A NEW METHOD OF MANUFACTURING GAS ALCOHOL BY MEANS OF DILUTED ACIDS ACTING INDEFINITELY WITHOUT RECONCENTRATION
Year: 1863

page_text: LETTERS PATENT to Eugène Alphonse Cotelle, of 29; Boulevart St.
Martin, Paris, Empire of France, Distiller, for the Invention of "A
NEW METHOD OF MANUFACTURING GAS ALCOHOL BY MEANS OF DILUTED ACIDS
ACTING INDEFINITELY WITHOUT RECONCENTRATION."
Sealed the 19th January 1864, and dated the 4th August 1863.
PROVISIONAL SPECIFICATION left by the said Eugène Alphonse Cotelle
at the Office of the Commissioners of Patents, with his Petition, on the
4th August 1863.
I, EUGÈNE ALPHONSE COTELLE, of 29, Boulevart St. Martin, Paris, Empire
of France, Distiller, do hereby declare the nature of the said Invention for
"A NEW METHOD OF MANUFACTURING GAS ALCOHOL BY MEANS OF DILUTED ACIDS
ACTING INDEFINITELY WITHOUT RECONCENTRATION," to be as follows:-
My Invention relates to the manufacture of alcohol with any kind of gas
containing olefiant gas, and also to employing it as an agent in the combina-
tion of bodies acting indefinitely without revivification. The principles on
which my Invention is based are as follows:-
1st alcohol (CHO), consists of one part olefiant gas (C'H'), and two
parts water (2HO); 2ndly, if starch for example, be treated with a diluted™
acid, which only differs from glucose by four equivalents of water at least, this
acid fixes the water in the starch, and transforms it into glucose, further, the
acid is not changed, which is a characteristic of its action; 3rdly, it results

page_text: from the two foregoing principles, that if olefiant gas be treated with diluted
acid, said acid will fix the water in the olefiant gas, and form alcohol. This
is in effect which I have learned from experience, but the success is sub-
ordinate to several important conditions to be fulfilled, and which I will now
proceed to describe, as also the apparatus and means with which I have
obtained the best results hitherto.
In order to render myself as clear as possible, I will at once describe the
operation generally without entering into any details.
The manufacture presents three distinct stages, which are, first, the produc-
tion of gas, and its purification; secondly, the formation of alcohol; and,
thirdly, distillation and rectification. I will here only refer to the formation
of alcohol, as the other two stages only require some slight modifications in
detail.
In an apparatus arranged for multiplying the points of contact, I intro-
duce at the lower part a jet of gas and of steam, while I introduce warm
acidulated water from above, and again repeatedly raise it from the lower
part, and introduce it afresh from above. In this contact between the gas,
steam, and acidulated water, the acid fixes two equivalents of water, and
transforms it into alcohol. This alcohol which is in a state of vapour, escapes
with the gas which is still uncombined into a refrigerator to be liquified,
whence it passes into a closed vessel furnished with a cock for the emission of
the
This alcohol is then distilled in order to increase its strength, and is
gas.
afterwards rectified. It will thus be seen that the same acidulated water
serves throughout, which is further kept constantly heated by the jet of steam.
This being understood, I will proceed to describe the details of the three
phases of the operation.
1st. Production and purification of the gas.-There is little to be said under
this head. The matters to be distilled, such as coal, boghead, oil, or others,
should be distilled at a temperature productive of the greatest quantity of
olefiant gas without regard to the total amount of the gas. The purification
should also remove all carburets with the exception of the olefiant gas, and
protocarbonated hydrogen, such as propylene or amylene, it is also well to agitate
the gas in a little concentrated sulphuric acid or olive oil.
2ndly. Formation of alcohol.-As before mentioned I do not confine myself
to any peculiar form of apparatus which may be varied as desired, as provided
the gas is in contact for a sufficient length of time with the acidulated water
heated to a suitable degree, the formation of alcohol will be ensured.
I will now proceed to describe three apparatus of simple arrangement, pro-
ducing the best results hitherto without giving preference to one or the other,

