A Process for Facilitating the Oxidation of Sulphurous Acid for the Manufacture of Sulphuric Acid and of Hydrochloric Acid and Chlorine and for other Industrial Purposes.
Year: 1888

page_text: A Process for Facilitating the Oxidation of Sulphurous Acid for the
Manufacture of Sulphuric Acid and of Hydrochloric Acid and
Chlorine and for other Industrial Purposes.
1.
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 Jean Baptiste Daguin, of 44, Rue de Château Landon, Paris, France, Manufacturer of
Chemical Products) to be as follows:-
This Invention relates to a new process for facilitating the oxidation of sulphurous
acid by means of the oxygen of the air or other source.
The process consists essentially in treating a mixture of sulphurous acid and air or
oxygen with or without the addition of aqueous vapor in the presence of salts of
manganese, copper, iron, tin etc.; or to speak more generally in the presence of
body capable of acting as a catalytic agent that is to say, capable of favoring the
oxidation of sulphurous acid, by means of the oxygen of the air.
any-
This improved process is applicable in all cases where it is desired to effect the
oxidation of sulphurous acid in the course of any operation, but the invention will be
here described with reference to its two principal applications-vist.-the manufacture
of sulphuric acid and the manufacture of hydrochloric acid and chlorine.
I. Manufacture of sulphuric acid. In this case the catalytic agents which it is
preferred to employ are the sulphates of manganese, copper, iron, tin, etc.; which
act merely by their presence, sulphuric acid being produced according to the following
reaction

page_text: caused to traverse a column filled with coke or other material unattackable by sulphuric
acid and impregnated with said solution. In both cases the resulting liquid contains
sulphuric acid mixed with the sulphate employed, which acid may be separated by
distillation. Moreover when employing the second mode of operation and by raising
the coke column to a sufficient temperature a great proportion of the sulphuric acid
may be obtained direct from the apparatus.
II. Manufacture of hydrochloric acid and chlorine. In applying the invention to
this purpose, any chloride is treated with a mixture of sulphurous acid and air or
oxygen with or without aqueous vapor, in presence of the catalytic agents above
indicated. The operation may be performed either in the wet or in the dry way. If
the wet process be employed, operating on sodium chloride for example in presence
of chloride of manganese by causing the gases to bubble through the chlorides in
solution, the following reactions take place
As will be seen the chloride of manganese is recovered at the end of the operation in
which it merely acts by its presence, which is of great importance as above mentioned.
The hydrochloric acid formed may be separated by distillation and utilised direct or
it may be employed in the preparation of chlorine by means of binoxide of manganese.
The binoxide of manganese may however be added to the liquor resulting from the
second reaction, whereby chlorine is obtained direct. After the chlorine has been
separated, the residual liquid may be treated in any suitable manner for the purpose of
regenerating the hinoxide of manganese. Or the binoxide of manganese may be added
at the commencement of the operation (first reaction) which gives :-
Na Cl + Mn 0² + SO² + 0 = Na O SO3 + Mn Cl + Cl
For the sake of clearness I have not included in the formula the chloride of man-
ganese, copper, iron, etc., whose presence is necessary and constitutes as above
mentioned the great feature of the invention.
The sulphate obtained at the end of the reaction may according to its nature be
separated for sale as such or be otherwise utilised.
If the chloride to be treated, is decomposable with difficulty by the sulphurous acid
and oxygen even in the presence of the catalytic agents, it may be converted by double
decomposition into a chloride which will more readily produce this reaction. I may
employ for this purpose a sulphate or other salt of the base selected. Suppose for
example barium chloride is to be treated; it would be converted by the action of
magnesium sulphate into magnésium chloride which is more easily treated. The
following is the reaction:-
(1) Mg Cl Mn Cl+SO + 0 +
(2) Mn O, SO³ + Mg Cl + H CI
-
HO = Mn O, SO3 + Mg Cl + HCl
Mg O, SO3 + Mn Cl + H Cl.
In this manner, hydrochloric acid is obtained, the magnesium sulphate being
regenerated and utilized for converting a fresh quantity of barium chloride into
magnesium chloride.
The apparatus employed in these reactions may be any of those ordinarily used in
similar chemical operations.

