Improved Process and Apparatus for the Manufacture or Production of Hydrogen and Chlorine from Hydrochloric Acid.
Year: 1891

page_text: Date of Application, 18th Nov., 1891
Complete Specification Left, 4th Dec., 1891-Accepted, 16th Jan., 1892
FROVISIONAL SPECIFICATION.
Improved Process and Apparatus for the Manufacture or Production
of Hydrogen and Chlorine from Hydrochloric Acid.
I, CARL KELLNER, Director of the Kellner-Partington-Paper-Pulp-Company,
Limited, Vienna, IX. Wasagasse 29, Austria, do hereby declare the nature of this
invention to be as follows:-
This invention has reference to the manufacture or production of chlorine by
electrolytically decomposing hydrochloric acid, instead of by the chemical action
of certain substances usually manganese oxides, on chlorine-containing substances
as heretofore usually employed.
My process is characterized from the usual processes, by a continuous and
uniform generation of chlorine, by which the great disadvantages of the violent
generation of chlorine gas immediately after charging the usual generating apparatus
with manganese oxides, and of the gradually weaker generation in the course of the
decomposition of the chlorine-containing substance, are obviated.
The hydrochloric acid to be decomposed electrolytically, is preferably heated
either within or external to the decomposing apparatus, in order to reduce the
electrical resistance, to accelerate the escape of the gases, and to render the liquid
flowing out of the apparatus as free from chlorine as possible.
Fig. 1 shews a chlorine generator partly in vertical cross section and partly in
side elevation.
Fig. 2 is a longitudinal section of the upper part of this generator.
Fig. 3 is a horizontal section on the line of Fig. 2.
Fig. 4 illustrates in longitudinal vertical section the upper part of a modified
arrangement of the decomposing apparatus, and
Fig. 5 is a horizontal section on the line y y of Fig. 4.
Fig. 6 is a portion, shewn to a larger scale, of a single receptacle of the decom-
posing apparatus, and shews the connection of the similar electrodes with one
another.
Fig. 7 shews the ends of the electrodes with their connecting pieces in side
elevation.
Fig. 8 is a modified arrangement of the apparatus illustrated in Fig. 6.
Figs. 9 and 10, are respectively a vertical central section and a horizontal
section of a decomposing apparatus of circular form in plan instead of the rectangular
form shewn in Fig. 1.
Figs. 11 to 16 inclusive illustrate an arrangement of chlorine generator with
vertically suspended electrodes.
Fig. 11 being a vertical section partly in end elevation;
Fig. 12 a vertical longitudinal section, partly in side elevation;
Fig. 13 a horizontal section and partial plan and
Fig. 14 a detail view.
Figs. 15 and 16 are respectively a section partly in elevation, and a side
elevation of a modified arrangement of the partitions which separate the electrode
cells.
The decomposing apparatus or chlorine generator consists of a number (to be
increased according to requirement) of receptacles 1, 2, 3, 4. ... (Fig. 1), which
are suitably made of stoneware or other acid-proof material, and fit one upon another
as shewn by means of upper and lower border-fillets, which are arranged to make a
gas-tight joint in such a manner as to form gas-tight outer walls.
The direction of morament of the liquid in the annaratus and of the cases formed

page_text: from said liquid by electrolytic decomposition are made to take place in opposite
directions, the hydrochloric acid flowing into the apparatus through the pipe a in a
continual and uniform stream traversing the same from top to bottom, flowing
through all the receptacles, and passing out of the apparatus at the bottom through
the pipe whilst the separately generated gases-hydrogen and chlorine-flow
through the apparatus from bottom to top and escape from the highest points of the
same through the pipes c and d respectively.
Each receptacle 1, 2, 3, 4, .., is divided into electrode cells by means of longi-
tudinal ribs m which project down from the bottom of the receptacle next above,
and dip in the liquid. All cells situated vertically over one another contain similar
electrodes, which are arranged horizontally in alternate order, a being anodes, and
ẞ cathodes (Fig. 6). The gas given off in the cells, viz. hydrogen at the cathodes,
and chlorine at the anodes, passes into the next receptacle above through ascension
pipes n that traverse the bottom of the said receptacles. The ascension pipes n are
arranged in the superposed receptacles in an alternate manner being at the right
hand end of one receptacle and at the left hand end of the receptacle next above it,
so that the gas is compelled to take a serpentine course through the apparatus,
until it passes out through one of the pipes c or d on the cover of the apparatus,
whence it is conveyed to any suitable place to be utilized.
