Improvements in Sulphonic Acids and in their Salts of Alkaline Earthy Metals and Metals Proper, and the Process of Making the same.
Year: 1899

page_text: Date of Application, 26th Aug., 1899
Complete Specification Left, 26th May, 1900-Accepted, 25th Aug., 1900
Improvements in Sulphonic Acids and in their Salts of Alkaline Earthy
Metals and Metals Proper, and the Process of Making the same.
I, LUDWIG OTTO HELMERS, Doctor of Philosophy, of 174, Fuhlsbüttelerstrasse,
Hamburg, in the Empire of Germany, Chemist, do hereby declare the nature
of this invention to be as follows:
In the Specification of my Application No. 14389, filed July 12th 1899, I
have described a process by which soluble salts, particularly distinguished by
their high percentage in sulphur, are to be separated from the insoluble part
of the sulphonic-acid salts of the alkaline-carthy metals and metals proper of
the "Ichthyol, Petrosulfol" and the like hitherto deemed to be in their totality
insoluble in water.
Like the salts of these sulphonic acids, containing sulphur in the form of
sulphide, also behave, towards the alkaline earths and metallic oxides, those
acids, which are obtained by the action of sulphuric acid upon mineral oils
and similar hydrocarbons free from sulphur, such as the sulphonic acids obtained
from bitumenous coal-oils paraffine oils resin oils and the like. Hitherto it
has been assumed, that the salts of the alkaline-earthy metals and metals proper
of these sulphonic acids, with the only exception of the salt of antimony and
mercury, are insoluble in water; however a closer examination has proved that
also in this case analogous to the sulphonic-acids containing sulphur in the
form of sulphide, a part of the sulphonized products deliver alkaline-earthy salts
and metal salts which are soluble in water, and that these salts and the corre-
sponding acids own strong reducing qualities. On account of this property the
salts with easily reducible base are not very permanent, and only after oxidation
of the original sulphonized product a metal salt (for instance a silver salt) which
remains permanent in aqueous solution, may be produced.
The production of these soluble and hitherto unknown alkaline earthy and
metal salts as well as of the corresponding free acids, thoroughly corresponds to
the process disclosed by my aforesaid pending application, as will be understood
from the following example.
The product obtained by the action of 1 kg. of fuming sulphuric acid upon
1 kg. rosin-oil is poured into water and neutralized with lime-milk, the liquid
decanted off from the sediment, then filtered, the filtrate saturated with carbonic
acid and evaporated to a nearly dry mass. The remaining liquid, to which about
a double volume of alcohol is to be added, is thereupon filtrated from the separated
sulphate of calcium, the filtrate liberated from the alcohol and evaporated to
dryness. The residue, the lime-salt of the sulphonic acid of the rosin-oil appears
as a brown substance which is easily pulverizable and readily soluble in water.
In order to obtain f.i. the silver-salt the sulphonized compound of rosin-oil
is oxidised with a solution of peroxide of hydrogen and then the lime-salt,
obtained from this oxidized product in the like manner as before, is mixed in
alcoholic solution with the corresponding quantity of sulphuric acid, the liquid

page_text: filtered off from the separated sulphate of calcium, the filtrate liberated from the
alcohol neutralized with argentic oxide and the clear solution evaporated to
dryness. The silver-salt, thus produced, forms a reddish brown powder easily
soluble in water.
Instead of oxidising the original sulphonized compound of rosin oil and
similar oils permanent salts with an easily reducible base may be obtained by
oxidizing the sulphonic acids, which form alkaline earthy salts soluble in water
and are obtained as aforesaid, whereupon the oxidised acids are neutralized with
the corresponding base in about the manner as explained in the specification of
my said pending application.
Dated this 26th day of August 1899
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.
Improvements in Sulphonic Acids and in their Salts of Alkaline Earthy
Metals and Metals Proper, and the Process of Making the same.
I, LUDWIG OTTO HELMERS, Doctor of Philosophy, of 174, Fuhlsbüttelerstrasse,
Hamburg, in the Empire of Germany, Chemist, do hereby declare the nature
of this invention and in what manner the same is to be performed, to be particu-
larly described and ascertained in and by the following statement:-
In the Specification of my British Patent No. 14389, of July 12th 1899, I
have described a process by which it is possible to obtain acids rich in sulphur
and forming soluble salts of alkaline earthy metals and metals proper from the
sulphonized products obtained by the action of sulphuric acid on sulphuretted
hydrocarbons.
Like the salts of these sulphonic acids, also behave towards the alkaline earths
and metallic oxides, those acids, which are obtained by the action of sulphuric
acid upon mineral oils and similar hydrocarbons free from sulphur, such as
the sulphonic acids obtained from bituminous coal-oils, paraffine oils, rosin-oils
and the like. Hitherto it has been assumed, that the salts of the alkaline-earthy
metals and metals proper of these sulphonic acids, with the only exception of
the salt of antimony and mercury, are insoluble in water, however a closer
examination has proved that also in this case, analogous to the sulphonic-acids
of sulphuretted hydrocarbons, a part of the sulphonized products form alkaline-
earthy salts and metal salts which are soluble in water, and that these salts
and the corresponding acids possess strong reducing qualities. On account of
this property also, the salts with an easily reducible base, are not very permanent,
and it is only after oxidation of the original sulphonized product that a metal
salt (for instance a silver salt) which remains permanent in aqueous solution,
may be produced.
The production of these soluble and hitherto unknown alkaline earthy and
metal salts, as well as of the corresponding free acids, thoroughly corresponds
to the process hereinbefore referred to. This process is performed by neutraliz-
ing the sulphonized products, obtained by the action of sulphuric acid on hydro-
carbons free from sulphur, in an aqueous solution with the oxide, hydroxide, or
carbonate of an earth alkali or metal proper, filtering off the liquid after some
time from the precipitated insoluble salts, evaporating the filtrate to dryness
and setting free from the salts thus obtained, the sulphonic acid by adding a
stronger acid or by precipitating the metal by means of sulphide of hydrogen.

