Improvements in Methods of Solidifying Carbon Dioxide, and of Utilizing the Solidifled Substance.
Year: 1895

page_text: Date of Application, 11th Apr., 1895
Complete Specification Left, 13th Jan., 1896-Accepted, 15th Feb., 1896
PROVISIONAL SPECIFICATION.
Improvements in Methods of Solidifying Carbon Dioxide, and of
Utilizing the Solidifled Substance.
We, HERBERT SAMUEL ELWORTHY, of 19, Hill Road, Bandra, Bombay, in
the Empire of India, Analytical Chemist, and PHILIP DURHAM HENDERSON, of
89, Philbeach Gardens, S.W., Gentleman, do hereby declare the nature of this
invention to be as follows:-
This process is intended to obviate the use of the heavy iron and steel vessels at
present used, for the storage and transport of liquefied carbon dioxide, or so called
carbonic acid.
For this purpose we convert it into the solid form, either by first converting it
into "carbonic acid snow," or by freezing the liquefied gas direct, to a form
resembling ordinary ice, both of which processes may be carried out, in the manner
hereinafter described.
In order to carry out the first part of this process namely, converting the
liquefied gas into "snow," we connect the outlet nozzles of the compressor direct
to a coil, or worm, or series of coils or worms, or convolutions of pipes, enclosed
in a larger pipe, or chamber, or room, or other suitable receptacle, which pipe,
chamber, room or other receptacle, may be jacketted with a non-conducting
material applied either direct, or placed between two casings. We prefer, however,
to use a double walled pipe, in which the coil, or series of coils, may be placed.
The chamber formed by the double walls of the pipe, may be of any suitable
dimensions, and hermetically sealed, and the space in them exhausted, so as to form
as complete a vacuum as possible, preferably in the manner proposed and used, by
Professor Dewar, in his late researches, at the Royal Institute, though any other
method of producing a good vacuum may alternatively be used.
In
The end of the coil, or coils, may now be conducted into a chamber, which may
also be vacuum-jacketted, or protected in any other suitable way. The liquefied
gas is allowed to escape into this chamber, through a nozzle, and by the sudden
expansion, a large proportion of the liquid is converted into "snow," whilst the
remainder at a very low temperature, is returned through the external double-
walled pipe, enclosing the coil, either direct to the gas holder, for re-compression,
or preferably through a jacket surrounding the cylinders of the compressor.
this way the gas, which is at an extremely low temperature, first cools the liquefied
gas contained in the coils, leading from the compressor, to such an extent that a
much larger proportion of the liquid is converted into snow, on expansion in the
chamber, and finally acts as an exceedingly efficient means of cooling the
compression cylinders of the pump, whereby it is possible to liquefy the gas, at a
comparatively low pressure.
Instead of conducting the liquefied gas direct into the above-mentioned chamber,
it may be conducted to a suitable pump motor cylinder, where, by its expansion, it
may be caused to assist in the compression of another portion of gas, and finally
be allowed to escape into the above-described chamber. In this way, the first
expansion taking place, whilst the gas is doing work, a very considerable cooling
of the gas takes place, before it is sent into the chamber, and a much larger
proportion of the liquid is, in consequence, solidified. After expansion in the
chamber, the gas still remaining is sent through the pipe and the compressor jacket,
as above described.

page_text: The snow may be removed from the chamber, either at intervals, or continuously,
by means of a conveyor screw, or other suitable means, and compressed by
hydraulic, or other power, direct to solid blocks, or in the manner hereinafter
described.
Instead of first converting the liquefied gas into snow, the highly cooled liquid,
passing out of the coil, may be allowed to run into a vessel of any suitable form
and which may be made strong enough to withstand the necessary pressure.
Round this vessel is coiled a sufficiently large pipe fitted at one end with a nozzle
and regulating valve, and open at the other end, which is in free communication
with the double-walled pipe, jacketting the coil from the compressor. This coiled
pipe, is enclosed in an outer, double-walled vessel, having a high vacuum between
the walls, preferably formed by Professor Dewar's method, or a modification of it.
The space in which the coil rests may either be filled with air, or a liquid which
will not freeze at the solidifying temperature of carbon dioxide, such as pure
alcohol.