As will be understood from the foregoing description, the ribs m which dip in
the liquid and form the limits of the electrode cells, constitute in conjunction with
such liquid a hydraulic seal for the generated gases which consequently flow through
the cells.
For maintaining the level of liquid in the several receptacles and for preventing
liquid from entering the ascension pipes n, the receptacles are provided with over-
flow walls o (Figs. 2 and 3) which are not quite so high as the top edge of the
pipes ; or with overflow pipes (Figs 4 and 5) which are arranged at the opposite
sides of the receptacles to that of the ascension pipes n.
When overflow walls o (as in Figs. 2 and 3) are employed, lateral passages
and are formed between the said walls o and the outer walls of the apparatus, in
every two superposed receptacles, and through which passages liquid flows from
cacli receptacle into the next lower one. To prevent the gas in the cells from
entering these passages, bottom ribs o are provided to limit the electrode cells in
the direction of their length; thus the gases in the cell flowing in the opposite
direction to that of the movement of the liquid, are shut off hermetically from the
passages and
Opposite to and extending upwards towards the lower bottom ribs or incomplete
cell walls m of each receptacle are upper bottom ribs m¹ (Fig. 6) on the next lower
receptacle. Between the ribs m and m', there may be inserted, as shown in Fig. 8.
diaphragms m², whereby the electrode cells can be entirely closed, when it is desired
to effect the electrolytic decomposition of compounds, the splitting-up of which is
less advantageous without diaphragms between the electrodes. The upper rib m
might also extend down into contact with the rib m', in which case it would have
to be perforated, in order to facilitate the mingling of the liquid flowing in two
adjacent cells, by obviating the formation of a stagnant layer of liquid.
The electrodes a and B which are best made of carbon rods, are in the arrange-
ments illustrated in Figs. 1-8, arranged horizontally in the cells.
All the similar electrodes of a receptacle are connected together by lead con-
ductors which somewhat resemble spectacle frames in shape (see Fig. 6) and are
provided on their upper surface with a covering of good insulating material and
are cast on the electrodes. The rows of electrodes located in the several receptacles
may advantageously be connected in successive order as follows:-The last
electrode in each receptacle is electrically connected with the dissimilar row of
electrodes in the next lower receptacle. The uppermost row of cathodes (or
anodes) and the lowest row of anodes (or cathodes) are connected to a suitable
source of electricity.
For heating the liquid in the gas generator there may advantageously be

page_text: employed a coiled pipe into which steam enters through the pipe e, and from which
the waste steam and water of condensation pass out at el.
The flow of liquid through the chlorine generator is regulated in such a manner
that the liquid passing out at b shall contain the least possible amount of undecom-
posed hydrochloric acid.
In large industrial works, to prevent waste of even very small quantities of
hydrochloric acid, the escaping liquid is saturated with hydrochloric acid gas and
again conducted through the decomposing apparatus, so that the same water always
flows through the apparatus, fresh quantities of hydrochloric acid being supplied
each time for decomposition.
The operation of the apparatus is as follows:-.
The hydrochloric acid to be decomposed enters in a continuous stream through
the pipe a, flows through the longitudinal cells of the uppermost receptacle con-
taining the electrodes and formed by the ribs m, and flows over the overflow wall o
or through the pipe into the next lower receptacle through the cells of which it
flows in the opposite direction, and flows into the next lower receptacle, and so on.
