Improvements in and Apparatus for the Production and Retention of Chlorine in a Liquid State suitable for Transport or Storage.
Year: 1888

page_text: Date of Application, 10th Sept., 1888
Complete Specification Left, 11th June, 1889-Accepted; 13th July, 1889
PROVISIONAL SPECIFICATION.
Improvements in and Apparatus for the Production and Retention
of Chlorine in a Liquid State suitable for Transport or Storage.
I, BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex,
Patent Agent do hereby declare the nature of this Invention which has been
communicated to me from abroad by the Badische Anilin and Soda Fabrik of
Ludwigshafen on Rhein in the Empire of Germany to be as follows:-
This Invention has for its object to provide means whereby chlorine is liquified and
retained in a liquified state and in such a condition free from watery moisture that it
can he passed into vessels (in the construction of which are used cast or wrought iron
or steel phosphor-bronze brass, copper, zinc or lead) and be retained therein for
transport or storage without injury to the vessel. For this purpose chlorine gas is
subjected to a pressure sufficient to liquify it whilst at the same time it is kept out
of contact with the external air and is passed directly into the vessel in which it is to
be retained for transport or storage. The compression of the chlorine gas is effected
in a closed vessel in which the pressure is applied with the intervention of a liquid
medium which will not to any objectionable extent combine with Chlorine such as
concentrated sulphuric acid this medium being in its turn protected from liability to
take up moisture from the air by means of a material which will prevent the passage
of moisture from the air to the said medium. Such a material is petroleum or mineral
oil or distillates thereof.
The apparatus employed for the purpose may be arranged to work either inter-
mittently or continuously.
An apparatus to work intermittently may be arranged as follows-Two vessels are
connected together and communicate with each other at their lower ends and may take
a U shape. In the upper part of one of these vessels are pipes furnished with stop
cocks and being respectively for the admission of Chlorine gas and for the outlet of
the compressed chlorine to a cooler whence it passes in a liquified condition in to the
vessels in which it is stored. The upper part of the said first vessel is fitted with a
gauge glass. The second vessel is in communication by a pipe furnished with a stop
cock with a vessel provided with a pump or forcing device the outlet of which com-
municates with the upper part of the said second vessel. The first vessel contains
concentrated sulphuric acid which enters also the second vessel and above it in this
vessel is petroleum or the like. When the stop cock on the outlet pipe leading to the
cooler is closed and the stop cocks on the inlet pipe for chlorine gas to above the
sulphuric acid in the first vessel and on the pipe leading from the second vessel to the
vessel carrying the pump are opened and chlorine gas is admitted to the upper part of
the first vessel (which is preferably made as a contracted space) and will force back
the sulphuric acid and petroleum which will enter the aforesaid vessel in connection
with the pump. When the charge of chlorine gas is admitted the inlet cock for gas
and that on the pipe leading to the receiver are closed and the outlet cock on the first
vessel is opened and the pump worked when the petroleum and sulphuric acid are
forced forward and the chlorine is compressed the first vessel being during such
compression warmed to about 50° to 80° centrigrade which may be conveniently
effected by means of a hot water jacket surrounding the said vessel. This prevents
liquid chlorine from settling and the sulphuric acid from absorbing chlorine and also
prevents at the next operation there being left any objectionable space caused by the
escape of chlorine from the sulphuric acid when the pressure is relieved.
The compressed chlorine passes through the cooler and thence in a liquified condition
to the vessels in which it is finally received and stored. The foregoing operations are
then repeated for compressing a fresh charge of chlorine gas.