page_text: The process herein described, as performed in the wet way may also be applied in
the dry way with or without the aid of aqueous vapor (as before mentioned) and also
serve for obtaining hydrochloric acid or chlorine which is liberated direct and
collected for use.
A. MELVILLE CLARK.
By A. M. & Wm. Clark,
53, Chancery Lane, London,
Patent Agents.
COMPLETE SPECIFICATION.
A Process for Facilitating the Oxidation of Sulphurous Acid for the
Manufacture of Sulphuric Acid and of Hydrochloric Acid and
Chlorine and for other Industrial Purposes.
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 Jean Baptiste Daguin, of 44 Rue de Château Landon, Paris, France, Manufacturer
of Chemical Products) and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
This Invention relates to a new process for facilitating the oxidation of sulphurous
acid, by means of the oxygen of the air or other source.
The process consists essentially in treating a mixture of sulphurous acid and air or
oxygen with or without the addition of aqueous vapor in the presence of salts of manganese,
copper, iron, tin, etc.; or, to speak more generally, in the presence of any body capable
of acting as a catalytic agent, that is to say, capable of favoring the oxidation of
sulphurous acid, by means of the oxygen of the air.
This improved process is applicable in all cases where it is desired to effect the
oxidation of sulphurous acid in the course of any operation, but the invention will
be here described with reference to its two principal applications-vizt.-the manufacture
of sulphuric acid and the manufacture of hydrochloric acid and chlorine.
1. Manufacture of sulphuric acid. In this case the catalytic agents which it is
preferred to employ are the sulphates of manganese, copper, iron, tin, etc.; which act
merely by their presence, sulphuric acid being produced according to the following
reaction.

page_text: In order to bring the sulphurous acid and oxygen into the presence of the above catalytic
agents they may be caused to bubble through a solution of the same, or be caused to
traverse a column filled with coke or other material unattackable by sulphuric acid
and impregnated with said solution. In both cases the resulting liquid contains
sulphuric acid mixed with the sulphate employed, which acid may be separated by
distillation. Moreover when employing the second mode of operation and by raising
the coke column to a sufficient temperature a great proportion of the sulphuric acid
may be obtained direct from the apparatus.
II. Manufacture of hydrochloric acid and chlorine. In applying the invention to
this purpose, any chloride is treated with a mixture of sulphurous acid and air or
oxygen with or without aqueous vapor in presence of the catalytic agents above in-
dicated. The operation may be performed either in the wet or in the dry way. If
the wet process be employed, operating on sodium chloride for example in presence of
chloride of manganese by causing the gases to bubble through the chlorides in solution,
the following reactions take place -
(1) Na Cl + Mn Cl + SO² + 0 +
(2) Mn O, SO3 + Na Cl + HC
=
HO = Mn 0,80 + Na Cl + H CI
Na O, SO3 + Mn Cl + H CI.
As will be seen the choride of manganese is recovered at the end of the operation
in which it merely acts by its presence, which is of great importance as above
mentioned.
The hydrochloric acid formed may be separated by di..tillation and utilised direct or
it may be employed in the preparation of chlorine by means of binoxide of manganese.
The binoxide of manganese may, however be added to the liquor resulting from the
second reaction, whereby chlorine is obtained direct. After the chlorine has been
separated, the residual liquid may be treated in any suitable manner for the
purpose ol
regenerating the binoxide of manganese. Or the binoxide of manganese may be
added at the commencement of the operation (first reaction) which gives :-
:-
Na Cl + Mn 0² + SO² + 0 = Na O SO3 + Mn !+ Cl.
(1) Mg Cl + MnCl + SO² + 0
(2) Mn 0, SO3 + Mg Cl + HC
+
====
HO = Mn O, SO3 + Mg Cl + HCl
Mg O, SO3 + Mn Cl + H Cl.
Mg Cl + Mn C + SO² + 0 +
(2) Mn O, SO3 + Mg Cl + H CI
=
HO = Mn O, SO³ + Mg Cl + HCl
Mg O, SO3 + Mn Cl + HCl.
In this manner, hydrochloric acid is obtained the
agnosin

page_text: The apparatus employed in these reactions may be any of those ordinarily used in
similar chemical operations.
The process herein described, as performed in the wet way may also be applied in
the dry way with or without the aid of aqueous vapor (as before mentioned) and also
serve for obtaining hydrochloric acid or chlorine which is liberated direct and collected
for use.
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 I
claim is
1st. The herein described process of oxidising sulphurous acid by means of the
oxygen of the air or other source which consists in producing a reaction between
them in presence of the salts of manganese, copper, iron, tin, etc. or other body
acting catalytically to promote oxidation, substantially as specified.
2nd. The herein described process of manufacturing sulphuric acid by the employ-
ment as catalytic agents promoting oxidation, of sulphates of manganese, copper, iron,
tin, etc., as specified.
3rd. The herein described process of manufacturing hydrochloric acid and chlorine,
by treating chloridos either in the dry or humid way with a mixture of sulphurous acid
and air or oxygen, together or not with aqueous vapor in presence of catalytic agents
promoting oxidation, substantially as specified.
4th. The conversion by double decomposition of chlorides difficultly decomposable
by the herein described process, into chlorides more easily decomposable, such as
magnesium chloride for example, substantially as specified.
5th. The application and use of this improved process in any industrial operations in
which it is desired to effect the oxidation of sulphurous acid.
Dated this 10th day of December 1888.
A. M. CLARK.
By A. M. & Wm. Clark,
53, Chancery Lane, London,
Patent Agents.