In
The liquefied gas, coming from the compressor coils, is allowed to run into the
inner vessel, at a sufficient pressure to keep it liquid, whilst a sraall proportion is
allowed to escape, by means of a bye-pass, into the coil surrounding the vessel.
this way, the expansion of the gas, in the coil of pipe, which should be of rather
large size, so as to get the full effect of the expansion on the surrounding air or
liquid, is cooled to such an extent that the liquefied gas contained in the inner
cylinder, is solidified. The cylinder may then be removed and the frozen carbon
dioxide taken out in any suitable way.
The solid carbon dioxide, either in the form of snow or broken ice, may be
compressed into any of the following forms, for convenience of manipulation, and
thus rendered available for nearly all purposes for which ice is now used, as well
as for many other purposes, amongst which will be the manufacture of aërated
waters, or other beverages, without machines of any kind.
The solidified dioxide, is compressed into the form of blocks or slabs, and these
blocks or slabs may be scored, or divided, in such a way as to facilitate their being
broken up into squares, or cubes, or tablets, or other forms of any suitable weight,
and their weight, and also the quantity of gas they will produce, at atmospheric
pressure, may be impressed on each block, either at the time of compression, or at
a subsequent operation. In this way a known weight, or volume, may be readily
broken off, and sold, or used in an ordinary ice box, or in the improved form of ice
box, hereinafter to be described. This form of the solid, is also useful for providing
the gas, in the present type of aërating machines, as any desired quantity can at
once be placed in the gas holder of such a machine, whereby, on volatilization, it
will be ready for use in the ordinary way.
Instead of compressing it into the form of large slabs or blocks, the solidified
dioxide may be compressed into thin sheets, or slabs, and these slabs may be so
constructed, that they may be readily broken up into sticks, rods, tablets or other
small pieces. For the manufacture of aërated beverages without a machine, these
pieces may be of such a size, as to give off the proper quantity of gas to aërate
the water in any given bottle. Each of the pieces may be stamped with the
weight or volume of gas of which they consist, and also with the size of bottle
which they will aërate. By simply dropping one of these pieces into a bottle of
water, and shaking it by hand, or by a simple rocking machine, the water will
almost immediately become impregnated with the gas. In this way the aërating
machine, with all its complications, is completely done away with.
By the use of this solidified gas, all danger from bursting storage vessels, is done
away with, and also the large amount of freight now paid, for the transport of
these vessels, the weight of which is from 2 to 3 times the weight of the liquefied
gas with which they are charged. The solidified gas can be carried in simple felt
bags, or bags of other non-conducting material. It can also be stored or
transported in an ordinary ice box, or in the improved form of ice box now 'to be
described.

page_text: These improved ice boxes are made with either double or triple walls. The two
inner walls may be of metal, or glass, and these may be so secured together that
the joints are absolutely air-tight. The walls should have as few points of contact
as possible. The space between the walls is now exhausted, and the highest
possible vacuum produced, either by Professor Dewar's method, or any other
method capable of giving a very high vacuum. In order to protect the box from
injury, and to further increase its non-conducting power, the box may be enclosed
in an outer case of wood, paper boards, or any other strong non-conducting
material, or of metal, and if preferred the space between this outer box and the
internal one, may be filled with non-conducting material.
By these improved means of preparing, and transporting, solidified carbon
dioxide, this material will be rendered available for all, or nearly all, purposes for
which ice is now used, as well as for any other purposes for which the latter is
unsuitable. By placing a small quantity of the solidified gas in a small box
preferably made of silver, or aluminium, and which box may also coutain ether, or
alcohol, and immersing the box in any liquid or solution, the latter may be cooled
without contact with the gas, and in this way the delicate bouquet of wines, and
other liquors, is preserved. The box should have an escape tube, which may be of
sufficient length, and of such a shape, as to act as a handle.
Dat this 10th day of In 1905
EDWARDS & Co.,
65 and 66, Chancery Lane, London, Agents for the Applicants.
Improvements in Methods of Solidifying Carbon Dioxide, and of
Utilizing the Solidifled Substance.
We, HERBERT SAMUEL ELWORTHY, of 19, Hill Road, Bandra, Bombay, in
the Empire of India, Analytical Chemist, and PHILIP DURHAM HENDERSON,
of 89, Philbeach Gardens, S.W., Gentleman, 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 and accompanying
drawings that is to say :-
This process is intended to obviate the use of the heavy iron and steel vessels at.
present used, for the storage and transport of liquefied carbon dioxide, or so-called.
carbonic acid.
