IMPROVEMENTS IN THE MANU- FACTURE OF ALCOHOL
Year: 1862

page_text: LETTERS PATENT to Alphonse Cotelle, of Saint Quentin, in the Empire
of France, Distiller, for the Invention of "IMPROVEMENTS IN THE MANU-
FACTURE OF ALCOHOL."
Sealed the 25th November 1862, and dated the 19th July 1862..
PROVISIONAL SPECIFICATION left by the said Alphonse Cotelle, at
the Office of the Commissioners of Patents, with his Petition, on 'the
19th July 1862.
I, ALPHONSE COTELLE, of Saint Quentin, in the Empire of France, Distiller,
5 do hereby declare the nature of the Invention for "IMPROVEMENTS IN THE
MANUFACTURE OF ALCOHOL," to be as follows:-
This Invention has for its object improvements in the manufacture of alcohol
or spirit, and consists in producing the same from olefiant gas and water.
For this purpose sulphuric acid is saturated with olefiant gas, which may be
done by bringing the acid into intimate contact with coal or other illuminating
gas, which has first been well purified, the acid so saturated is then mixed
with water and the olefiant gas leaves the acid and combines with the water,
so producing alcohol or spirit, which may be concentrated and purified by
distillation and otherwise.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Alphonse Cotelle in the Great Seal Patent Office on the
19th January 1863.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, ALPHONSE
COTELLE, of Saint Quentin, in the Empire of France, Distiller, send
greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Nineteenth day of July, in the year of our Lord
One thousand eight hundred and sixty-two, in the twenty-sixth year of Her
reign, did, for Herself, Her heirs and successors, give and grant unto me, the
said Alphonse Cotelle, Her special licence, that I, the said Alphonse Cotelle,
my executors, administrators, and assigns, or such others as I, the said
Alphonse Cotelle, my executors, administrators, and assigns, should at any
time agree with, and no others, from time to time and at all times thereafter
during the term therein expressed, should and lawfully might make, use,
exercise, and vend, within the United Kingdom of Great Britain and Ireland,
the Channel Islands, and Isle of Man, an Invention for "IMPROVEMENTS IN
THE MANUFACTURE OF ALCOHOL," upon the condition (amongst others) that I,
the said Alphonse Cotelle, my executors or administrators, by an instrument
in writing under my, or their, or one of their hands and seals, should par-
ticularly describe and ascertain the nature of the said Invention, and in
what manner the same was to be performed, and cause the same to be.
filed in the Great Seal Patent Office, within six calendar months 'next and
immediately after the date of the said Letters Patent.
NOW KNOW YE, that I, the said Alphonse Cotelle, do hereby declare
the nature of the said Invention, and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following
statement thereof, that is to say:-
This Invention has for its object improvements in the manufacture of alcohol,
and consists in the following process intended to manufacture alcohol by
means of its component parts, bicarbonated hydrogen (olefiant gas) and
water.
The well known chemical parts of alcohol are as follows:-A volume of
vapour from alcohol is composed of one volume of bi-carbonated hydrogen, and
one volume of vapour from water condensed into one volume. Hence it will
be understood that the secret of making alcohol by means of its component
parts is reduced to combining chemically bi-carbonated hydrogen and water

page_text: in a suitable proportion by a process which does not belong exclusively to
the laboratory, and that might be applied to its manufacture on a large
scale.
Before giving all the necessary details of the manipulations and the
precautions to take, we will cast a rapid glance at the process in order to
understand it thoroughly.
The bi-carbonated hydrogen not combining perfectly with water, it is combined
with sulphuric acid, with which it forms the etyl-sulphuric acid (an acid
composed of sulphuric acid, and bi-carbonated hydrogen), which remains in
solution in an excess of sulphuric acid. To this must be added a volume of
water equal to five times that of the acid. A great deal of the water combines
with the sulphuric acid for which it has more affinity than the bi-carbonated
bydrogen and the etyl-sulphuric acid decomposes. The bi-carbonated hydrogen
is then found in a nascent state, and combines with a certain quantity of.
water in forming alcohol, which remains in solution in the liquor. This liquor
should be filtered to purify it, then it should be distilled, and the alcohol
which evaporates at a lower temperature than the water and the acid will be
evaporated first.
One can see by this cursory view that the only bodies used are, 1, bi-
carbonated hydrogen; 2, sulphuric acid; 3, water. These several materials
may be employed in the following states:-
1st. Bi-carbonated hydrogen.-The bi-carbonated hydrogen gas may be
used mixed with pure hydrogen, proto-carbonated hydrogen, oxide of carbon,.
and sulphide of carbon, in other words common coal gas, may be employed
because the aforesaid foreign gases do not combine with the sulphuric acid in.
the process in which the combination of the bi-carbonated hydrogen with that
acid takes place, and do not prevent the formation of this last compound.
Their action being only to check a little the combination, but which is but of
trifling importance, considering how much time must be spent to isolate
completely the bi-carbonated hydrogen, and the enormous expense that it
would evolve. An essential point is that the gas used, whether it be extracted
from pit coal, oils, rosins, or any other matter should be entirely freed from the
empyreumatic oils, sulphuric, hydro-sulphuric, and carbonic acids, propylene
and amylene (carburets), &c., by careful refining. Besides the ordinary
refining apparatus, which absorbs or condenses tar, ammonia, sulphurous and
hydro-sulphuric acids, I use sandstone or leaden vases containing concentrated;
sulphuric acid, in which the gas is washed, and where it leaves the propylene, the
amylène and other analogous carburets. By unskilful refining the alcohol would

