Improvements in and relating to Sulphur Compounds of Mineral Oils and similar Hydrocarbons.
Year: 1898

page_text: PROVISIONAL SPECIFICATION.
Improvements in and relating to Sulphur Compounds of Mineral Oils
and similar Hydrocarbons.
I, Dr. LUDWIG OTTO HELMERS, of 21, Bohnenstrasse, in the City of Hamburg,
in the Empire of Germany, Chemist, do hereby declare the nature of this inven-
tion to be as follows;-
-
My invention relates to improvements in sulphonized carbon compounds, ob-
tained by the action of sulphuric acids or its substitutes on mineral oils or simi-
lar hydrocarbons and the object of the same consists in rendering such substance
odourless or nearly so.
It is a well known fact that the sulphonized carbon compound produced of
Seefeld mineral oil and known under the name of "ichthyol" possesses a very
intense and peculiar smell derived from a volatile oil generated during the pro-
duction of the said compound. This volatile oil, may, of course, be removed by
distillation with the aid of a current of steam; according to Fischer (Real
Encyclopädie der gesammten Pharmacie) this treatment, however, will cause a
decomposition of the said compound itself.
"
"
During experiments made with the products of oxidation of the substances
obtained by the action of sulphuric acid upon sulphuretted mineral oils and simi-
lar hydro-carbons, it has however been observed that, for instance, the offensive
smelling substances of the "ichthyol are proportionately easiest oxidisable and
transformed into nearly odourless products by oxidation. If the oxidation is in-
creased also the remaining constituents of the "ichthyol" undergo oxidation and
a characteristically smelling product is again obtained, which, however, is parti-
cularly distinguished from the "ichthyol" by its physical and chemical proper-
ties. If, therefore, a nearly odourless preparation is to be obtained care should
be taken that an extremely small oxidizing action upon the product takes place.
In consequence of this fact it has been proved by experiments that upon one
hundred kilogrammes of "ichthyol as brought into the market one third of a
kilogramme of oxygen is sufficient to destroy the peculiar smell of the product.
On oxidation of the " ichthyol" within this limit only the odourous substances
are substantially oxidized, whilst all remaining constituents, viz.: the sulphonic
acid salts, the sulfones and sulfone-like bodies, are still unaltered. Conse-
quently, the preparation obtain still possesses strongly reducing properties.
As an oxidizing agent peroxide of hydrogen has proved to be the most applic-
able for the said purpose since by this means no foreign substances, the removal
of which is accompanied with considerable difficulties, are admitted into the
preparation. The traces of aromatic smelling substances, which might be formed
by an excess of the oxidising agent, are volatile with the vapourizing water and
may be removed therefore, by employing a current of steam or by simply heating
the preparation, either in vacuo or under diminished or atmospheric pressure.
Like the ichthyol-ammonium also behave the other ichthyol salts and the

page_text: ichthyol-sulphonic acid, as well as all corresponding substances derived from
sulphuretted mineral oils and similar hydro-carbons combined with sulphuric
acid.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.
Improvements in and relating to Sulphur Compounds of Mineral Oils
and similar Hydrocarbons,
I, Dr. LUDWIG OTTO HELMERS, of 21, Bohnenstrasse, in the City of Hamburg,
in the Empire of Germany, Chemist, do hereby declare the nature of this inven-
tion and in what manner the same is to be performed, to be particularly des-
cribed and ascertained in and by the following statement; -
My invention relates to improvements in sulphonized carbon compounds, ob-
tained by the action of sulphuric acid or its substitutes on mineral oils or simi-
lar hydrocarbons and the object of the same consists in rendering such substances
odourless or nearly so.
It is a well known fact that the sulphonized carbon compound produced from
Seefeld mineral oil and known under the name of ichthyol" possesses a very
intense and peculiar smell derived from a volatile on generated during the pro-
duction of the said compound. This volatile oil may, of course, be removed by
distillation with the aid of a current of steam; according to Fischer (Real
Encyclopädie der gesammten Pharmacie) this treatment, however, will cause a
decomposition of the said compound itself.
*
During experiments made with the products of oxidation of the substances
obtained by the action of sulphuric acid upon sulphuretted mineral oils and
similar bydrocarbons, it has however been observed that, for instance, the offen-
sive smelling substances of the ichthyol are proportionately more readily
oxidisable and transformed into nearly odourless products by the absorption of
oxygen. If the oxidation is increased, the remaining constituents of the "ich-
thyol" also undergo oxidation and a product of characteristic odour is again ob-
tained, which, however, is particularly distinguished from the "ichthyol" by
its physical and chemical properties. If, therefore, a nearly odourless prepara-
tion is to be obtained care should be taken that an extremely small oxidizing
action upon the product takes place.
23
In consequence of this fact it has been proved by experiments that upon one
hundred kilogrammes of "ichthyol" as brought into the market, one third of a
kilogramme of oxygen is sufficient to destroy the peculiar scent of the product.
On oxidation of the ichthyol within this limit only the odourous substancès
are substantially oxidized, whilst all remaining constituents, viz.; the sulphonic
acid salts, the sulphones and sulphone-like bodies, are still unaltered. Conse-
quently, the preparation obtained still possesses strong reducing properties.
As the oxidizing agent peroxide of hydrogen has proved to be best applica-
able for the purpose since by this means no foreign substances, the removal of
which is accompanied with considerable difficulties, get admitted into the pre-
paration. The peroxide of hydrogen hereby dissociates into water and oxygen,
and the latter unites with the smelling substances to form odourless substances.
The traces of aromatic smelling substances, which might be formed by an excess

page_text: of the oxidizing agent, are volatile with the vaporizing water and may be removed,
therefore, by employing a current of steam or by simply heating the preparation,
either in vacuo or under diminished or atmospheric pressure.
Like the ichthyol-ammonium also behave the other ichthyol salts and the
ichthyol-sulphonic acid, as well as all corresponding substances derived from
sulphuretted mineral oils and similar hydro-carbons combined with sulphuric
acid.
In order to make my invention more clearly understood I will proceed to
describe the same by way of an example, as follows.
Ten kilogrammes of ichthyol-ammonium are mixed with about 7.5 litres of
water and to this mixture is added 2.5 kilogrammes of a solution of peroxide of
hydrogen as brought into the market (containing about 3 per cent. of peroxide
of hydrogen) whereupon the whole is left at rest while kept cool. The charac-
teristic odour of the ichthyol" then escapes successively instead of which a
mild aromatic odour will be observed. After the lapse of 24 to 48 hours the
mixture is decanted into a shallow vessel and then concentrated by heating.
Together with the evaporizing water the minute quantities of the aromatic
smelling substances then also escape. Finally, the residue is again dissolved in
water, neutralized by ammonia and evaporated to the originally, weight, that
is to say 10 kilogrammes.
Having now particularly described and ascertained the nature of my said in-
vention and in what manner the same is to be performed, I declare that what I
claim is:-
:
1. The process of rendering odourless, or nearly so, preparations from sul-
phonized compounds derived from sulphuretted mineral oils or similar hydro-
carbons by treatment with sulphuric acid, which consists in treating aqueous
solutions of such substances while kept cool, with an oxydizing agent and then
concentrating the same by heating, substantially as set forth.
2. As a new product of manufacture the hereindescribed preparations consist-
ing of oxidised sulphonized compounds derived from sulphuretted mineral oils
or similar hydro-carbons which preparations are soluble in water and nearly
free from odour.
Dated this 10th day of February 1899.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.