For this purpose we convert it into the solid form, either by first converting it.
into "carbonic acid snow," or by freezing the liquefied gas direct, to a form
resembling ordinary ice, both of which processes may be carried out, in the
manner hereinafter described.
The accompanying drawing is in illustration of the invention, Figure 1 being a
side view, partly in section, of the apparatus which we employ in our improved
process. b is an ordinary stage compressor, such as is now in general use for
liquefying, or highly compressing, gases, and having the inlet pipe which brings
the gas from the gas holder or producing plant to the first cylinder of the
compressor, whence after passing through the cooling coils, and the other cylinders
in succession, it passes away in a liquefied state to the regenerative-refrigerating
apparatus B.
This regenerative-refrigerating apparatus consists of a double-walled vertical or
horizontal vessel, this vessel may have an outer non-conducting covering 2, of any
suitable material, and has between its double walls a space d which is exhausted im
as complete a manner as possible, thus forming a vacuum-jacket.
Inside the

page_text: C
(
refrigerating vessel the coil of pipe c is placed. The vessel is fitted into the
base 8, and any spaces may be filled with non-conducting material. The vacuum-
jacket is exhausted through the pipe 5, which is afterwards closed by means ‹ f
a good valve or stop-cock. The liquefied gas coming from the compressor enters
the coil c through the pipe a and after passing through, is carried away by pipe e
to the motor cylinder C, whence it passes by pipe 12 to the chamber f. The gas
remaining unsolidified in the solidifying chamber f (Figure 1) returns through
pipe i, and passing through the regenerative-refrigerator, round the outside of the
coil c, goes away by pipe 3 to cylinder C2 of the combined motor-pump / where it
is partially compressed by means of the expansion of another portion of liquefied
carbon dioxide in the cylinder C¹, and is then returned to the compressor b by
pipe 4, the latter being preferably connected to the intermediate cylinder of the
compressor.
In the combined motor-pump 1, shown in outline in Figure 1, the liquefied gas
coming from the regenerative-refrigerator coil c, first enters cylinder C', where, by
its expansion, it drives the motor and pump, and is itself very greatly cooled in the
operation, after which it is exhausted into the solidifying chamber f where it
becomes partially solidified into the form of snow. The unsolidified gas first
returns to the regenerative-refrigerator, to cool the liquefied gas, and thence back
again to cylinder C' of the motor-pump, where after being partially compressed it
is returned to the compressor as above described.
fis the double-walled solidifying chamber, also vacuum-jacketted, the bottom of
the chamber is preferably made tapering, or funnel shaped as shewn, and leads
direct into a hydraulic press, the ram or platten of which compresses any snow
formed, into the removable box at m. The hydraulic press inay however be
entirely separate, and the snow being removed from the bottom of the solidifying
chamber by any suitable means, may then be placed in the box, and compressed in
the usual way.
When the box at m is full, it may be removed and another be put
in its place, and the slab of compressed snow may then be taken out.
The liquefied
gas, either direct from the regenerative-refrigerator, or after passing through the
motor cylinder C¹, enters the solidifying chamber fat by the pipe 12, and the
unsolidified gas passes away by the pipe i, the baffle plate 10 serving to prevent
the pipe being choked by particles of the snow being carried along with the
escaping gas.
The snow may be removed from the chamber f, either at intervals, or
continuously, by means of a conveyor screw, or other suitable means, and
compressed by hydraulic, or other power, direct to solid blocks, or in the manner
hereinafter described. Instead of converting the liquefied gas first into snow, the
highly cooled liquid, passing out of the coil, may be allowed to run into a vessel of
any suitable form, (not shewn in the drawing), and which may be made strong
enough to withstand the necessary pressure.
Round this vessel is coiled a sufficiently large pipe, fitted at one end with a
nozzle and regulating valve, and open at the other end, which is in free communi-
cation with the double walled pipe, jacketting the coil e from the compressor.
This coiled pipe is enclosed in an outer, double-walled vessel, having a high
vacuum between the walls, preferably formed by Professor Dewar's method, or a
modification of it. The space in which the coil rests may either be filled with air,
or a liquid which will not freeze at the solidifying temperature of carbon dioxide,
such as pure alcohol.
The liquefied gas, coming from the compressor coils, is allowed to run into the
inner vessel, at a sufficient pressure to keep it liquid, whilst a small proportion is
allowed to escape, by means of a bye-pass, into the coil surrounding the vessel.