The chlorine gas generated at the anodes and the hydrogen liberated at the cathodes,
ascend in an opposite direction to that of the movement of the liquid. They pass
through the ascension pipes n from the generating cells into the overlying cells,
traverse the latter and ascend on the other side into the next higher cells and so
on, so that say all the even superposed cells serve as a passage for the hydrogen,
and all the odd superposed cells serve as a passage for the chlorine. One of the
collecting pipes c and d', which lead to the gas discharge pipes c and d on the
cover of the decomposing apparatus, is in communication with the even cells of
the uppermost receptacle but not with the odd cells. The other collecting pipe on
the contrary is in communication with the odd cells, but not with the even cells,
so that the two gases pass separately out of the apparatus for subsequent
utilization.
The round chlorine generator illustrated in Figs. 9 and 10, is composed of a
number of superposed trays or receptacles. Each of these is divided by the annular
rib m (which hangs down from the bottom of the overlying receptacle, and dips
into the liquid in the next lower one) into an inner circular chamber and an
annular chamber that surrounds. These chambers serve for the reception of rows
of radially arranged electrodes a and B or electrodes arranged at right angles to the
radial direction as shewn. The liquid is supplied to the central chamber of the
uppermost tray through the supply pipe a, and to the annular chamber enclosing
the same by the supply pipe a'. The liquid flows from the central chamber through
the central overflow pipes p which are covered with deflecting caps 7, into the next
lower central spaces, whilst liquid flows from the annular chamber through the
overflow pipes p' (which are arranged alternately at opposite sides of the apparatus)
into the next lower annular chamber, and flows off from the lowermost tray through
the discharge pipe b. As hereinabove stated, this liquid which still contains a
small quantity of undecomposed hydrochloric acid, may be again saturated with
hydrochloric acid gas and re-used for charging the decomposing apparatus.
The gas generated in the central chambers, ascends through the central over-
The
flow pipes p and finally flows off from the uppermost tray through the pipe c.
gas liberated in the annular chambers "passes into the lateral ascension passages n'.
The inlet to cach of these passages is at a point above the level of the liquid in the
receptacle below it so as to allow the gas to freely enter the passage. The outlet
end of each of the passages terminates at a point above the top of the adjacent
overflow pipe in order to prevent liquid from entering the passage. The gas
generated in each annular chamber flows through the same around the dividing
rib m to the corresponding ascension passage n' through which it passes into the
next higher annular chamber, and so ou, and finally passes off from the uppermost
receptacle through the pipe d. In this construction a greater electrical resistance
has to be overcome than in the hereinbefore described arrangement, owing to the
greater distance apart of the electrodes a and B.

page_text: In the decomposing apparatus illustrated in Figs. 11 to 16 inclusive vertically
suspended electrodes are used instead of horizontal ones. As will be seen, the said
apparatus consists of a number of cells closed at the top and separated from each
other by perforated partitions g and in which cells there are suspended alternately
rows of anodes a and cathodes ẞ. All the cells are located in a common trough
of acid proof material above a perforated bottom through which the solution of
hydrochloric acid gas (which enters from below through the pipe a and is heated
by means of the steam pipe e) flows upwards and after decomposition of the
hydrochloric acid (or of the greater part of the same) flows out of the cells through
upper lateral openings formed in opposite sides of the wall of the trough alternately
into the collecting pipes 2 and 3, and thence out of the apparatus. The gases
liberated in the electrode cells ascend through the ascension pipes-n and n' which
pass through the bar k carrying the electrodes, into its respective collecting pipe.
All the electrodes of cach cell are fixed in an upper removable supporting bar k.
This may be effected by casting in with lead into a metallic perforated supporting
bar k, or, as shown in the drawing, by means of tight joints produced by caoutchouc
rings k¹.
For the purpose of effecting a gas tight upper closure of each electrode cell,
each supporting bar has extending entirely around it a downwardly projecting
which enters a gutter-shaped recess ³ formed in the upper
part of the cell and filled with putty or cement.
strip of sheet metal
Instead of using undivided and perforated partitions g as shewn in Figs. 11-14,
there may be employed partitions which are composed of a number of horizontal
superposed rectangular shaped bars or rods s (Figs. 15 and 16) that are provided
on their upper and lower sides with recesses forming suitable openings when the
bars or rods are placed one upon another. Upon the uppermost of these bars or
rods which is suitably shaped as shewn in Fig. 15 there rests the upper portion g
of the cell, which is now independent au dnot perforated and constitutes a bell-shaped
hydraulic closure, as shown in Fig. 15.