page_text: When it is desired that the process shall be conducted as a continuous one an
apparatus may be used consisting of two vessels charged with concentrated sulphuric
acid and petroleum as before but the inlet for chlorine gas passes up through a vertical
pipe entering the first vessel and provided at top with a lift valve and above this is an
opening also closed by a lift valve leading into a chamber above with which communi-
cates the outlet for the compressed gas to the cooler and receivers for the liquified
chlorine. It is preferred that the second vessel at the part where the sulphuric acid
and petroleum meet be enlarged to diminish the perpendicular movement of the liquid
and prevent the formation of an emulsion. The upper part of the second vessel is
furnished with a forcing device so that when this is raised the inlet valve opens and the
chlorine gas is drawn in to the space in the first vessel above the sulphuric acid and
when the forcing device is forced down, the chlorine gas is pressed through the valve
above into the chamber into which the outlet opens and thence to the cooler and
receiver as described. A small passage controlled by a stop valve passes from this
last named chamber to the space between the two lift valves and serves the purpose
of preventing any objectionable space as before mentioned as through the said small
passage when the forcing device is forced down, sulphuric acid passes into the upper
chamber and returns therefrom by the said small passage when the forcing device
commences its lift. The receiving vessels for the liquid chlorine we prefer to make of
iron or steel lined with lead copper or brass.
Dated this 10th day of September 1888:
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C.,
A gents
COMPLETE SPECIFICATION.
Improvements in and Apparatus for the Production and Retention
of Chlorine in a Liquid State suitable for Transport or Storage.
I BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex Patent
Agent do hereby declare the nature of this Invention (which has been communicated
to nie from abroad by The Badische Anilin & Soda Fabrik of Ludwigshafen
on Rhine in the Empire of Germany) and in what manner the same is to be
performed to be particularly described and ascertained in and by the following
statement:
The object of this Invention is to provide suitable processes and apparatus to effect
the liquifaction of chlorine in a practical form and so obtain it in a convenient form for
storage or transport. The process can be conducted either in an intermittent or in a
continuous manner as hereinafter explained.
When the process is conducted in an intermittent manner a volume of chlorine
gas depending on the capacity of the apparatus is liquified by pressure and cooling
and then the apparatus is charged anew. When the process is conducted in a con-
tinuous manner a relatively small quantity of chlorine gas is continually admitted to
the apparatus through suction and delivery valves and liquified.
Figure 1. of the accompanying drawings represents in elevation partly in section an
arrangement of apparatus according to this Invention for effecting the process in
an intermittent manner. The description of this apparatus and its functions will serve
also to explain the process according to this Invention.
Two vessels A and B are connected together and communicate with each other at
their lower ends. They may be separate vessels connected at their lower ends by a
passage or they may be formed in one as shewn in the drawing. In the upper part
of the vessel A are pipes furnished with stop cocks g and the pipe and cock g being
for the admission of chlorine gas and the pipe and cock f being for the outlet of
the compressed chlorine to a cooler K whence it passes in a liquified condition into
the vessels L in which is stored. The upper part of the said vessel A is fitted with
a gauge glass e. The vessel B is in communication by a pipe d furnished with a
stop cock d' with a vessel D provided with a pump or forcing device D² the outlet of

page_text: d
which communicates with the upper part of the said vessel B. The vessel A contains
sulphuric acid (y to =) which enters also the lower part of the vessel B and above
and floating on the said acid in this vessel is petroleum (r to y). To charge the
vessel A with chlorine the stop cock on the outlet pipe leading to the cooler Kis
closed and the stop cocks g and d are opened and chlorine gas is admitted to the
upper part of the vessel A (which is preferably made as a contracted space as
indicated at E) and will force back the sulphuric acid and petroleum which latter
(or part of it) will enter the aforesaid vessel in connection with the
pump. When
the charge of chlorine gas is admitted the inlet cock g for the said gas and the cock d'
on the pipe a leading to the receiver or vessel D are closed and the outlet cock fon
the pipe leading to the cooler K is opened and the pump is then worked so as to force
the petroleum back through the pipe d into the vessel B and the sulphuric acid up in the
vessel A and the chlorine is compressed the vessel A being during such compression
warmed to from about 50° to 50° Centigrade. This warming prevents liquid chlorine
from settling and the sulphuric acid from absorbing chlorine and also prevents at the
next operation there being left any objectionable space (which might be equal to as
much as 50 per cent. of the volume of chlorine) caused by the escape of chlorine
from the sulphuric acid when the pressure is relieved. This heating may be effected
in any convenient way. There is shown for the purpose a jacket A2 into which a
heating medium is passed. The compressed chlorine from the space E passes through
the cooler K and thence in a liquified condition to the vessel L in which it is finally
received and stored. The operation is known to be completed when the level of the
sulphuric acid seen in the gauge glass connected to the vessel A has reached the highest
point. The foregoing operations are then repeated for compressing a fresh charge of
chlorine gas the cock being closed and the cocks g and d¹ opened. The vessel Lis
shewn as being provided with two valves and 12. To the former the pipe from the
cooler K is joined by the union 13 so that if it be desired to remove the vessel L when
charged the valve can be closed and the union unfastened. The valve l² is provided
for the outlet of the gas for use.
Figure 2 represents in vertical section an apparatus for conducting the process.in
a continuous manner. It consists of two vessels A and B charged with concentrated
sulphuric acid so that the vessels A and B contain liquid as indicated from y to z
petroleum occupying the space from a to y. The inlet for chlorine gas passes up
through a vertical pipe entering the vessel A and provided at top with a lift
valve and above, this is an opening also closed by a lift valve k leading into a
chamber m above, with which communicates the outlet pipe f" for the compressed
gas to the cooler K and thence to the receiver L for the liquified chlorine. The
chamber m is provided with a gauge glass' e. It is preferred that the vessel B
at the part y where the sulphuric acid and petroleum meet be enlarged to diminish
the perpendicular movement of the liquid and prevent the formation of an emulsion.
The upper part of the vessel B is furnished with a forcing device or plunger D2 so
that when this is raised the sulphuric acids descends below the level of the inlet
valve i which opens and the chlorine gas is drawn into the space above it in the
vessel A and when the forcing device is forced down the valve i closes and the chlorine
gas by the rise of the liquid is pressed through the valve k above into the chamber m
into which the outlet opens and thence the chlorine passes to the cooler K and
receiver L. A small passage controlled by a stop valve p passes from the
chamber m to the space between the valves i and k and serves the purpose of preventing
any objectionable space as before mentioned with regard to Figure 1, as when the
forcing device depressed sulphuric acid passes through the said small passage
into the upper chamber m and returns therefrom by the said small, passage when the
forcing device commences its lift. The receiving vessels for the liquid chlorine I
prefer to make of iron or steel lined with lead copper or brass.
The vessel or chamber A is heated to from about 50 to 80 degrees Centigrade by
hot water or other heating medium contained in the jacket A. As before stated.
when the plunger D' is raised chlorine is drawn in through the pipe g² and valve i

