Method of and Appliances for the Collection, Purification, and Utilization of the Carbonic Acid Gas given off during Fermenta- tion of Saccharine and other substances.
Year: 1891

page_text: Date of Application, 19th Dec., 1891
Complete Specification Left, 19th Sept., 1892-Accepted, 22nd Oct., 1892
PROVISIONAL SPECIFICATION.
A Method of and Appliances for the Collection, Purification, and
Utilization of the Carbonic Acid Gas given off during Fermenta-
tion of Saccharine and other substances.
We, JOHN PULLMAN, of 17 Greek Street, Soho Square, in the County of
Middlesex, Manufacturer, and HERBERT SAMUEL ELWORTHY, of 31 Gurney
Road, Stratford, in the County of Essex, Analytical Chemist, do hereby declare
the nature of this invention to be as follows:-
This invention consists of a method whereby the carbonic acid gas given off
during fermentation, more especially the fermentation of amylaceous or saccharine
matters for the manufacture of alcoholic liquors such as beer, spirits of wine,
whiskey, gin, wine, &c., may be collected and purified so as to render it fit for use
for aerating water, beer, wine, &c., and also for the various other purposes for
which carbonic acid gas is or may be used.
Where closed vats are used I collect the gas under low pressure say 2 to 3 inches
water pressure by means of the following device.
The vat being hermetically closed by means of a screw-down lid or other device
a small bellows shaped apparatus is placed on and fastened air tight to the cover of
To the
the vat, but communicating with the interior by means of a small hole.
top of the bellows a rod or wire is attached and passes down through the hole in
the cover of the vat being fastened at its lower end to one arm of a lever, and the
other end of the lever carries a valve which is held in place by means of a spring,
or the lever may be loaded.
When the gas in the vat attains a certain pressure regulated by means of the
spring or weight, the gas passing up through the hole in the cover expands the
bellows and lifting the lever opens the valve at the other end and allows the gas to
escape, closing it again as the pressure falls. Over this valve is placed an outlet
pipe leading to any simple form of low pressure air pump or double action bellows
or to a gas holder, the pump drawing the gas from the vat or from the gas holder
and passing it through the purifying apparatus.
For collecting the carbonic acid gas from open fermenting vats or tuns the
following device may be used.
A cover is provided made of any suitable material, such for instance as galvanized,
buckled, or corrugated, steel or iron plates, of a rather larger diameter than the top
of the rat, and having a deep flange or rim.
Round the outside of the vat and a little below the top, is fixed a deep narrow
annular channel into which the rim or flange of the cover fits loosely. This channel
is partially filled with any suitable liquid such as water, mercury &c. which acts as
a lute preventing escape of carbonic acid gas, and also the entrance of air into the
vat, except under excessive pressures.
The automatic regulator as described above for closed vats may be attached to
this cover so as to collect the gas at any required pressure. This regulator being
so arranged as to close automatically when the pressure in the vat falls below a
certain fixed amount, no atmospheric air can enter the vat.
In order to reduce the number of covers required for a given number of vats or
tuns, the covers may be suspended by means of pulley locks and rollers or other
suitable means to an overhead rail whereby they can be transferred from one vat to
another as required.
The purifying apparatus is arranged as follows:-
1st A vertical eslinder is used fitted with a syphon gas trap and inlet pipe for

page_text: the gas, and an outlet pipe at the top and having also a device for sprinkling water,
which may be caused to revolve by the issuing gas or by an external motor, and
the cylinder is also fitted with charging and discharging manholes. This cylinder
may be filled with any suitable material such as coke, charcoal, pumice stone, flints,
&c. over which the water from the sprinkler is caused to flow slowly and con-
tinuously. The carbonic acid gas being forced in at the bottom, and passing
upwards is brought continually in contact with fresh water whereby all the soluble
impurities such as alcohol, acetic ether, &c. are removed. The gas after passing
through this scrubber is passed through a second scrubber fitted similarly to the
first but through which a melted fat or oil, preferably mineral oil or a liquid or
liquifiable hydrocarbon (such for instance as melted paraffin wax, or vaseline) as
free as possible from odour and taste is made to flow instead of water.. The gas
passing upwards through the interstices of the coke or other material is brought into
intimate contact with the oil or other substance, which having a great affinity for
the ethers removes them from the gas.