The hydrogen, drawn from any one of the decomposing apparatus hereinbefore
described, may advantageously be passed through a light hydrocarbon, and when
thus carburetted, can be employed for heating or lighting purposes.
Chlorine gas obtained in the manner hereinbefore described can be used for
producing bleaching agents, particularly chloride of lime, in the manufacture of
paper cellulose and for other purposes.
Dated this 18th day of November 1891.
W. LLOYD WISE,
Per F. J. Brougham,
46, Lincoln's Inn Fields, London, W.C., Agent for the Applicant.
COMPLETE SPECIFICATION.
Improved Process and Apparatus for the Manufacture or Production
of Hydrogen and Chlorine from Hydrochloric Acid.
I, CARL KELLNER, Director of the Kellner-Partington-Paper-Pulp-Company,
Limited, of IX. Wasagasse No. 29 Vienna, 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:-
This invention has reference to the manufacture or production of chlorine by
electrolytically decomposing hydrochloric acid, instead of by the chemical action
of certain substances usually manganese oxides, on chlorine-containing substances
as heretofore usually employed.
My process is characterized from the usual processes, by a continuous and uniform
generation of chlorine, by which the great disadvantages of the violent generation
of chlorine gas immediately after charging the usual generating apparatus with

page_text: next above it, so that the gas is compelled to take a serpentine course through
the apparatus, until it passes out through one of the pipes e or d on the cover
of the apparatus, whence it is conveyed to any suitable place to be utilized.
As will be understood from the foregoing description, the ribs m which dip in
the liquid and form the limits of the electrode cells, constitute in conjunction with
such liquid a hydraulic seal for the generated gases which consequently.flow through
the cells.
For maintaining the level of liquid in the several receptacles and for preventing
liquid from entering the ascension pipes n, the receptacles are provided with
overflow walls o (Figs. 2 and 3) which are not quite as high as the top edge of the
pipes nor with overflow pipes p (Figs. 4 and 5) which are arranged at the
opposite sides of the receptacles to that of the ascension pipes n.
When overflow walls (as in Figs. 2 and 3) are employed, lateral passages r
and are formed between the said walls o and the outer walls of the apparatus, in
every two superposed receptacles, and through which passages liquid flows from
each receptacle into the next lower one. To prevent the gas in the cells from
entering these passages, bottom ribs o are provided to limit the electrode cells
in the direction of their length; thus the gases in the cell flowing in the opposite
direction to that of the movement of the liquid, are shut off hermetically from the
passages and 2ª.
Opposite to and extending upwards towards the lower bottom ribs or incomplete
cell walls of cach receptacle are upper bottom ribs m³ (Fig. 6) on the next lower
receptacle. Between the ribs m and m³, there may be inserted, as shewn in Fig. 8,
diaphragms m, whereby the electrode cells can be entirely closed, when it is desired
to effect the electrolytic decomposition of compounds, the splitting up of which is
less advantageous without diaphragms between the electrodes. The upper rib 772
might also extend down into contact with the rib m', in which case it would have
to be perforated, in order to render more difficult, the mingling of the liquid flowing
in two adjacent cells, by the stagnant layer of liquid in the perforations, without
interfering with the regular function of the electrolytic process.
The electrodes a and B which are best made of carbon rods, are in the arrange-
ment illustrated in Figs. 1-8 arranged horizontally in the cells.
All the similar electrodes of a receptacle are connected together by lead
conductors y which somewhat resemble. spectacle frames in shape (see Fig. 6) and
are provided on their surfaces with a covering of good insulating material and are
cast on the electrodes. The rows of electrodes located in the several receptacles
may advantageously be connected in series by electrically connecting the last
electrode in each receptacle with the dissimilar row of electrodes in the next lower
receptacle. The uppermost row of cathodes (or anodes) and the lowest row of
anodes (or cathodes) are connected to a suitable source of electricity.
For heating the liquid in the gas generator there may advantageously be employed
a coiled pipe into which steam enters through the pipe e, and from which the waste
steam and water of condensation pass out at e¹.