page_text: retain an unpleasant taste, and the impurities would in some cases prevent
its forming. It is necessary that the refining should be as. complete as
possible.
2. Sulphuric acid.-The sulphuric acid to be used is of the commercial
quality of 66 degrees of Beaumé's aerometer, and freed by ebullition of foreign
gases it might have absorbed. Ono must be careful not to employ the
Nordhausen's fuming acid, although its combination with the bi-carbonated
hydrogen is quicker than the ordinary acid; the reason is this, the combination
of that acid with the bi-carbonated hydrogen makes isethionic acid instead of
etylsulphuric acid, and that combination of the bi-carburet of hydrogen changes
itself into an isomeric carburet unfit for making alcohol.
3. Water. The water employed should be as pure as possible, and one
should avoid as much to use that which contains salts in solution; these salts
would not prevent the formation of the alcohol, but they would injure it more
or less, because in the presence of the sulphuric acid they might give rise to
reactions not desired. The bi-carbonated hydrogen, such as I have previously
described, is not capable of combining alone with water, it is necessary. that
an auxiliary agent (sulphuric acid) should be employed to effect that combina-
tion. The bi-carbonated hydrogen when put simply in contact with sulphuric
acid combines with it too slowly, it is therefore necessary for facility of manufac-
ture to employ quicker means.
There are four modes which may be employed, each having its advan-
tages according to local circumstances, and especially according to the
outlay, which it is desired to make, I therefore think it necessary to describe
them all.
First manner-The first manner is based on the principle of increasing
as much as possible the contact between the gas and the acid, for the
greater the contact the quicker will be the absorption of the gas by the
acid. The apparatus that I have invented to obtain that result is shewn at
Figure 1.
A, A, A, Figure 1, a leaden vat filled with concentrated sulphuric acid;
B, B, B, a leaden receiver floating in the vat containing the acid; C'a cast
iron or copper suction pump and solid piston; D, D, D, lenden pipe in con-
nection with the pump; E, ball perforated with a multitude of small holes;
F, india-rubber valve fitted to the pipe D, D, D, for the purpose of filling
it with acid during the return stroke of the pump; II, cock to permit the
ingress of the air to the pump if there is not sufficient.
The manner of working this apparatus is as follows:-The vat A, A,,A,

page_text: being filled with acid, the receiver B, B, B, must be filled with coal gas
by means of a pipe, which I have not drawn on the plan. By means of the
valve F, which opens inwards, the pipe D, D, D, is filled with acid- to the
height of the acid outside. If the piston of the pump is worked up and down
the compressed air drives back the acid, which remains in the pipe D,,D, D,
and the acid escapes by the perforated ball E, and falls again. like rain.
In lowering the piston the pipe D, D, D, again fills, and in working the
piston again upwards the acid escapes by the ball E, and so on. To work
the piston up and down without interruption care must be taken that the air
compressed. by it in its course be less than sufficient to fill the pipe D, D,. D.
It will be understood that by this means the gas which fills the receiver
B, B; B, is always in contact with small particles of acid, which accelerates
its absorption. It will be seen that all the bi-carbonated hydrogen contained
in the gas of the receiver is absorbed when the receiver no longer descends,
because the other gases are not absorbed by the acid. The lowering of the
receiver should be only about 18 for coal gas. When that result is obtained
it is necessary to allow the remaining gas to escape by a pipe, which is not shewn
on the Drawing, and it may be taken wherever convenient for burning or
lighting purposes. The receiver must be refilled, and the work continued in the
same manner as above.
The operation is continued in this manner till the acid in the vat has
lost its absorbing power. To know how many times the receiver should
be refilled with gas before renewing the acid, it is sufficient to know that one
measure of acid will absorb all the bi-carbonated hydrogen contained in 1500
measures of coal gas.
The size of the apparatuses and their number should be calculated in such
In all cases
a manner as to employ the gas as soon as the retorts make it.
it will be necessary to have at least two for constant work, and not to have a
special gasometer for the storing of the gas.
I will describe hereafter what is necessary to be done with the acid saturated
with olefiant gas.
Second manner. The second manner is based on the same principle as the
first. It bas the advantage of requiring only one apparatus continually working,
but it is more expensive than the first.
The description is as follows:-A, (Figure 2,) reservoir for the concentrated
sulphuric acid; B, B, B, B, leaden column or pipes of sandstone, divided
into receptacles by leaden plates a, a, a, a, a, a; C, reservoir made to receive
the acid saturated with bi-carbonated hydrogen; b, b, b, delivery pipe for the