page_text: at same time each one has its advantages according to circumstances. I will
describe the apparatus in the order in which they have been tried.
First apparatus. This apparatus consists of a column A, A, Fig. 1, of the
Drawing annexed, made of lead, wood, or earthenware, divided into stages or
compartments by sheets of lead b, b, which are pierced with small holes for
the passage of the vapour and gases. These stages are each furnished with
overflow pipes c, c, through which the liquid passes. At the base of the
column is placed a pipe C, into which the gas is injected by means of a
pump B. D, D, is a pipe for injecting steam; L, syphon, by means of which
the liquid descending from the column is caused to flow freely into reservoir M;
K, K, pipe for conveying the liquid from reservoir M by means of a pump
into the funnel-mouthed syphon J, which is allowed again to pass into the
column; E, pipe for conducting the vapours and gases into the refrigerating
worm tubo F, and thence into a closed vessel G, in which the liquid remains.
while the gases escape by pipe H. This vessel G is furnished at the lower
part with a discharge cock I. In order to use the apparatus steam is
admitted at pipe D, the acidulated water containing fifteen per cent. of acid,
being introduced at funnel J, preference is given to sulphuric acid in con-
sequence of its low price and great stability. When ebullition of the liquid
commences, the gas is introduced by means of pump B. The gas and steam
being thus in presence of, and in contact with the diluted heated acid and
olefiant gas, combine with a certain quantity of water and form alcohol, which
escapes in a vapour at pipe E, and becoming liquified in refrigerator F, finally
passes into vessel G, while the gases which are still uncombined escape at
pipe H, which conducts them into a receiver to serve for the heating. The
diaphragms b, b, always retain a certain depth of liquid which the gases are
forced to traverso as they rise, for the sole purpose of multiplying the points
of contact. It should be remarked that the heated acidulated water flows
continually into the column, and as continually rises to the upper part. The
injection of steam should be regulated in such manner that the density of the
liquid be not sensibly changed. The liquid in vessel G, which contains about
five per cent. of alcohol, is submitted to a first distillation as will be herein-
after described. The injection of gas should be regulated in such manner as
to require about fifteen minutes to traverse the column.
Second apparatus.-The second apparatus consists of a series of chambers,
thirty in number, communicating with each other by means of bent pipes.
A, A', A, as shown in Fig. 2 of the annexed Drawing, two-thirds of these:
chambers are heated by a sand bath, the other third are not heated; these
chambers are furnished with pipes C, C', C, perforated with small holes at

page_text: their lower ends for the introduction of the gas, also having each a pipe D,
D', D", for the admission of the liquid. The gas is supplied to the first
chamber by force pump B. A pipe E conveys the steam and gases into the
-refrigerator F as in the preceding arrangement. In order to set the apparatus
in action the chambers are half. filled with acidulated water containing about i
ten per cent. of acid, which is then heated. When the chambers which are
out of the sand bath commence to heat, the gas is injected by pump B. This
gas after traversing the first chamber A, escapes with the steam introduced by
pipe C, C', into the second chamber A', and so on through all the others in
succession until it reaches A". In its passage the olefiant gas combines with
the water and forms alcohol, which escapes with the gases at pipe E into
reservoir G as above described. The water which may evaporate in the
chambers is replaced by stopping the pump momentarily, and introducing hot
water by means of pipes D, D', D". The level of the liquid may be ascer-
tained by removing the stem of the cock, and introducing into the pipe a small
cork float suspended by a string.
Third apparatus. --The third apparatus to which I give preference on
account of the simplicity of its construction and action, is composed of two
large wood cases A, A, A¹, A¹, Fig. 3, each furnished with a funnel cock for
the introduction of the liquid, an overflow syphon for keeping the liquid at a
constant level, a tube indicator of the level of the water and discharge cock,
these parts are not represented in the Drawing to avoid confusion. The first
chamber is furnished with a steam pipe D, D, and worm tube c, c, through
which the force pump B forces the gas which is introduced into the liquid.
The steam and gases pass from the first to the second chamber by pipe C', C',
in order to act on the liquid afterwards escaping at pipe C", to be cooled in
refrigerator G, finally passing into reservoir H as in the preceding apparatus.
At the centre of the bottom of each chamber is placed a cylindrical chamber
E, E, each furnished with an india-rubber valve F, F, opening inwards, the
upper parts of these chambers are contracted, and each terminate in a small
rose, perforated with numerous small holes, said chambers are also placed in
communication one with the upper, and the other with the lower part of a
force pump K, which cannot be injured by the dilute acids. In order to use
the apparatus, acidulated water is introduced into the chambers containing about
twelve per cent. of acid, until the chambers E, E¹, are covered, a jet of steam
being also introduced at pipe D. When the liquid is heated, the gas is in-
jected by pump B. The pump K also introduces a jet of liquid alternately
into each of the two chambers, which falls like rain therein. The alcohol
which forms, escapes with the gases at pipe C", C", as in the preceding arrange-
2.