The flow of liquid through the chlorine generator is regulated in such a manner
that the liquid passing out at b shall contain the least possible amount of
undecomposed hydrochloric acid.
In large industrial works, to prevent waste of even very small quantities of
hydrochloric acid, the escaping liquid is saturated with hydrochloric acid gas and
again conducted through the decomposing apparatus, so that the same water always
flows through the apparatus, fresh quantities of hydrochloric acid being supplied
each time for decomposition.
The operation of the apparatus is as follows:-
The hydrochloric acid to be decomposed enters in a continuous stream through
the pipe a, flows through the longitudinal cells of the uppermost receptacle
containing the electrodes and formed by the ribs m, and flows over the overflow
wall o or through the pipe p into the next lower receptacle through the cells of

page_text: 12
which it flows in the opposite direction, and flows into the next lower receptacle,
and so on. The chlorine gas generated at the anodes and the hydrogen liberated
at the cathodes, ascend in an opposite direction to that of the movement of the
liquid. They pass through the ascension pipes from the generating cells into the
overlying cells, traverse the latter and ascend on the other side into the next higher
cells and so on, so that say all the even superposed cells serve as a passage for the
hydrogen, and all the odd superposed cells serve as a passage for the chlorine.
One of the collecting pipes c and d', which lead to the gas discharge pipes c and d
on the cover of the decomposing apparatus, is in communication with the even cells
of the uppermost receptacle but not with the odd cells. The other collecting
pipe on the contrary is in communication with the odd cells but not with the even
cells, so that the two gases pass separately out of the apparatus for subsequent
utilization.
The round chlorine generator illustrated in Figs. 9 and 10, is composed of a
number of superposed trays or receptacles. Each of these is divided by the annular
rib m (which hangs down from the bottom of the overlying receptacle, and dips
into the liquid in the next lower one) into an inner circular chamber and an
annular chamber that surrounds. These chambers serve for the reception of
rows of radially arranged electrodes a and ẞ or electrodes arranged at right angles
to the radial direction as shewn. The liquid is supplied to the central chamber of
the uppermost tray through the supply pipe a, and to the annular chamber enclosing
the same by the supply pipe a'. The liquid flows from the central chamber through
the central overflow pipes p which are covered with deflecting caps 7, into the next
lower central spaces, whilst liquid flows from the annular chamber through the
overflow pipes (which are arranged alternately at opposite sides of the apparatus)
into the next lower annular chamber, and flows off from the lowermost tray through
the discharge pipe b. As hereinabove stated, this liquid which still contains a
small quantity of undecomposed hydrochloric acid, may be again saturated with
hydrochloric acid gas and re-used for charging the decomposing apparatus.
I
The gas generated in the central chambers f, ascends through the central over-
flow pipes and finally flows off from the uppermost tray through the pipe c. The
gas liberated in the annular chambers ƒ passes into the lateral ascension passages n'.
The inlet to each of these passages is at a point above the level of the liquid in the
receptacle below it so as to allow the gas to freely enter the passage. The outlet
end of each of the passages terminates at a point above the top of the adjacent
overflow pipe in order to prevent liquid from entering the passage. The gas
generated in each annular chamber f¹ flows through the same around the dividing
rib m to the corresponding ascension passage n' through which it passes into the
next higher annular chamber, and so on, and finally passes off from the uppermost
receptacle through the pipe d. In this construction a greater electrical resistance
has to be overcome than in the hereinbefore described arrangement, owing to the
greater distance apart of the electrodes a and ẞ.
y
In the decomposing apparatus illustrated in Figs. 11 to 16 inclusive vertically
suspended electrodes are used instead of horizontal ones. As will be seen, the said
apparatus consists of a number of cells closed at the top and separated from each
other by perforated partitions and in which cells there are suspended alternately
rows of anodes a and cathodes ẞ. All the cells are located in a common trough h
of acid proof material above a perforated bottom ' through which the solution of
hydrochloric acid gas (which enters from below through the pipe a and is heated
by means of the steam pipe e) flows upwards and after decomposition of the hydro-
chloric acid (or of the greater part of the same) flows out of the cells through upper
lateral openings formed in opposite sides of the wall of the trough alternately into
the collecting pipes 2 and 3, and thence out of the apparatus. The gases liberated
in the electrode cells ascend through the ascension pipes n and n which pass
through the bar & carrying the electrodes, into its respective collecting pipe.