page_text: "
gas. This pipe dips in the acid, and ends in a worm perforated with small
holes from whence the gas escapes. This pipe communicates with a lift, and
force pump, , which takes the gas from the retorts, and forces it into the column
B. Each leaden plate a, a, has under it a small leaden pipe g, in the form
of a screw, and perforated with small holes, from which the acid falls as rain.
Above it has a leaden pipo much larger, (about 20 times,) of the form of
a swan's neck, and falls back on the plate to assume the form of a screw.
The screw form pipe is perforated with small holes, from which the gas escapes
in bubbles through the acid; c, funnel for the reception of the acid; d, wasto
gas pipe; f, cock to empty the reservoir C.
The way to work the apparatus is as follows;-The cock of the gas delivery
pipe b is opened, as also the cock of the reservoir A containing the acid, and
as long as the reservoir contains any acid, and the retorts continue to furnish
gas, and the lift and force pump forces the gas by the pipe b, b, b, the com-
bination goes on regularly without manual labour or stoppage. The acid
falling in the funnel c passes to the first worm g, and falls in the shape of
rain on the first plate, from that plate it passes to the second worm to fall again
as rain on the next plate, and so on to the reservoir C. The gas coming out
of the pipe b, b, b, fills the reservoir C, escapes by the pipe h of the first plate,
and escapes from that pipe, and passes through the acid, which covers that
plate, from which the gas escapes by the pipe h of the second plate by passing
through tho acid, which covers that second plate, and so on to the last
receptacle, from which it escapes by the pipe d, for burning or for lighting
purposes.
It is to be noticed that the gas and the acid follow two different directions.
The gas ascends, the acid falls. The gas to arrive at the top of the column
is caused to pass through as many layers of acid as there are plates, and finds
itself an oqual number of times in contact with a shower of acid, so that the
greater the number of plates the more does the gas give off to the acid its
bi-carbonated hydrogen. (It is necessary to have at least 50 plates to obtain
a satisfactory result.) The falling acid becomes charged with bi-carbonated
hydrogen, and as long as the quantity, which runs from the reservoir A is not
'too great it falls into the reservoir C saturated with olefiant gas. (One
measure of acid should only be allowed to run to 1500 measures of gas
traversing the column.) I take from the reservoir C by the cock the quantity
of saturated acid required, and which I treat as will be described hereafter.
Third manner. The third manner of absorption of gas by acid is based on
the same principle as the manufacture of soda water, that is to say, that the