page_text: and on the descent of the plunger this chlorine is forced through the valve into
the chamber m. If the smallest bubble of chlorine is left behind in the space above
the valve i a large part of the void produced on the return of the plunger is occupied
by the objectionable space herein before referred to as the chlorine has to be com-
pressed to about 1 of its original volume before it is liquified. The passage
herein before referred to is provided for the purpose of preventing this objectionable
space. Whenever the pressure is relieved in the space above the valve a small
quantity of sulphuric acid escapes from the space m into the said space above the
valve and this causes somewhat less chlorine to be drawn in than the quantity
exactly corresponding to the displacement of the plunger D2 and consequently on the
return stroke of the plunger not only is the whole of the chlorine forced out but also
'a small quantity of sulphuric acid equivalent to what had previously passed down the
passage. The valve p is adjusted according to the position of the liquid in the
chamber m.
My foreign correspondents have found that cast iron, wrought iron, steel, phosphor-
bronze, brass, copper, zinc, and lead are not affected by dry compressed, chlorine
alone or by contact with concentrated sulphuric acid. These metals are consequently
by preference used in the construction of the apparatus according to this invention.
For example the vessels A and B may be made of wrought iron, the bottle L of
steel the cooling worm or coil K of copper the valves or cocks f of phosphor
bronze and lead, rubber or asbestos are employed for packing the flanges and valve
spindles.
For storing or carriage of the liquified chlorine the bottles or vessels are preferably
made partly of iron or steel being constructed with an inner lining of lead copper or
brass in order to protect these thick and expensive vessels from possible injury arising
from contact with damp air or moist chlorine.
The moving parts of the apparatus which are in contact with air may be protected
from the action of the sulphuric acid by any suitable liquid but preferably by means
of mineral oil as herein before explained, petroleum Jigroin or melted vaseline
being preferably employed for the purpose. These liquids must be carefully purified
before being placed in contact with the sulphuric acid.
The chlorine may be liquified without the employment of an intermediate liquid the
pressure being transmitted directly through the sulphuric acid but this is done at the
expense of the apparatus.
Having now particularly described and ascertained the nature of the said Inven-
tion and in what manner the same is to be perforined I declare that what I
claim is
1. A process for the production and retention of chlorine in a liquid state con-
sisting in subjecting it to compression and passing it through a cooler directly
into the receiving bottle or vessel substantially in the manner herein before described.
2. As a means for liquifying chlorine the combination of a compressing or suction
and compressing.device arranged for transmitting pressure by the intervention of
concentrated sulphuric acid and a mineral oil or other neutral material not mixable
with or acted upon by sulphuric acid both being contained in communicating vessels
so arranged that the sulphuric acid is prevented by the interposition of the said neutral
material from coming into contact with the moving compressing parts the said
sulphuric acid being heated at the part where it comes into contact with the chlorine
gas and a cooling apparatus for the compressed chlorine and a closed vessel for the
storage and transport of the liquified chlorine all substantially as hereinbefore
described.
3. In a process and apparatus for liquifying chlorine after the manner hereinbefore
described the employment of an insulating or separating layer of mineral oil or other
analogous liquid indifferent to and not mixable with sulphuric acid for protecting the
moveable parts of the compressing or suction and compressing arrangements which
are in communication with atmospheric air substantially as herein before explained.

page_text: 4. The arrangement and combination of parts substantially as hereinbefore
described and shewn in Figure 1 of the accompanying drawings for the purposes
described.
5. The arrangement and combination of parts substantially as hereinbefore described
and shewn in Figure 2 of the accompanying drawings for the purposes described
and whether the passage be used therewith or not.
Dated 11th
ST1000
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.