In this way, the expansion of the gas, in the coil of pipe, which should be of
rather large size, so as to get the full effect of the expansion on the surrounding
air or liquid, is cooled to such an extent that the liquefied gas contained in the
inner cylinder, is solidified. The cylinder may then be removed and the frozen
carbon dioxide taken out in any suitable way.

page_text: A somewhat modified method of making the carbonic acid "ice," is as follows
(as illustrated in Figures 2 and 3):-
The liquefied carbon dioxide is run through a coil of pipe r, immersed in a tank s
containing methylated alcohol or pure alcohol, the tank being made preferably with
double walls o and p and vacuum jacketted as above described. The carbon
dioxide direct from the compressor is allowed to expand in the coil of pipe, down
to about 5 or 10 atmospheres, and in doing so the spirit in the tank s is cooled
down to a very low temperature. In the tank are placed a number of covered
metallic cylinders or boxes t, or other suitable vessels, with air tight covers, and
the expanded gas is allowed to flow partly into these boxes by the pipes and
valves r, where it is solidified into ice, by the cold produced by the expansion of
the liquefied gas. The remaining portion of the expanded gas, from the coil, is.
first sent by the pipe w into the cylinder of a motor, driving an air or gas
compressor, and caused to do work, by compressing another portion of carbonic
acid gas, and in doing this work, great cold is produced, and the gas which is
exhausted from the motor cylinder is at a very low temperature. This gas is then
sent through the above described regenerative, double-walled pipe, in which the
coils (Figure 1) from the compressor nozzles are placed and in consequence the
gas going to the coil in the spirit tank, is cooled to a very low temperature before
it reaches this coil, and therefore the cold produced by its expansion is greatly
increased.
Carbon dioxide freezes to a solid under a pressure of from 5 to 10 atmospheres,
at a temperature of about 87° Centigrade.
If found preferable in practice, the compressed or liquefied gas can first be
caused to do work in a motor cylinder, and can then be allowed to expand still
further in the coil of pipe immersed in the spirit tank, and in this way also great
cold is produced. The re-expanded gas from the coil may also be caused to do
work, as hereinbefore described.
When the solidifying boxes t have been filled with ice they are removed from
the spirit tank, the pipes being uncoupled, and allowed to stand in the air for a
few minutes, and then opened, and the block of ice taken out, which can be readily
done, as the walls of the box have become slightly warmed by standing in the air.
The boxes are also made slightly tapering for the purpose of facilitating the
removal of the ice blocks. The block may now be marked in the manner herein-
after described, and either be broken up for use in making the smaller slabs, or sent
out in the state as removed from the box.
Instead of cooling the spirit in the tank with carbon dioxide, any other cooling
medium may be used, such for instance, as air, ammonia, ether, or the so called
"Pictet" fluid, which consists in a mixture of carbon dioxide, and sulphur dioxide,
and in this case the carbon dioxide is simply compressed into the boxes immersed
in the spirit tank, and any waste is returned by a suitable arrangement of pipes to.
the compressor, or the gas holder. Any two or more substances may be used for
cooling the gas, or it may be partially cooled by its own expansion and further
cooled by the action of the other substances.
The solid carbon dioxide, either in the form of snow or broken ice, may be
compressed into any of the following forms, for convenience of manipulation, and
thus rendered available for nearly all purposes for which ice is now used, as well as
for many other purposes, amongst which will be the manufacture of aërated waters,
or other beverages, without machines of any kind.
The solidified dioxide is compressed into the form of blocks or slabs, and these.
blocks or slabs may be scored, or divided, in such a way as to facilitate their being
broken up into squares, or cubes, or tablets, or other forms of any suitable weight;.
and their weight, and also the quantity of gas they will produce, at atmospheric
pressure, may be impressed on each block, either at the time of compression, or at
a subsequent operation. In this way a known weight, or volume, may be readily
broken off, and sold, or used in an ordinary ice box, or in the improved form of ice.

page_text: .
box, hereinafter described. This form of the solid is also useful for providing the
gas, in the present type of aërating machines, as any desired quantity can at once
be placed in the gas holder of such a machine, whereby, on volatilization, it will
be ready for use in the ordinary way.