page_text: absorption is effected by means of compression. This mode requires first a
forcing pump equal to the pressure of 4 or 5 atmospheres, and a great number
of leaden or other vases, which are capable of resisting the action of the acid,
in each of which is placed, say, one quart of acid. The gas having been com-
pressed in each vase, it is necessary to allow the vases to remain undisturbed
for two days, during which time the combination of the olefiant gas and the acid
is effected. Then I allow the exhausted gas to escape for the purpose of
lighting or heating, and the saturated acid is emptied for use in the way that
I will presently describe. Some fresh acid is introduced and compressed,
and so on.
Fourth manner. The fourth mode is more simple than the three others,
but on account of a platinum boiler being required it is more expensive, but
there is no fear of accidents. It consists in placing the sulphuric acid in the
form of vapour in contact with the gas. The mixture is very intimate, and
when cool the liquid acid is found to have absorbed all the bi-carbonated
hydrogen gas contained in the gaseous mixture.
The following is a description of the apparatus, by means of which the
result may be obtained. A is a platinum or glass boiler, two-thirds filled with
sulphuric acid; C, D, large pipe of the same material, lengthened to such an
extent as to obtain a slow and gradual cooling; B, pipe conveying the coal
gas taken from the gasometer; E, a leaden worm passing through a reservoir
filled with cold water; F, leaden reservoir, hermetically sealed, into which
the condensed vapours and the incondensible gases run; G, pipe, for the
escape of the gas deprived of bi-carbonated hydrogen. This gas may be
carried under boilers to be burnt. To work by means of this apparatus the
boiler A must be heated, and when the acid is in ebullition the cock B which
conveys the gas must be opened. The gas and the vapour mix in the part
C, D, cool in the worm E, and are carried into the reservoir F. The con-
densed vapours remain in the reservoir F, and the uncondensed gases escape
by the pipe G. When the reservoir F is three-quarters full the liquid should
be run off by the pipe at the bottom. It should be understood that this
apparatus requires safety valves, which are not shewn on the plan.
By these four modes, just described, may be obtained the combination of
sulphuric acid with bi-carbonated hydrogen, or the etyl-sulphuric acid. To make
the alcohol I pour into the last acid slowly, and at different times, to prevent
too much heat, a volume of water five times greater. The liquor, which was
tolerably limpid and of a reddish brown color, becomes disturbed and becomes
of a dirty yellow color. By adding a great quantity of. water the etyl-sulphuric

page_text: acid yields to the water the sulphuric acid, and the bi-carbonated hydrogen set
free combines in a mascent state with a certain quantity of water for making
the alcohol. This alcohol remains in solution in the liquor. To separate the
alcohol it is only necessary to distil the liquor; but before distilling it
the liquor must be purified, or it would impart a bad taste to the alcohol.
The filtering may be effected by means of a leaden plate perforated with a
great number of small holes, and covered with a layer of fine charcoal dross,
or, still better, with powdered animal charcoal. After filtering the liquor is
distilled in a leaden still till half the liquor contained in the reservoir is dis-
tilled. The result obtained still contains some traces of acid, which may
bo easily removed by adding a little carbonate of lime. The liquor being
deprived of acid contains nothing but alcohol and water, and can be concentrated
in the ordinary distillatory apparatus.
Although the preceding description is sufficiently clear to obtain alcohol by
means of coal gas, it is necessary to complete it by some general observations
on the manufacture on a large scale.
The first observation to be noticed for continuous work is, that it is of the
utmost utility to have two similar apparatuses to Figure 1 for the first manner
of combination, and Figure 3 for the fourth mode, because without them the
works would be intermittent.
The second observation shews that gas deprived of olefiant gas being a com-
bustible of the greatest calorific power, it is necessary to place the piping in
such a position as to be able to utilize it under the various boilers used.
The third observation is for the purpose of shewing that except losses,
which can never be prevented in great concerns, the sulphuric acid that is
employed may serve almost indefinitely. In fact, when the liquor is distilled
for the first time in the leaden still (Figure 4), the acid does not distil sinco
it only evaporates by the application of heat greater than 300° centigrade. It
may be concentrated in sandstone, glass, or platinum evaporating receptacles
until it marks when cool 66 degrees of Beaumé's aerometer, and so on.
At length, as fourth and last remark, I will observe that the reservoirs
which contain cold sulphuric acid should bo in lead, sandstone, or glass not
liable to corrosion by tho acid, and that those in which the acid is heated to
a heat of more than 250 degrees centigrade should not be in lead from its
liability to melt, and from the sandstone and glass being very brittle; it scems
to me of the utmost necessity to use platinum receptacles.
The process that I have just described for the manufacture of alcohol will
give an economy of more than 60 per cent. over the manufacture with beet-

page_text: root or molasses, whatever may be the material from which the gas has been
extracted. This economy is still more considerable if the gas has been
extracted from pit coal, because the coke repays nearly the price of the coal;
but this depends on local causes. If we consider the first expenses of an
establishment, advantages might be derived in using other substances than
coal; oils, for example, because to an equal volume of gas the bi-carbonated
bydrogen is found in a greater quantity in oil gas than in coal. But taking
it altogether I believe that coal cannot be equalled. Besides, in coal mining
countries the alcohol extracted would only cost the manual labour.
In witness whereof, I, the said Alphonse Cotelle, have hereunto set my
hand and seal, this Fifteenth day of January, in the year of our Lord
One thousand eight hundred and sixty-three.