page_text: ments. The jet of steam should be regulated in such manner as neither to
increase nor diminish the volume of liquid contained in the chambers. The jet.
of steam should also be regulated, so that it remains in the second chamber at
least twenty minutes.
Observations. In the first apparatus described I may apply subdividers on
the several stages in order to multiply the points of contact. The second.
apparatus may also be similarly furnished. Care should be taken in all cases
not to employ coke, which produces sulphurous acid. I may also in the first
apparatus dispense with the stages, and fill the column from top to bottom
with bulbs, having three apertures as in the columns employed in the manu-
facture of sulphuric acid.
3rdly. Distillation and rectification.-The liquid obtained in the foregoing.
apparatus possesses but a small degree of strength, it is therefore necessary
that it should be distilled before being rectified. For this purpose the appa-
ratus is furnished with a refrigerator for collecting the ether which always
forms to a small extent. The greater part of the essential oils should also be
eliminated in order that the liquid may be readily and properly rectified. In
conclusion, I would observe that I do not confine myself to any peculiar form of
apparatus, which may be varied as experience may prove desirable. The Inven-
tion comprises simply the principle of forming alcohol with olefiant gas and
water, by means of weak acids acting without reconcentration or revivification.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Eugène Alphonse Cotelle in the Great Seal Patent Office
on the 3rd February 1864.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, EUGÈNE
ALPHONSE COTELLE, of 29, Boulevard St. Martin, Paris, Empire of France,
Distiller, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Fourth day of August, in the year of our Lord
One thousand eight hundred and sixty-three, in the twenty-seventh year of
Her reign, did, for Herself, Her heirs and successors, give and grant unto
me, the said I Eugène Alphonse Cotelle, Her' special licence that I, the said
Eugène Alphonse Cotelle, .executors, administrators, and assigns, or such
others as I, the said Eugène Alphonse Cotelle, 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

page_text: lawfully might make, use, exercise, and vend, within the United Kingdom of
Great Britain and Ireland, the Channel Islands, and Isle of Man, an Inven-
tion for "A NEW METHOD OF MANUFACTURING GAS ALCOHOL BY MEANS OF DILUTED
ACIDS ACTING INDEFINITELY WITHOUT RECONCENTRATION," upon the condition
(amongst others) that I, the said Eugène Alphonse Cotelle, my executors 'or
administrators, by an instrument in writing under my, or their, or one of
their hands and seals, should particularly 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 Eugène Alphonse Cotelle, do, hereby
declare tho nature of my said Invention, and in what manner the same is
to be performed, to be particularly described and ascertained in and bý
the following statement; reference being had to the annexed Sheet of
Drawings.
The object of my Invention is to manufacture alcohol with any gas what-.
éver containing olefiant gas, and by using, as combining agents, certain bodies
acting indefinitely without revivification: The following are the principles
upon which this Invention is based,-.
1st, one equivalent of alcohol, C'HO', is composed of one equivalent of
olefiant gas, C'H', plus two equivalents of water 2HO; 2nd, if I treat
starch or amylum, for instance, which only differs from glucose by minus
four equivalents of water with a diluted acid, this will fix water upon the
starch and transform it into glucose, further the acid will not be in any wise
impaired or altered, which is a characteristic of its action; 3rd, from the
two above principles there results that if olefiant gas is treated with a
diluted acid this will fix water in the olefiant gas, and form alcohol. I have
been made conscious of this fact by practice, but complete success is sub-
ordinated to various important conditions which should be fulfilled, and which
I shall minutely detail when describing the apparatus and manipulations
which till now have best answered my purpose.
In order to enable persons skilful in the art to understand and work my
Invention, I shall describe summarily my operations without entering for the
moment into any particulars. There are three distinct stages in this manu-
facture: 1st, producing and purifying the gas; 2nd, forming the alcohol; 3rd,
distilling and rectifying.
I will here only refer to the formation of the alcohol, the first and third
stages in the operations having to undergo but very slight modifications in the

