodies, by the aid of sulphuric acid of 70%, then
heated to 80° C. As soon
as this temperature is reached, 20 lbs. of fuming
sulphuric acid, testing 10% of sulphuric anhydride, are rapidly stirred in. There
is a rise of temperature and a considerable evolution of sulphur dioxide. The liquid
is allowed to cool down and settle whereupon the supernatant oily part is decanted
and the remaining acid sirupy part run into boiling water while vigorously stirring
the latter. So far as the sulphuric acid present does not of itself precipitate the
sulphonic acids, common salt is added to throw down the sulphonated products
which are next collected on a filter dissolved in water and re-precipitated by the
addition of common salt until all sulphuric acid is removed. Finally, the syrup is
mechanically freed from the adhering brine. It now presents a mixture of the
tumenolsulphonic acids with tumenol-sulphones. As will be shewn, this mixture is
soluble in water although its last named component by itself is insoluble in water.
It may be separated into its constituent parts by converting it into the soda salt
and extracting the latter with ether or naphtha. The ether dissolves the sulphones
and leaves them on evaporation as a thick yellow or brownish fluid soluble in ether
or benzene naphtha or spirits of wine.
The sulphones are bodies derived from the same unsaturated hydrocarbons as the
tumenolsulphonic acids but are less highly sulphonated and less highly oxidized.
By acting more energetically on them with sulphuric acid they are easily converted
into the sulphonic acids.
The soda-salt extracted as before stated yields the free sulphonic acids having
the properties above described on dissolving it in water, precipitating with hydro-
chloric acid, washing to remove the chlorides, and drying to expel all traces of

page_text: hydrochloric acid.
The elastic substance resulting from the combination of
tumenolsulphonic acid with glue size or gelatine is prepared as follows-10 lbs. of
tumenolsulphonic acid are dissolved in 10 gallons of water, the solution is slightly
acidulated with acetic acid and then poured into a nearly cold solution of 5 lbs. of
glue in 20 gallons of water. On stirring the precipitate soon collects and may
be freed from adhering water by squeezing the lumps. It is of a brownish color,
elastic and forming threads on drawing.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what 1
claim is :-
1. The manufacture and production of tumenolsulphonic acids and sulphones
from any mineral oil poor in sulphur or from rosin oil free from sulphur or from
mineral wax (whether found ready formed or artificially prepared by dry distillation
of bituminous schists or lignite) by treating the mineral oil rosin oil or mineral wax
with fuming sulphuric acid or its substitutes at ordinary temperature or with a less-
strongly fuming acid at 80° C. or with concentrated sulphuric acid at 120° C. or
by treating the bodies previously separated at 15° C. from the oil or wax by means
of concentrated sulphuric acid in any of the aforesaid ways, freeing the sirupy
products of sulphonation from sulphuric acid by washing with water and brine and
separating the sulphonic acids and the sulphones by extracting the salts with ether,
naphtha, or other suitable solvent.
2. The manufacture and production of the elastic precipitate obtained by the
addition of tumenolsulphonic acid to size, glue, or gelatine.
Dated this 20th day of August 1891.
A. MELVILLE CLARK,
By A. M. & Wm. Clark,
53, Chancery Lane, London, Patent Agents.