These ethers may be recovered from the fat or oil or hydrocarbon and utilized
for the manufacture of fruit essences or other suitable purposes and the oil purified,
by distilling them off preferably with steam, superheated if necessary. The alcohol
may also be recovered from the first wash water by any suitable means of well
known kind.
The carbonic acid gas after passing through the two scrubbers above mentioned,
and containing now only mere traces of impurities, and a certain amount of moisture
is passed through a desiccator containing any suitable desiccating material such as
dry carbonate of potash, chloride of calcium, sulphuric acid or materials soaked in
sulphuric acid &c., but preferably carbonate of potash or chloride of calcium. The
desiccator consists of a vessel containing a number of shelves (preferably moveable
over which the gas is compelled to flow, the desiccating material being placed on
these shelves, and the gas in passing over loses its moisture and escapes at the
upper end nearly or quite dry. If preferred, two or more desiccating materials may
be used either in separate vessels or on different shelves of the same vessel. These
desiccating materials may also be recovered and used over again by driving off the
moisture either by direct firing or by passing a current of hot dry air over them.
The latter process may be performed without removal of the substance from the
desiccator.
The dry carbonic acid gas is now passed through a series of tubes or pipes,
preferably of cast iron, arranged in a furnace and heated red hot. The first of
these tubes may contain coke, or metallic copper or iron or zinc preferably in the
form of turnings, to remove any traces of oxygen which the gas may contain, the
other tubes containing oxide of copper or other easily reducible oxide.
We prefer
to use however oxide of copper formed in the following manner. All the tubes
except the first being closely filled with copper turnings are heated to a red heat
and a current of air is passed through them whereby a coating of oxide is formed
on the surface of the turnings, which oxide may be renewed in the same way
whenever it has become reduced. Copper wire or copper nails may be substituted
for the copper turnings, or the ordinary commercial black oxide of copper may be
used. Or the oxide of copper may be formed in the pores and on the surface of a
porous or fibrous material such as firebrick pumice stone, asbestos or the like by
saturating the material with a solution of nitrate of copper or a solution of an
inorganic salt of copper such as the acetate and then drying, and finally decom-
posing the copper salt at a high temperature in the presence of air, the treatment
being repeated if necessary. Other chemical substances such as chromate of lead,
bichromate of potash or soda, hinoxide of manganese, or other substance which at
a high temperature parts with its oxygen in the presence of organic matter may be
substituted for the oxide of copper. When the carbonic acid gas is brought into
contact with the hot oxide of copper, by being passed through the tubes containing
it all the remaining impurities are removed being for the most part converted into
carbonic acid gas and water. Should sensible traces of oxygen be found resulting

page_text: from the decomposition of organic compounds containing this gas, it may be com-
pletely removed by placing a small amount of metallic copper, in the shape of
turnings, wire, gauze, or nails, in the last tube.
When the oxide of copper becomes reduced by the action of the organic matter
contained in the impure carbonic acid gas, it may be completely regenerated by
passing air over it, and the hot air thus obtained may be utilized for redrying the
desiccating material.
The carbonic acid gas now perfectly purified may be cooled in an ordinary
condenser, and compressed or liquified by any suitable compressor and placed in iron
or steel bottles or other suitable holders for sale or use.
Dated this 19th day of December 1891.
EDWARDS & Co.,
35, Southampton Buildings, London, Agents for the Applicants.
COMPLETE SPECIFICATION.
A Method of and Appliances for the Collection, Purification, and
Utilization of the Carbonic Acid Gas given off during Fermenta-
tion of Saccharine and other substances.
We, JOHN PULLMAN, of 17 Greek Street, Soho Square, in the County of
Middlesex, Manufacturer, and HERBERT SAMUEL ELWORTHY, of 31 Gurney
Road, Stratford, in the County of Essex, Analytical Chemist, 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 drawing, that is to say :-
This invention consists of a method whereby the carbonic acid gas given off
during fermentation, more especially the fermentation of amylaceous or saccharine
matters for the manufacture of alcoholic liquors such as beer, spirits of wine,
whiskey, gin, wine, etc., may be collected and purified so as to render it fit for use
for aërating water, beer, wine, etc., and also for the various other purposes for
which carbonic acid gas is or may be used.
The accompanying drawing is in illustration of the invention.