page_text: The following example may more clearly elucidate the present invention:-
The product obtained by the action of 1 kg. of fuming sulphuric acid upon
1 kg. of rosin-oil is poured into water and neutralized with lime-milk, the
liquid decanted off from the sediment, then filtered, the filtrate saturated with
carbonic acid and evaporated to a nearly dry mass. The remaining liquid, to
which about the double volume of alcohol is to be added, is thereupon filtered
from the separated sulphate of calcium, the filtrate liberated from the alcohol
by distillation and then evaporated to dryness. The residue, the lime salt of
the sulphonic acid of the rosin-oil, appears as a brown substance which is easily
pulverizable and readily soluble in water.
The free acid of this salt is obtained by dissolving the lime-salt in diluted
alcohol, adding sulphuric acid in about a quantity corresponding to that of the
lime, filtering off the precipitated sulphate of lime, and removing the alcohol
by distillation from the filtrate. The residue is then concentrated and the acid
forms a dark greenish, syrup-like mass.
In order to obtain, for instance, the silver-salt, the sulphonized compound of
rosin-oil is oxidized with a solution of peroxide of hydrogen, chromic acid or the
like and then the lime-salt, obtained from this oxidized product in a like manner
as before, is mixed in alcoholic solution with the corresponding quantity of
sulphuric acid, the liquid filtered off from the separated sulphate of calcium,
the filtrate liberated from the alcohol, neutralized with argentic oxide, and the
clear solution evaporated to dryness. The silver-salt, thus produced, forms a
reddish-brown powder easily soluble in water.
Instead of oxidizing the original sulphonized compound of rosin oil and similar
oils, permanent salts with an easily reducible base may be obtained by oxidizing
the sulphonic acids, which form alkaline earthy salts soluble in water and are
obtained as above described, whereupon the oxidised acids are neutralized with
the corresponding base in the manner as explained in the Specification of my said
prior British Patent.
The process will be clearly explained by the following example:-
A solution of kg. of the sulphonic acid obtained from sulphonized rosin-
oil in the manner set forth in the first part of the former example is mixed with
2 kg. of a solution containing 3% of peroxide of hydrogen and heated several
hours on a water bath. The brown solution is then concentrated to about one
litre and neutralized with argentic oxide. Finally, the filtered liquid is
evaporated to dryness, the residue pulverized and completely dried. The reddish
brown powder, which is easily soluble in water entirely resembles the silver-
salt obtained from the oxidised sulphonized compound derived from rosin-oil
in the manner aforesaid.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare that what
I claim is :-
1. The process of producing sulphonic acids, having reducing qualities and
forming salts of alkaline-earthy metals and metals proper, soluble in water con-
sisting in neutralizing the reaction product of sulphuric acid on hydrocarbons
free from sulphur with the corresponding base, filtering off the liquid from the
precipitate, setting free the sulphonic acid by adding a stronger acid or sulphide
of hydrogen to the filtrate and evaporating the filtered solution to dryness, sub-
stantially as set forth.
2. The process of producing permanent metal salts of sulphonic acids, which
consists in neutralizing the reaction product of sulphuric acid on hydrocarbons
free from sulphur with the base of an earth alkali or metal proper, filtering off
the liquid from the precipitate, setting free the sulphonic acid by adding a
stronger acid or sulphide of hydrogen to the filtrate, oxidising the sulphonic acid,
neutralizing the solution with the base of the corresponding metal and evaporat-
ing the filtered liquid to dryness, substantially as set forth.

page_text: 3. The process of producing permanent metal salts of sulphonic acids, which
consists in oxidizing the reaction mixture of sulphuric acid on hydrocarbons free
from sulphur, neutralizing the oxidized product with an alkaline earthy base,
filtering off the liquid from the precipitated insoluble salt, setting free the
sulphonic acid by precipitating the earth alkali, neutralizing the filtrate with
a metallic base and evaporating the liquid to dryness, substantially as set forth.
4. The hereinbefore described soluble sulphonic acids and their salts which
derive from mineral oils, rosin oils and hydrocarbons free from sulphur com-
bined with sulphuric acid, substantially as and for the purpose set forth.
Dated this 26th day of May 1900.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.