page_text: details. In an apparatus so arranged as to multiply the points of contact, I
inject through the bottom a film of gas and steam through the top, I pour
some acidulated hot water, which I collect constantly from the bottom and
pour in again from the top. In this contact between the gas, the steam and
acidulated water, the acid fixes upon the olefiant gas two equivalents of
water, and transforms it into alcohol. This alcohol, which is in the state of
vapor, escapes with the non-combined gases, passes into a refrigerator to bo
liquefied, and thence into a closed vessel provided with a tube for the escape of
the gases. This alcohol is submitted to distillation to increase its degree of
strength, and passes afterwards to the rectifying process. As may be seen it
is always the same acidulated water which is employed, being constantly kept
hot by the jet of steam. This being once well understood, I will proceed to
explain in detail the three stages of the operation.
1st. Producing and purifying the gas.-I have but little to say on this
subject, it is important that the matters such as coal, boghead, oil, &c. be
distilled at a temperaturo which 'permits of obtaining the greatest amount
of olefiant gas without regard to the whole quantity of gas. As regards
purification, this must be as perfect as possible, and in order to remove all
other carburets except the olefiant gas, and proto-carbonated hydrogen, such
as propylene, amylene, &c., the gas should be agitated in a little concentrated
sulphuric acid or olive oil.
2ndly. Forming the alcohol.-As I observed in the beginning, I do not limit
myself to the form or shape of the apparatus, which may be infinitely varied,
provided the gas be long enough in contact with the acidulated water, heated
to a suitable degree, the formation of the alcohol will take place. I might there-
fore, limit myself to set forth the conditions to be fulfilled; I will describe,
however, three very simple apparatus which have always yielded good results.
Without any preference for either of them, as each has its advantages, I will
describe them in the same order as I have experimented with them.
.
First apparatus.-This first apparatus is composed of a column A, A, A, A,
Fig. 1, which may be of lead, wood, or earthenware, divided into compart-
ments by lead sheets b, b, b, b, perforated with small holes for the passage of
steam and gases. These plates have discharge holes c, c, c, c, through
which the liquid in excess escapes. At the bottom of the column there is a
tube C, C, through which the gas is injected by a pump B; D, D, tube for the
injection of steam; L, syphon for allowing of the free passage of the liquid
descending from the column into the recipient M; K, K, tube for returning
by means of a pump, the liquid from the recipient M, into the syphon funnel
J, which allows of its again passing into tho column; E, E, tube conducting

page_text: the vapours and gases into the refrigerating worm F, and thence into a closed
vessel G, in which the liquid remains, whilst the gases escape through the tube
H. At the bottom of this last vessel there is a discharge cock 1. In order
to work this apparatus steam is injected through the tube D, and acidulated
water, containing about 15% of acid introduced into the funnel J. I prefer
using sulphuric acid on account of its low price and its great strength.
When the liquid has reached the boiling point I inject some gas by means of
the pump B. The gas and steam are then brought in contact in presence of
the diluted heated acid, and the olefiant gas combines with a certain
quantity of water in order to form alcohol, which escapes like vapor through
the tubo E, E, is liquefied in the refrigerator F, and finally passes into the
vessel G, whilst the non-combined gases escape through the tube H, which
conveys them into a receiver for heating purposes.
The diaphragms b, b, b, b, upon which is kept a film of liquid, through which
the gases are obliged to pass in their ascent, are merely intended to multiply
the points of contact. I will observe that the hot acidulated water is in-
cessantly poured into the column, from whence it is constantly raised and-
poured in again, the injection of steam should be so regulated as to not sensibly.
change the density of the liquid. The liquid which is in the vessel G, and
which contains about 5% of alcohol, is submitted to a first distillation, as will
soon be hercin-after explained. The injection of gas should be so calculated
as to take about 15 minutes to pass through the column.
.
Second apparatus. The second apparatus consists of about thirty vessels:
A, A', to A", as represented in Fig. 2, two-thirds of which are heated in a
sand bath and the other third are not heated. These carry, each of them, a
tube c, c, c, c', to c", c", perforated at the bottom to allow of the agitation
of the gas, and another tube with a funnel cock D, D', to D, for the intro-
duction of the liquid. A force pump B is used for introducing the gas into
the first vessel. A tube E leads the steam and gases into the refrigerator F,
as in the before described apparatus. In order to work this apparatus the
vessels are half filled with acidulated water containing about 10% of acid,
and heat is then applied. When the vessels which are out of the sand batlı
begin to get heated, gas is injected by means of the pump B, which gas
agitates in the first vessel A, escapes with the steam formed through the tube
C', C', to be then agitated in the second vessel A', and so forth until it has
reached A". In this passage the olefiant gas is combined with water so as to
form alcohol, which escapes with the gases through the tube E, E, to enter
the receiver G as precedently. In order to renew the water which is evaporated
in the vessels, the pump is stopped for a moment, and hot water is introduced
"

