Soluble Sulphonic Acid Salts of Alkaline Earthy Metals and Metals proper and Corresponding Sulphonic Acids, and Process of Making same.
Year: 1899

page_text: Date of Application, 12th July, 1899
Complete Specification Left, 11th Apr., 1500-Accepted, 12th May, 1900
PROVISIONAL
SPECIFICATION.
Soluble Sulphonic Acid Salts of Alkaline Earthy Metals and Metals
proper and Corresponding Sulphonic Acids, and Process of Making
same.
I, Dr. LUDWIG OTTO HELMERS, of 174, Fuhlsbüttelerstrasse, in the City of
Hamburg and Empire of Germany, Chemist, do hereby declare the nature of
this invention to be as follows:-
In the Specification of my former British Letters Patent No. 5004 of 1898 it
is stated that the earth alkali salts and metal salts of ichthyol sulphonic acid and
other similar acids obtained by causing sulphuric acid to act upon mineral oils
and other hydrocarbons containing fixed sulphur in the form of sulphide, are
insoluble in water. This statement is only partially correct inasmuch as the
largest part of the acids contained in the so-called ichthyol sulphonic-acid and
in similar substances form insoluble earth-alkali and metal salts, while only a
small quantity remains dissolved in the water on its conversion into earth-
alkali and metal salts.
Closer examination has shown these sulphonic-acids which form soluble earth
alkali salts and metal salts are distinctive on account of their high percentage
in sulphur (they contain generally 21% of sulphur as against 15% in the in-
soluble product) further on account of their highly acidic character (they com-
bine for example nearly 8% of calcium while the product insoluble in water
only contains 2% of calcium) and finally on account of the capability of their
salts to convert substances, insoluble in water, such as cresol, in far larger
quantity into an aqueous solution than the alkali salts which correspond to the
insoluble earth alkali and metal salts.
These sulphonic-acids or their salts are produced by neutralizing the pro-
ducts, obtained from. the action of sulphuric acid on mineral oils, in an aqueous
solution with the corresponding oxide, hydroxide, or carbonate. After some time
the liquid is filtered off from the precipitated insoluble salts, the filtrate is dried
and from the salts thus obtained the sulphonic-acid is liberated by adding a
stronger acid or by precipitating the metal by means of hydric sulphide.
The sulphonic-acids and their salts thus obtained have strong reducing quali-
ties. This reducing action is so efficient that several salts, for example silver
salts and mercury salts which have an easily reducible base in aqueous solution
give up slowly the reduced metal already when left standing, quicker, of course,
when heat is applied.
In order to obtain permanent solutions of such metal salts it is necessary to
partly oxidize the sulphonic-acid. This can be done conveniently by taking the
sulphonic-acid, obtained for instance from the action of sulphuric acid on
calcium salt, and oxidize it with peroxide of hydrogen and then producing from
this oxidized acid the metal salt by neutralization with silver oxide or the like.
Double salts may be obtained in the same manner. Of these compounds the
ammonia double salts, for example argentic ammonia salts, are of importance

page_text: because the presence of ammonia salts prevents or at least greatly reduces the
precipitation of albumin by metal salts.
Dotad this 19th day of T1 1900
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.
Soluble Sulphonic Acid Salts of Alkaline Earthy Metals and Metals
proper and Corresponding Sulphonic Acids, and Process of Making
same.
I, Dr. LUDWIG OTTO HELMERS, of 174, Fuhlsbüttelerstrasse, in the City of
Hamburg and Empire of Germany, Chemist, do hereby declare the nature of
this invention and in what manner the same is to be performed, to be particularly
described and ascertained in and by the following statement:-
In the Specification of my former British Letters Patent No. 5004 of 1898 it
is stated that the earth alkali salts and metal salts of ichthyol sulphonic acid and
other similar acids obtained by causing sulphuric acid to act upon mineral oils
and other hydrocarbons containing fixed sulphur, are insoluble in water. This
statement is only partially correct inasmuch as the largest part of the acids con-
tained in the so called ichthyol sulphonic acid and in similar substances form
insoluble earth alkali and metal salts, while only a small quantity remains dis-
solved in the water on its conversion into earth alkali and metal salts.
Closer examination has shown that these sulphonic acids which form soluble earth
alkali salts and metal salts are distinctive on account of their high percentage
in sulphur (they contain generally 21% of sulphur as against 15% in the in-
soluble product) further on account of their highly acidic character (they con-
tain for example nearly 8% of calcium while the product insoluble in water
only contains 21% of calcium) and finally on account of the capability of their
salts to convert substances, insoluble in water, such as cresol, in far larger
quantity into an aqueous solution than the alkali salts which correspond to the
insoluble earth alkali and metal salts.
These sulphonic-acids or their salts are produced by neutralizing the pro-
ducts, obtained from the action of sulphuric acid on mineral oils, in an aqueous
solution with the corresponding oxide, hydroxide, or carbonate. After some time
the liquid is filtered off from the precipitated insoluble salts, the filtrate is dried
and from the salts thus obtained the sulphonic-acid is liberated by adding a
stronger acid or by precipitating the metal by means of hydric sulphide.
The following examples may more fully elucidate the present invention.
1. The solution of 1 kg. of the sulphonic product, obtained by the action of
concentrated sulphuric acid upon Seefeld oil, in 3 kgs. of water is heated and
gradually mixed under continuous stirring with baryta-water until the solution
shows a weak alkaline reaction. The change or turn of the green colour of the
sulphonic product into a yellowish brown one indicates clearly the beginning of
the neutralisation. The neutralized mass or substance is then left to rest, where-
upon the brown coloured liquid is decanted off, filtered and finally the filtrate
evaporated to dryness.
The baryta salt forming the residue appears as a yellowish brown, easily
pulverizable, scarcely hygroscopic mass or substance which possesses a bitter
taste and may be readily and clearly dissolved in water; the solution having a
yellowish colour.