The compressing apparatus is indicated in Figure 1, m being a receptacle, below
the chamber f, into which the carbonic acid suow passes, and is very forcibly.com-
pressed in the receptacle by means of a pressure ram actuated by a hydraulic
cylinder n, valves of the usual kind being provided by which water under pressure
can be admitted into the cylinder n. When the snow has thus been compressed,
the ram is withdrawn and the block of carbonic acid ice removed.
Instead of compressing it into the form of large slabs or blocks, the solidified
dioxide may be compressed into thin sheets, or slabs, and these slabs may be so
constructed, that they may be readily broken up into sticks, rods, tablets, or other
small pieces. For the manufacture of aërated beverages without a machine, these
pieces may be of such a size, as to give off the proper quantity of gas to aërate the
water in any given bottle. Each of the pieces may be stamped with the weight or
volume of gas of which they consist, and also with the size of bottle which they
will aĕrate. By simply dropping one of these pieces into a bottle of water, aud
shaking it by hand, or by a simple rocking machine, the water will almost
immediately become impregnated with the gas. In this way the aërating machine,
with all its complications, is completely done away with.
By the use of this solidified gas, all danger from bursting storage vessels, is done
away with, and also the large amount of freight now paid for the transport of
these vessels, the weight of which is from 2 to 3 times the weight of the liquefied
gas with which they are charged. The solidified gas can be carried in simple
felt bags, or bags of other non-conducting material. It can also be stored or
transported in an ordinary ice-box, or in the improved form of ice-box now to be
described.
These improved ice-boxes are made with either double or triple walls. The
walls may be of metal, or glass, and these may be so secured together that the
joints are absolutely air-tight. The walls should have as few points of contact as
possible. The space between the walls is now exhausted, and the highest possible
vacuum produced, either by Professor Dewar's method, or any other method
capable of giving a very high vacuum. In order to protect the box from injury,
and to further increase its non-conducting power, the box may be enclosed in au
outer case of wood, paper-boards, or any other strong non-conducting material, or
of metal, and if preferred the space between this outer box and the internal one,
may be filled with non-conducting material.
By these improved means of preparing, and transporting, solidified carbon
dioxide, this material will be rendered available for all,-or nearly all-purposes
for which ice is now used, as well as for many other purposes for which the latter
is unsuitable. By placing a small quantity of the solidified gas in a small box
preferably made of silver, or aluminium, and which box may also contain ether, or
alcohol, and immersing the box in any liquid or solution, the latter may be cooled
without contact with the gas, and in this way the delicate bouquet of wines, and.
other liquors, is preserved. The boxes should have an escape tube, which may
be of sufficient length, and of such a shape, as to act as a handle.
Having now particularly described and ascertained the nature of my said inven-
tion, and in what manner the same is to be performed, declare that what I
claim is :-
1. For the manufacture of solid carbon dioxide, the use, and application of the
regenerative cooling apparatus, substantially as set forth, and illustrated.
2. The use of the vacuum-jacketted pipes, chambers or vessels, substantially in
the manner and for the purpose set forth, and illustrated.
3. The combination of the gas compressor delivering the liquefied carbon

page_text: dioxide to the regenerative cooling apparatus, and expansion chamber, for the
purpose of producing solidified carbon dioxide, substantially as set forth and
illustrated.
4. For the manufacture of solid carbon dioxide, the combination of the gas
compressor, delivering the liquid gas to a coil of pipe immersed in a tank coutaining
alcohol and having non-conducting walls, in which tank the gas is allowed to
expand, cooling the alcohol to a very low temperature, part of the expanded gas
passing into separate ice vessels, and the remainder driving a gas compressor and
after expansion passing through the double walled pipe in which the coils from
the compressor are placed, substantially as set forth and illustrated.
"
5. The compression of the carbon dioxide " snow or broken "ice," into slabs
or cakes, divided in such a manner as to be easily broken into pieces of known
weight or volume, substantially as set forth.
6. The marking or stamping of these pieces with their weight or volume, or the
size of bottle which they will aërate, substantially as set forth.
'
7. The manufacture of aërated waters, or other beverages, by means of the
solidified gas, without the use of a machine, or by the use of a simple rocking
machine, substantially as set forth.
8. The cooling of beverages by means of a box or bollow vessel, containing a
piece of the solidified gas, and either with or without alcohol.
9. The ice-box having double air-tight walls, in which as perfect a vacuum as
possible is maintained, substantially as set forth.
Deted this 12th der of Tenuary 1806
EDWARDS & Co.,
65 and 66, Chancery Lane, London, Agents for the Applicants.