Where closed vats are used we collect the gas under low pressure, say 2 to
3 inches water pressure, by means of the following device, as illustrated in Figure 1.
The vat being hermetically closed by means of a cover, a screw down lid, or
other device at a a small bellows shaped apparatus & is placed on and fastened air
tight to the cover a of the vat, but communicating with the interior by means of a
small hole. To the top of the bellows a rod or wire c is attached and passes down
through the hole in the cover of the vat being fastened at its lower end to one arm
of a lever d, the other end of which carries a valve e which is held in its place by
means of a spring, or the lever may be loaded with an adjustable weight.
When the gas in the vat attains a certain pressure regulated by means of the
spring for weight the gas passing up through the hole in the cover expands the
bellows and lifting the lever d opens the valve e at the other end and allows
the gas to escape, closing it again as the pressure falls. Over the valve e is placed
an outlet pipe 9 leading to any simple form of low pressure air pump or double
action bellows or to a gas holder, the pump drawing the gas from the vat or from
the gas holder and passing it through the purifying apparatus.
For collecting the carbonic acid gas from open fermenting vats or tuns the
following device may be used.
A cover is provided made of any suitable material, such for instance as galvanized,
buckled, or corrugated steel or iron plates, of a rather larger diameter than the top
of the vat, and having a deep flange or rim.
Round the outside of the vat and a little below the top, is fixed a deep narrow
annular channel into which the rim or flange of the cover fits loosely. This channel

page_text: is partially filled with any suitable liquid such as water, mercury, etc., which acts
as a lute or seal to prevent the escape of carbonic acid gas, and also the entrance of
air into the vat, except under excessive pressures.
The automatic regulator as described and illustrated above for closed vats may
be attached to this cover so as to collect the gas at any required pressure.
This regulator being so arranged as to close automatically when the pressure in
the vat falls below a certain fixed amount, no atmospheric air can enter the vat.
In order to reduce the number of covers required for a given number of vats or
tuns, the covers may be suspended by means of pulley blocks and rollers or other
suitable means to an overhead rail whereby they can be transferred from one vat
to another as required.
The purifying apparatus is arranged as follows :--
The gras is passed through a syphon gas trap (such as those illustrated in Figures 2
and 3), and thence :-
1st, to a vertical cylinder fitted with an inlet pipe for the gas, and an outlet pipe
at the top and having also a device for sprinkling water, which may be caused to
revolve by the issuing gas or by an external motor, in the usual well known way,
and the cylinder is also fitted with charging and discharging manholes. This
cylinder may be filled with any suitable material such as coke, charcoal, pumice
stone, flints, etc., over which the water from the sprinkler is caused to flow slowly
and continuously. The carbonic acid gas being forced in at the bottom, and
passing upwards is brought continually in contact with fresh water whereby all the
soluble impurities such as alcohol, acetic ether, etc., are removed.
The gas after passing through this scrubber is passed (2nd) through a second
scrubber similar to the first and fitted similarly but through which a melted fat or
oil, preferably mineral oil or a liquid or liquifiable hydrocarbon (such for instance
as melted paraffin wax or vaseline) as free as possible from odour and taste is made
to flow instead of water. The gas passing upwards through interstices of the coke
or other material is brought into intimate contact with the oil or other substance,
which having a great affinity for the ethers removes them from the gas.
These ethers may be recovered from the fat or oil or hydrocarbon and utilized
for the manufacture of fruit essences or other suitable purposes and the oil purified,
by distilling them off preferably with steam, superheated if necessary. The alcohol
may also be recovered from the first wash water by any suitable means of the well
known kind.
The carbonic acid gas after passing through the two scrubbers above mentioned,
and containing now only mere traces of impurities, and a certain amount of moisture
is passed through a desiccator containing any suitable material such as dry carbonate
of potash, chloride of calcium, sulphuric acid, or materials soaked in sulphuric
acid, etc., but preferably carbonate of potash or chloride of calcium. The desiccator
consists of a vessel containing a number of shelves (preferably moveable over
which the gas is compelled to flow, the desiccating material being placed on these
shelves, and the gas in passing over loses its moisture and escapes at the upper end
nearly or quite dry.
