Improvements in and Apparatus for or connected with the Liquefying and Storage of Chlorine.
Year: 1890

page_text: Date of Application, 6th May, 1890
Complete Specification Left, 5th Mar., 1891-Accepted, 18th Apr., 1891
PROVISIONAL SPECIFICATION.
Improvements in and Apparatus for or connected with the
Liquefying and Storage of Chlorine.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of
Middlesex, Gentleman, do hereby declare the nature of this invention, which has
been communicated to ine from abroad by Julius Marx, of Sachsenhausen:
Frankfort-on-Maine, Chemist, and Doctor Weller, of Sachsenhausen, Gentleman,
both in the Empire of Germany, to be as follows:-
It will be found often convenient to employ chlorine alone instead of in the form
of a compound such as for example chloride of lime and the liquid form of chlorine
is the most convenient especially for storing and transporting.
By the process hereinafter described liquid chlorine is obtained with facility and
economy.
Chlorine from any source may be used provided it does not contain objectionable
quantities of air carbonic acid hydrochloric acid water and the like.
In most cases chlorine produced on a large scale requires to be purified but by
employing electrolysis a sufficiently pure chlorine can be manufactured suitable for
being liquefied immediately after the removal of the watery vapour.
The chlorine may be liquefied either directly by generating it under pressure or
indirectly by combining it first with a substance which readily absorbs and liberates
chlorine and subsequently effecting the liquefaction.
Refrigeration must always accompany the liquefying process. Any apparatus
which is arranged or constructed so as to prevent chlorine escaping from the
chamber in which its liquefaction takes place may be employed to liquefy chlorine
under the pressure resulting from its generation.
The chlorine is conducted through a receiving chamber. A jet of cold water is
delivered into this chamber by a nozzle to form hydrate of chlorine. The excess
of water escapes through a perforated plate or false bottom which retains the
hydrate the said water being drawn off by a pump which draws the said water
through a cooling vessel and through a closed tank and finally redelivers it by the
nozzle into the receiving chamber.
A series of receiving chambers may be provided they being each in connection
with the pump and with the chlorine outlet pipe. The chlorine being passed
regularly through them all and when one receiving chamber is found to contain a
sufficient quantity of hydrate of chlorine it is disconnected from the others and
hot water (or a small quantity of steam) is passed through a pipe or pipes which
enter or enters the said chamber. The chlorine given off is dried condensed or
liquefier.
In-tead of making liquid chlorine the hydrate of chlorine may be employed for
storing and transport. An advantage is that I can employ vessels which need not
be so strong as those required for liquid chlorine. Thus glass or china vessels may
be used they being strengthened and protected by a suitable jacket of sheet iron.
The drawback is that the hydrate of chlorine attacks metals more powerfully than
liquid chlorine furthermore that it contains less than 33 per cent. of chlorine.
Instead of combining the chlorine with water before liquefying it, it may be
associated with other substances which will yield it up again readily. Such
substances are for instance protochloride of copper or of antimony or similar
protochlorides especially the protochloride of gold which absorbs and readily yields
up again chlorine at a comparatively moderate temperature. But any of these

page_text: boilies present the disadvantage of decomposing with increasing difficulty as the
pressure rises. Hydrate of chlorine decomposes much more easily and it further
to a certain degree serve for drying the chlorine.
It is well known that chlorine can be liquefied directly by pressure but owing to
its great affinity for them it destroys more or less rapidly the parts or materials
composing the apparatus used for obtaining the pressure. This drawback can be
reduced somewhat by causing the compressing piston to net indirectly by the inter-
position of a suitable liquid or a readily melting organic or inorganic chloride,
This defeet is entirely avoided by this invention as the pumps do not come into
contact with the chlorine or only with a very cold and very poor solution thereof
under a pressure low enough to allow the employment of pumps of ebonite or the
like. The apparato described may have combined with it a warming device or a
device for creating a varmuum to remove the rest of the chlorine.
The process described dispenses with the work of pumping gases a very
uneconomical operation requiring special cooling and contrivances for preventing
leakage but in the process is described this is easily provided for.
As no jumping to compress gas is applied in the method hereinbefore described
chlorine from any source may be made use of whereas when the co-
pressed by pumping many kinds of chlorine cannot be conveniently utilized for
example chlorine obtained by heat from hydrochloric neid or chloride of
magnesium.
Dry or anhydrous liquid chlorine attacks iron steel and the like to a very small
extent compared to gaseon chlorine and to avoid the destruction of the costly strong
bottles for containing liquid chlorine these receptacles are not used except for
storing and transport and pre replaced at other times by bottles or tubuler Vessels
of gutta percha chonite glass or china.