page_text: By dissolving the baryta salt in a small quantity of water and mixing this
solution with a quantity of sulphuric acid corresponding to the amount of baryia
a solution of the free sulphonic acid is obtained which when evaporated to dryness
after the separated or precipitated sulphate of baryta has been filtered off, forms
a green coloured hygroscopic residue.
2. The soluble earth alkali and metal salts may also easily be produced from
the commercial ammonia salts of the said sulphonic products, as will be evident
from the following example.
1 kg. of petrosulphol is mixed with lime-milk containing about 30 grammes
of caustic lime, and then heated until the escape of ammonia ceases. The lime-
salts obtained from the sulphonic acids are washed with water, whereupon the
water which has been used in washing is liberated from the lime in excess by
the introduction of carbonic acid and by boiling the said water, then filtered
and finally evaporated to dryness.
The sulphonic-acids and their salts thus obtained have strong reducing quali-
ties. This reducing action is so efficient that several salts, for example silver
salts and mercury salts which have an easily reducible base in aqueous solution
give up slowly the reduced metal when left standing, and more quickly, of course,
when heat is applied.
In order to obtain permanent solutions of such metal salts it is necessary to
partly oxidize the sulphonic-acid. This can be done conveniently by taking the
sulphonic-acid, obtained for instance from the action of sulphuric acid on
calcium salt, and oxidize it with peroxide of hydrogen and then producing from
this oxidized acid the metal salt by neutralization with silver oxide or the like.
Example: kg. of the sulphonic acid obtained in the manner above described
is dissolved in kg. of water; this solution is mixed with about 21 kg. of a
peroxide of hydrogen solution (containing 3% H2 02) and the mixture for several
hours heated by means of a water-bath nearly to boiling.. The now brown
coloured liquid is then neutralized with silver oxide, filtered off from the silver
oxide in excess and the filtrate finally evaporated in vacuo. After being fully
dried, the silver salt forms a brown substance which is easily pulverizable and
readily soluble in water.
Metal salts which are permanent in aqueous solutions, may also be produced
by subjecting the original product obtained by the action of concentrated
sulphuric acid upon hydrocarbons containing fixed sulphur to a moderate oxida-
tion and then by treating this oxidized product according to the above described
process; in this case there are directly obtained metal salts which are permanent in
aqueous solutions.
The salts produced by the process hereindescribed may be used for many pur-
poses, amongst others, for dissolving hydrocarbons, phenols, ethereal oils and
the like.
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 acid salts of alkaline earth metals and
metals proper from sulphureted tar-oils and similar hydrocarbons combined with
sulphuric acid, which consists in neutralizing the aqueous solutions of such sub-
stances or their ammonia salts with a base, filtering off the liquid from the
precipitated insoluble salts and evaporating the filtrate to dryness, substantially
as and for the purpose set forth.
2. The process of producing sulphonic acid salts of alkaline earth metals and
metals proper from sulphureted tar-oils and similar hydrocarbons combined with
sulphuric acid, which consists in neutralizing the oxidized product of such sub-
stances or their ammonia salts in aqueous solution with a base, filtering off the
liquid from the precipitated insoluble salts and evaporating the latter to dryness,
substantially as and for the purpose set forth.

page_text: 3. The process of producing sulphonic acids readily soluble in water and
having reducing properties, which consists in liberating the sulphonic acid from
the hereindescribed sulphonic acid salts of the metals or earth metals of the
alkalies, removing the liberated sulphonic acid by filtration and evaporating the
same to dryness, substantially as and for the purpose set forth.
4. The process of producing metal salts permanent in aqueous solution by
partly oxidizing the herein described sulphonic acids and neutralising the
oxidised product with the corresponding metallic oxide, substantially as and for
the purpose set forth.
5. As a new product of manufacture the herein described sulphonic acids and
their salts derived from sulphureted tar oils and similar hydrocarbons combined
with sulphuric acid, which substances are soluble in water.
Dated this 11th day of April 1900.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
agents for the Applicant.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.