page_text: through the tubes D, D',... ... D. The level of the liquid is ascertained
by taking off the key of the cock and introducing into the tube a small cock
float suspended from a string.
Third apparatus.-This third apparatus, which I somewhat prefer on
account of its simple construction and action, is composed of two large
wooden boxes A, A, A, A, A', A', A', A', Fig. 3, cach provided with a funnel
cock for introducing the liquid, a discharge syphon for maintaining the
level of said liquid, a tube indicating the level of the water, and a discharge
cock, which four parts are not indicated in the Drawing in order to avoid
.confusion. The first box carries a steam tube D,, D, and a worm' C, C,
through which a force pump B injects gas which agitates the liquid. The
steam and gas from the first box are conveyed into the second by the tube
C, C, C, where they still agitate the liquid, from whenco they escape
through the tube C", C", become cooled in the refrigerator G, and enter the
receiver H, as in the above-described apparatus. In the centre of the bottom
of each box there is a leaden cylindrical vessel E, E', with an india-rubber
valve opening inwards. The upper parts of these vessels are narrowed, and
terminate in a watering rose provided with some small holes. These vessels
are set in communication, the one with the bottom and the other with the top
of a force pump K, which is proof against any action of the diluted acids.
In order to work this apparatus I introduce into the boxes some acidulated
water containing about 12° of acid, so that the vessels E, E, may be covered,
and I inject a jet of steam through the tube D, D, when the liquor is heated.
I inject gas by means of the pump B, & also work the pump K, which
alternately introduces a shower of liquid in each of the two boxes.. The
alcohol formed escapes with the gases through the tube C", C", as in the
above apparatus. The jet of steam should be so regulated as to neither
increase nor diminish the amount of the liquid in the boxes. The jet of gas
should be so regulated as to not escape from the second box for twenty
minutes at least.
The foregoing apparatus may undergo some slight modifications (see
Fig. 3, wherein the same letters of reference indicate the same parts as in
Fig. 3). In Fig. 3b, instead of the parts E, E', I substitute injectors m, m',
m", m, operating as follows:-The gas supplied by the pump B is stored in
the receiver R.till it has reached a pressure of three atmospheres, which it
must not exceed, and which number is ascertained by a gauge placed at the
upper part. By means of a force pump I fill the receiver N with hot acidu-
lated water so as to three parts fill it by means of the tube O; if then the
cocks of the small tubes 9, 2, 2", 2", are opened so as to supply to each

page_text: injector an equal quantity of liquid, and if at same time the cock of the gas
tube L is opened; the liquid will escape like a shower through the injectors.
The tube M, M, is necessary to produce pressure on the liquid in vessel N
without which pressure the liquid would not descend. The tube C, C, in com-
munication with the receiver R is provided with a cock through which gas
passes should the pressure rise above three atmospheres. Every other part is
the same as in the above-described apparatus.
In the first apparatus described dividing surfaces may be placed upon the
plates for increasing the points of contact. The vessels of the second apparatus
may likewise be similarly fitted, care however must be taken that coke be not
employed, as it would produce sulphurous acid. I may also dispense with the
stages in the first apparatus, and the column may be filled from top to bottom
with bulbs having three apertures such as are employed in the denitrifying
columns of sulphuric acid works.
Distilling and rectifying.-The liquid obtained in the foregoing apparatus
being at a low degree must be distilled before being rectified, it is proper
that the apparatus should be provided with a refrigerator for collecting the
ether, which is always formed in small quantities. It is also necessary that
part of the essential oils should be eliminated so as to easily obtain a good
rectification.
Having thus described the nature of my Invention, I wish it to be distinctly
understood that I do not confine myself to the exact form or shape of the
apparatus, which may be infinitely varied, and which will undoubtedly be
modified after long practico; but what I claim is the principle itself, that is
to say, the formation of alcohol with olefiant gas and water, by means of s
diluted acids acting merely by their presence without reconcentration or
revivification; and to conclude I will observe that with some modifications,
which it is unnecessary to describe, I may likewise form various bodies
composed of water and any carburet.
In witness whereof, I, the said Eugène Alphonse Cotelle, have hereunto
set my hand and seal, this Twenty-eighth day of January, in the year
of our Lord One thousand eight hundred and sixty-four.