The following is a suitable apparatus for transferring the liquid. An iron
hottle l a glass bottle cor tubes) are employed the latter being provided with a
metal heud and having an iron jacket ronil it with a enating of boiled linseed
oil gutta percha india rubber or glue or other coment mixed with glycerine
intervening. The jacket serves likewise to keep the metal head in place.
The plugs of the glass bottle are unscrewed and the metal hend thereof is -crewed
into the heat of the iron bottle.
Both bottles are then fixed in a frame wherein they are secured by means of
screw. This frame is pivotted in bearings in a Support und provided with
lubricators.
The iron bottle is placed in the lower position and its plugs are unserewed very
slowly. After a shot interval the frame is turned over so as to bring the glass
bottle murmust and so the liquid chlorine runs into it. After the chlorine has
been tren forrol the plugs are screwed up and the bottles are discommented.
A small quantity of chlorine remains in the iron bottle. It may be discharged
directly into the feeding apparatus or into the air. To remove all the chlorine a
current of air is driven through when the bottle is ready for further use.
If the iron bottle he intended to have a lead lining it should receive first a
galvanic lining or deposit upon which the lead is fused.
Betore refilling the bottle the lead lining houdd be carefully examined and if
necessary it should be repaired or the bottle relined.
The cooling which has been hereinbefore referred to as being employed in
conducting the process may be done by a refrigerating machine or by means of
ice packed around the pipes or to bring the cooling medium to the required
low temperature the heat absorbing power of the liquid chlorine in becoming
gaseous again may be utilised by causing the medium to pass in contact with the
bottles as they are being discharged of chlorine.
TL:
"
J. II. JOHNSON & Co.,
47, Lincoln's Inn Fields, Agents.

page_text: COMPLETE SPECIFICATION.
Improvements in and Apparatus for or connected with the
Liquefying and Storage of Chlorine.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of
Middlesex, Gentleman, do hereby declare the nature of this invention (which
has been communicated to me from abroad by Julius Marx, late of Sachsen-
hausen, Frankfort-on-Maine, now of Bad-Nauheim, in the Empire of Germany,
Manufacturing Chemist, and Dr. Weller, of Sachsenhausen, in the Empire of
Germany, Chemist), and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
In many cases it is more convenient to employ chlorine as such than in the form
of a compound such as, for example, chloride of lime, and the liquid form of
chlorine is usually the most convenient especially for storing and transporting.
By the process hereinafter described liquid chlorine is obtained with facility and
economy. Chlorine gas from any source may be used provided it does not contain
objectionable quantities of impurities such as air, carbonic oxide, carbonic acid,
hydrochloric acid, water and the like.
In most cases chlorine produced on a large scale requires to be purified, but by
electrolysis a sufficiently pure chlorine can be manufactured suitable for being
liquefied immediately after the removal of the watery vapour as hereinafter
explained.
The chlorine may be liquefied either directly by generating it under pressure,
or indirectly, by bringing it up to pressure by pumps, or by combining it first with
a substance which readily absorbs and liberates chlorine, and subsequently
effecting the liquefaction. Refrigeration should always accompany the liquefying
process. Any apparatus which is arranged, or constructed, so as to prevent
chlorine escaping from the chamber in which its development occurs to any place
but the chamber in which its liquefaction takes place, may be employed to liquefy
chlorine under the pressure resulting from its generation. For such purpose an
electrolytical apparatus may easily be adapted.
It is well known that chlorine can be liquefied directly after development by
pressure but owing to its great affinity for most substances it destroys, more or
less rapidly, the parts, or materials, composing the apparatus used for obtaining
the pressure. This drawback can be reduced somewhat by causing the com-
pressing piston to act indirectly by the interposition of a suitable liquid, such
as, for instance, a liquid, or readily melting organic, or inorganic, neutral and
saturated chloride.
This defect is however entirely avoided by my invention as the pumps do
not come into contact with the chlorine but only with a very cold and very
poor solution thereof under a pressure low enough to allow of the employment of
pumps of ebonite, glass, or the like.
As no pumping is employer to compress gas in the method hereinafter described
chlorine may be inade use of from sources which cannot be conveniently utilized
when the gas is compressed by pumping, such for example, as chlorine obtained by
heat from hydrochloric acid, or from chloride of magnesium, as small quantities of
foreign gas remler direct and economical mechanical compression extremely difficult
if not impossible.
The process according to this invention dispenses with the work of pumping
gases; a very uneconomical operation, requiring special cooling and contrivances
for preventing leakage; but in the process according to this invention this is easily
provided for.
Referring to Figure 1 of the accompanying drawings the chlorine is conducted
through, or into, a receiving chamber A, by the pipe B, coming from the chamber
or place where it is generated, and a jet of cold water is delivered, by the pump G,
into this chamber, by a nozzle D, to form hydrate of chlorine. The excess of

page_text: water eapes through a perforated plate, or false bottom. E, which retains the
hydrate, the said water being drawn off by the pump G which draws the said water
by the pipe F through a cooling vessel H, through the pip: 4, and through a closed
tank J. and pipe and finally redelivers it by the nozzle D into the chamber A.