If preferred, two or more desiccating materials may be used either in separate
vessels or on different shelves of the same vessel. These desiccating materials may
also be recovered and used over again by driving off the moisture either by direct
firing or by passing a current of hot dry air over them. The latter process may be
performed without removal of the substance from the desiccator.
The dry carbonic acid gas is now passed through a series of tubes or pipes,
preferably of cast iron, arranged in a furnace and heated red hot. The first of
these tubes may contain coke, or metallic copper or iron or zinc preferably in the
form of turnings, to remove any traces of oxygen which the gas may contain, the
other tubes containing oxide of copper or other easily reducible oxide. We prefer
to use however oxide of copper formed in the following manner. All the tubes
except the first being closely filled with copper turnings are heated to a red heat
and a current of air is passed through them whereby a coating of oxide is formed

page_text: on the surface of the turnings, which oxide may be renewed in the same way
whenever it has become reduced. Copper wire or copper mails may be substituted
for the copper turnings or the ordinary commercial black oxide of copper may be
used. Or the oxide of copper may be formed in the pores and on the surface of a
porous or fibrous material such as firebrick, pumice stone, asbestos or the like by
saturating the material with a solution of nitrate of copper or a solution of an
inorganic salt of copper such as the acetate and then drying, and finally decom-
posing the copper salt at a high temperature in the presence of air, the treatment
being repeated if necessary.
Other chemical substances such as chromate of lead, bichromate of potash or
soda, binoxide of manganese, or other substance which at a high temperature parts
with its oxygen in the presence of organic matter may be substituted for the oxide
of copper.
When the carbonic acid gas is brought into contact with the hot oxide
of copper, by being passed through the tubes containing it, all the remaining
impurities are removed, being for the most part converted into carbonic acid gas
and water.
Should sensible traces of oxygen be found resulting from the decomposition of
organic compounds containing this gas, it may be completely removed by placing a
small amount of metallic copper, in the shape of turnings, wire gauze, or nails, in
the last tube.
When the oxide of copper described becomes reduced by the action of the
organic matter contained in the impure carbonic acid gas, it may be completely
regenerated by passing air over it, and the resulting hot air may be utilized for
redrying the desiccating material.
The carbonic acid gas, now perfectly purified, may be cooled in an ordinary
condenser, and compressed or liquified by any suitable compressor and placed in iron
or steel bottles or other suitable holders for sale or use.
In large vats such as are used by brewers, instead of a wooden or metallic cover,
the vats may be protected against contamination by atmospheric air by covering
them with a waterproof or oiled canvas sheet the edges of which are secured to the
vat in any convenient manner.
The gas may be run direct from the fermenting vats into a counterbalanced gas
holder of the usual kind, which itself acts as a regulator, without intermediate gas
traps or regulating valves. Where the vats are at a higher level than the
gas holder, the carbonic acid gas generated may be syphoned off into the gas holder,
great care being taken to prevent any air from being mixed with the gas withdrawn
from the vats.
Figures 2 and 3 represent two forms of gas traps, (where such are used) the
pressure being regulated by the level of the water in the trap. The baffle plates h
shewn in Figure 3 tend to dry the escaping gas, and similar plates may also be used
in the apparatus shewn in Figure 2.
We do not confine ourselves to the precise details or proportions of the
materials used, which may be varied more or less to suit varying circumstances, but
Having now particularly described and ascertained the nature of our said
invention and in what manner the same is to be performed, we declare that what
we claim is :-
1. The method of collecting carbonic acid gas obtained from closed fermentation
vats or tuns, or from other processes of fermentation, and of treating such carbonic
acid gas with melted fat, oil, or liquid hydrocarbon, substantially as and for the
purpose described.
2. The method of further purifying dried and partially purified carbonic acid gas
by passing it through heated tubes or chambers containing oxide of copper or other
easily reducible metallic oxide or salt or substance parting with its oxygen at a high
temperature, substantially as and for the purpose described.
3. The method of preparing, using, and re-oxidizing the metallic oxide for the
purpose of purifying carbonic acid gas, substantially as described.

page_text: 4. For collecting carbonic acid gas from a closed vat or tun, the automatic
apparatus consisting of the bellows b, rod c, valve e, and adjustable spring or weight f
substantially as described and illustrated.
Dated this 19th day of September 1892.
EDWARDS & Co.,
35, Southampton Buildings, London, Agents for the Applicants.