All the electrodes of each cell are fixed in an upper removable supporting bar k..

page_text: This may be effected by casting in with lead into a metallic perforated supporting
bar k, or, as shewn in the drawing, by means of tight joints produced by caoutchouc
rings ¹.
For the purpose of effecting a gas tight upper closure. of each electrode cell,
each supporting bark has extending entirely around it a downwardly projecting
strip of sheet metal which enters a gutter-shaped recess ³ formed in the upper
part of the cell and filled with putty or cement.
Instead of using undivided and perforated partitions as shewn in Figs. 11-14,
there may be employed partitions which are composed of a number of horizontal
superposed rectangular shaped bars or rods s (Figs. 15 and 16) that are provided
on their upper and lower sides with recesses_forming suitable openings when the
bars or rods are placed one upon another. Upon the uppermost of these bars or
rods which is suitably shaped as shewn in Fig. 15 there rests the upper portion g
of the cell, which is now independent and not perforated and constitutes a bell-
shaped hydraulic closure, as shewn in Fig. 15.
The hydrogen, drawn from any one of the decomposing apparatus hereinbefore
described, may advantageously be passed through a light hydrocarbon, and when
thus carburetted can be employed for heating or lighting purposes.
Chlorine gas obtained in the manner hereinbefore described can be used for
producing bleaching agents, particularly chloride of lime, in the manufacture of
paper, cellulose and for other purposes.
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 :-
1. The herein described continuous process for the manufacture or production of
chlorine from hydrochloric acid, consisting in electrolytically decomposing the acid
whilst a solution thereof in a heated condition flows through the decomposing
apparatus, and in re-introducing into such decomposing apparatus the liquid
flowing therefrom and containing a small quantity of undecomposed hydrochloric
acid, after such liquid has been again charged with a fresh quantity of hydrochloric
acid gas.
2. For carrying out the process referred to in the preceding claim, an electrolytic
decomposing apparatus comprising superposed receptacles each divided into com-
partments by ribs extending downward from the bottom of the receptacle above it,
or from the cover of the uppermost receptacle, and containing electrodes, the
arrangement being such that the receptacles can be traversed in succession by the
liquid to be decomposed which enters the apparatus at the top, and flows downward
over alternately arranged overflow walls or through alternately arranged overflow
pipes from receptacle to receptacle, whilst the chlorine liberated in the anode
compartments and the hydrogen liberated in the cathode compartments flow in
separate streams by means of alternately arranged ascension pipes through all
the superposed anode compartments and cathode compartments respectively in
succession.
3. For carrying out the process specified in Claim 1, an electrolytic decomposing
apparatus, consisting of a number of electrode-cells closed at the top, separated
from one another by perforated partitions, and located in a common trough, the
arrangement being such that the cells can be traversed by the electrolyte which
enters at the bottom, and, after decomposition of its contained hydrochloric acid,
passes through upper lateral openings in the wall of the trough into collecting pipes
arranged at both sides of the apparatus, whilst the gases liberated in the cells are
conveyed to other collecting pipes through ascension pipes which pass through the
supporting bars of the electrodes.
4. In electrolytic decomposing apparatus of the kind specified in the preceding
claim, providing each of the electrode-supporting bars constituting the covers of
the cells, with a downwardly projecting strip of sheet metal that extends entirely

page_text: around the said supporting bar, and projects into a gutter-shaped recess that is
formed in the upper end of the corresponding cell and is filled with material
such as putty or cement substantially as hercin described for the purpose specified.
5. An electrolytic decomposing apparatus of the kind specified in Claim 3, in
which the perforated partitions, are each made of a number of superposed horizontal
rods or bars formed with suitable recesses to form openings as set forth.
Dated this 4th day of December 1891.
C. KELLNER,
By L. W., per F. B.