If continuous working be desired a series of receiving chambers, such as A. inay
be provided, they being each in connection with the pump and with the chlorine
inlet and outlet pipe. The chlorine being passed regularly through them all, when
one receiving chamber is found to contain a sufficient quantity of hydrate of
chlorine it is disconnected from the others, and hot water (or a small quantity of
steam) is passed through a pipe, or pipes, K. which enters, or enter, the said
chamber. The chlorine is given off and is afterwards dried and condensed or
liquefied.
The w, ter, or solution, which passes through the false bottom E, and is drawn
by the pump G, and passed into the vessel J, does not retain much chlorine and the
quantity retained can be reduced still further by providing the vessel J. with a
warming device or a device for creating a vacum to remove the small quantity of
chlorine which is absorbed. The chlorine su removed can be utilized as desired.
The drying is effected very conveniently by the apparatus shewn in Figure 1.
The vessel L is cooled by the jacket, as hewn, so that the vapour coming from
the chamber A, by the pipe C, condenses into chlorine-hydrate in the vessel L, and
deposits upon a false perforated bottom at the lower part of the vessel L. From
the vessel 1, the chlorine enters the vessel or bottle M, by the pipe P, the said
vessel or bottle M, being in a enoling vessel, or jacket M. and after being filled
can be disconnected and replace by another. The quantity of water contained in
the chlorine, coming from the chainber A, depends very much upon the manner
of gasifying the hydrate. If too much hot water, or too much steam, be passed
through the pipe K, the rapid gasification taking place may even effect a mechanical
transport of particles of water by the chlorine, and in any case the passage of
vaporous water is increased with increase of temperature. It is preferred to work
with hot water, rather than with steam, as the former is much more easily
regulated. Unless special circumstances require a higher temperature, the tem-
perature should not exceed 80° Celsius but generally the more convenient way will
be to employ an ample supply of water 27° to 30° C'elsins.
I do not limit myself to the precise details shown: for instance, the water spray
hereinhefore referred to as coming through the jet D, may be obtained by various
other means, such for instance, as by a fine sprayer, or roses, and the perforated, or
false bottom E, may be kept in motion, if desired, for the purpose of causing the
water to run off more quickly and completely.
To condense chlorine under its own pressure I may employ any apparatus which
will not allow the gas to escape except into the receiver. Cooling for the liquefac-
tion is not always necessary but it acts well and is very economical. Instead of
employing liquid chlorine, the hydrate of chlorine may be employed for storing and
transport.
An advantage of this is that there can then he employed vessels which need
not be so strong as those required for liquid chlorine. This glass, or earthenware
vessels may be used, they being strengthened, and protected, by a strong jacket,
such as one of sheet iron. The drawback is that the hydrate of chlorine attacks
metals more powerfully than does liquid chlorine, furthermore that it contains
much less (usually less than 33 per cent.) chlorine.
Instead of combining the chlorine with water before liquefying it, it may be
associated with other substances which will yield it up again readily; such for
example as protochloride of copper, or of antimony, or similar protochlorides,
especially the protochloride of gold, which absorbs, and readily yields up again,
chlorine at a comparatively moderate temperature. But any of these bodies present
the disadvantage of decomposing with difficulty, which increases as the pressure
rises, whereas hydrate of chlorine decomposes much more easily, and its prepara-
tion further serves for drying the chlorine to a certain degree.

page_text: For developing it dryer still, a most convenient way is to add a suitable salt,
such as common salt, to the solution circulated by the pump, and then there results the
advantage that a smaller quantity of vapour is given off afterwards, moreover the
interchange of temperature is better conducted and the danger of freezing is better
avoided.
Anhydrous liquid chlorine attacks iron, steel, or the like, to a very small extent
compared to gaseous chlorine, and to avoid the destruction of the costly strong
bottles for containing liquid chlorine still more, these receptacles are not used
except for storing and transport, and are replaced at other times (especially when
feeding by liquid chlorine) by bottles, cylinders, or vessels, of gutta-percha, ebonite,
glass or earthenware. I have shown at Figure 2 a suitable apparatus for trans-
ferring the liquid chlorine from one vessel to the other. An iron bottle or tube A
and a glass (or other equivalent material) bottle or tube B are employed, the latter
being provided with a metal head C, and having an iron jacket D, round it, with
between the bottle and jacket a coating E, of a material such as for instance linseed
oil (boiled till it becomes thick) gutta-percha, india-rubber, or glue, or other cement
mixed with glycerine.
The metal head C may be secured in place by screwing the head C to the
jacket, or in other suitable way for instance, by forming them in one with
each other.
The plugs or valves F1 F" of the glass bottle being preferably screwed up, the
metal head C, thereof is screwed on to the head of the iron bottle ; both bottles are
then fixed in a frame K, wherein they are secured by means of screws L and L¹.
This frame is provided with trunnions &, turning in bearings n, in a support N-
mare lubricators for the said bearings and trunnions. The iron bottle A, is placed
in the lower position as shewn and first its plugs, or valves, H', H", are unscrewed,
or opened, very slowly; then the plugs, or valves, F, F, of the bottle B, are
slowly opened. After a short interval, the frame K, is turned over so as to bring
the glass bottle B, undermost and then the liquid chlorine runs into it from the
bottle A. After the chlorine has been transferred the plugs F, F", are screwed up
and the bottles are disconnected.
Obviously a small quantity of gaseous chlorine remains in the iron bottle. It
might be discharged directly into the feeding apparatus, or into the air, but to
remove all the chlorine, a current of air is driven through the bottle A, when it will
be ready for further use.
I have described the bottle to be filled as being first placed above the other but I
do not limit myself to this relative placement.
If the iron bottle B, be intended to have a lead lining, it should receive first
a galvanic lining, or deposit, of lead, upon which the lead lining is fused.
Before refilling the said bottle the lead liuing should be carefully examined and,
if necessary, it should be repaired, or the bottle relined.
The intermediate coating, herein before referred to, and shewn at E, may be
applied by being introduced whilst in a mouldable state into the space between B
and D as follows:-
The mouthpiece of the bottle B is closed by a plug, or the like, so that only the
bottle, and not the space between it and the jacket, is plugged up. Then the mass
intended for filling the space between B and D, is pressed in by a pump, or com-
pressor, screwed to the head C.
On the end of D, opposite to the piece (', or in other convenient position, is a hole
which can be closed by a screw. This screw being removed, in beginning to press
the mass into the space, the air is first driven out through the screw hole and when the
mass itself makes its appearance at the screw hole, the screw is replaced and the
said space will then be filled up with the mass, which, if it contracts in cooling
and hardening, must be supplemented by more of the mass often repeated till the
space is well filled up, and thus a perfectly tight filling intermediate jacket is
obtained. The plug and any material remaining in the neck are removed.
The cooling, in the apparatus described with reference to Figure 1, may be

page_text: effected very readily by cooling medium from a refrigerating machine, or by means
of ice, or of ice and salt, parked around the pipes, or, to bring the cooling medium
to the required low temperature, the heat absorbing power of the liquid chlorine in
becoming gaseous again, may be utilised, by causing the heat exchanging, or cooling
medium to pass in contact with the bottles as they are being discharged of chlorine.
It is obvious this way is only convenient for special cases.
Having now particularly described and ascertained the nature of this said inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is
1. Effecting the liquefy ing of chlorine, (without compressing the gaseous chlorine
to condensation by mechanicni means,) by bringing chlorine into contact with
particles of cooled matter which will readily yield it up again: and then applying
lent to develop ellerine under pressure from the compound so formed, and then
condensing the chlorine, all substantially as hereinbefore described,
2. Effecting the liquefying of chlorine, (without compressing the gaseous chlorine
to condensation by mechanical means,) by bringing chlorine into contact with
particles of cooled water, whereby the chlorine is condensed into hydrate; the
water, not entering into combination, being caused to run off, then applying heat to
develope chlorine under pressure from the hydrate, and condensing it in a receiver,
which may, or may not, also serve na storing, or transporting, vessel; all sub-
stantially hereinbefore described.
3. The apparatus arranged substantially as hereinbefore described and shown in
Figure of the accompanying drawings for the purpose claimed by the preceding
claiming clan-e
1. In combination with an apparatus such as that claimed under the last
preceding claiming clause, a vessel (between the gasifying and receiving apparatus),
provided with means for cooling it, so as to condense the water contained in the
chlorine, and to seperate it from the chlorine condensing in the receiver; substan-
tially as reinhefore described and illustrated in Figure 1, of the recompanying
drawings.
5. The device, or apparatus, for transferring chlorine from one vessel to another,
for preventing, or reducing, the deterioration of the metallic receiver. or huttle;
by transferring its contents into a vessel made of a material more resistant to the
action of chlorine, substantially as hereinbefore described and illustrated in
Figure 2 of the accompanying drawing.
6. A vessel for the storage of chlorine, made by covering a vessel resistant to
chlorine, with a strengthening outer jacket, and with an intermediate jacket of a
plastic and hardening substance, substantially as hereinbefore described and illus-
trated in Figure 2 of the accompanying drawings,
Datel this 7th the Vouch 1901
J. II. JOHNSON & Co.,
Agents.