IMPROVEMENTS IN THE METHOD OF AND APPARATUS FOR TREATING RESIDUA OF DISTILLATION, FERMENTATION, AND SIMILAR OPERATIONS IN ORDER TO OBTAIN AND UTILIZE AMMONIA, CARBONIC ACID, AMMONIACAL SALTS, ALKALINE CARBONATES, SALTPETRE, AND OTHER PRODUCTS
Year: 1874

page_text: PROVISIONAL SPECIFICATION left by Michael Henry at the Office
of the Commissioners of Patents; with his Petition, on the 16th
July 1874. A communication from abroad by Louis Charles
Emeric Faucheux, of 17, Boulevart Saint Martin, Paris, France.
I, MICHAEL HENRY, of Fleet Chambers, 68, Fleet Street, in the City
of London, Patent Agent, do hereby declare the nature of the said
Invention for "IMPROVEMENTS IN THE METHOD OF AND APPARATUS FOR TREATING
RESIDUA OF DISTILLATION, FERMENTATION, AND SIMILAR OPERATIONS IN ORDER TO
OBTAIN AND UTILIZE AMMONIA, CARBONIC ACID, AMMONIACAL SALTS, ALKALINE
CARBONATES, SALTPETRE, AND OTHER PRODUCTS" (communicated to me from
abroad by Louis Charles Emeric Faucheux, of 17, Boulevart Saint
Martin, Paris, France,) to be as follows:-
The object of this Invention is the treatment of the residua of
distillation, fermentation, and similar operations, in order to obtain and
utilize carbonic acid and ammonia, ammoniacal salts, alkaline carbonates
and bicarbonates, and saltpetre, and other products...

page_text: For producing carbonate and bicarbonate of soda and ammoniacal
salts, the Inventor relies on the following chemical reactions:-When
chloride of sodium and bicarbonate of ammonia are brought together,
hydrochlorate of ammonia is produced, also bicarbonate of soda which
is less soluble than those salts and which is precipitated :—When a
current of ammonia is passed through a concentrated solution of sea salt
until the quantity of ammonia in solution corresponds by the chemical
equivalents of the preceding reaction with the quantity of chloride
employed, and when afterwards a current of carbonic acid is passed
through the solution, the carbonic acid will first be absorbed by the
ammonia so as to form carbonate and sesquicarbonate of ammonia, and
then when the ammonia shall have been saturated with carbonic acid
bicarbonate of ammonia will be formed, and thereupon the bicarbonate
of soda will be precipitated.
In order to produce the ammonia, first, suppose for instance treacle,
molasses, or saccharine matter is under distillation. The molasses or
saccharine matter diluted with water and treated with sulphuric acid, and
then subjected to fermentation with yeast, or other leaven, or ferment, and
then distilled, yields a wash or residuum containing all the soluble salts
of beetroot juice, and the azotized matters which have escaped coagulation
in the manufacture of sugar. This wash is evaporated to 25° to 30°
Beaumé, and then calcined in reverberatory furnaces, and decomposition
taking place, the ammoniacal products escape through the chimney, and
the alkaline salts containing organic acids are converted into carbonates.
:
To extract the ammonia one or other of the two following methods is
adopted-First, for caustic alkalis (this is specially applicable for
distilleries in which the said potash is refined) when hydrate of
potassa, soda, or lime acts on azotized matter, ammonia is disengaged
and alkaline salts or salts of lime are formed corresponding with the
ammoniacal salts destroyed. Lime is usually objectionable for the
purpose, but when employed the ammoniacal liquors are led to a tank in
which they are subjected to the action of a current of carbonic acid
arising from the fermentation process, and continued until all the lime
is precipitated in a state of carbonate. The liquid is allowed to settle
and poured off, and then taken to the potass furnace. The deposit is
washed again and again until freed from all the alkaline salts...

page_text: In distilleries in which raw potassa is refined, the sulphates and
chlorides are first drawn off, and the alkaline carbonates remain. The
liquors containing these carbonates are boiled in a close vessel with pure
lime, and water is added to dissolve the salts, the insoluble carbonate of
lime is precipitated, and the liquors resulting will contain a solution of
hydrates of potassa and soda. Again, wash concentrated at 25 Beaumé
is carried off to an ammonia extracting apparatus and boiler, and instead
of lime a solution of caustic alkali is brought in at intervals; the
ammonia will be disengaged and carried off into a refrigerator and
thence into a solution of chloride of sodium; the potassa must be
admitted carefully a little at a time; oil or fat may be introduced to keep
down the froth; when the ammonia is removed the wash is taken to
the calcining furnace in which the organic matters are burnt; the
alkaline salts having organic acids are converted into carbonates, and
the resulting raw potassa is like ordinary potassa except that it con- .
tains the alkaline carbonates introduced therein.
2nd Process. For distilleries in which raw potassa is not refined the
azotized matters are decomposed in the potassa furnace; they are
especially formed by vegetable albumen which is decomposed by heat into
ammonia and other products. To obtain the ammonia contained in the
gases of combustion a hollow truncated cone is fitted at the upper part of
the chimney, through which a jet of steam is forced; this mixture of gas.
and steam is carried to a refrigerator cooled by water applied externally;
the ammonia dissolved by the steam is condensed and passes into a
receiver; the gases escape; the ammoniacal liquors thus obtained are
purified before being used for dissolving the chloride; for this purpose
they are treated in a distilling or extracting apparatus with lime to dis-
engage ammonia, which is conveyed to water saturated with chlorides,
or ammoniacal liquors may be obtained by showering water with or.
without sulphuric acid down the chimney.
:
Some residua of distilleries contain quantities of yeast, leaven, or
ferment which, after causing the molasses or saccharine matters to
ferment are deposited. There are also residua from distilleries in which
These residua are rich in
grain is worked by acid saccharification.
azotized matter, and when treated with lime in a Mallet's or other
extracting apparatus yield a large quantity of ammonia.

page_text: The residua or wash of distillation or fermentation of beetroot and
other vegetables and grain may be treated with lime to produce
ammonia. Carbonic acid is produced in a pure and cold state to effect
the reaction. For this purpose the fermenting vats are covered either
by a lid provided with a man-hole for cleansing, and a glass for inspect!
ing the interior, or the lid may cover only half the vat, the other half
being closed by a waterproof cover. A central tube carries off the
carbonic acid to a gas holder. The tubes of the various vats sometimes
lead into a single tube through which the carbonic acid passes. into a
refrigerator in which alcoholic vapours carried off by evaporation and
disengagement of the gas are condensed. The vats are open only when
the fermenting process is started and then closed. The fermentation is
started at a very low temperature to avoid sudden heating, and the vat
may be kept cool by a worm or otherwise. The gas holder is charged so
that there shall be a slight suction action in the vats. There may be
two gas holders, one drawing in gas and the other discharging it into
saline and ammoniacal liquors under slight pressure, or there may be one
gas holder with a suction pump.
To produce the reactions the carbonic acid and the ammonia are led
into separate vessels so that they may be at different pressures therein.
Large closed receivers and cylinders are used for the reaction. The
receivers are vats or shallow tanks coated with hydraulic lime, and
having cast-iron covers, or they may be very shallow cast-iron vats.
The cylinders should be tightly closed at top and furnished with an
agitator.
The solution of chloride proceeds as follows:-The solution is con-
ducted in a number of wood vats. The water should be well saturated.
The last batches of gas enter through a vertical shaft or tube filled with'
pieces of coke, on which water is showered to dissolve the salts. The
solution is first admitted through a horizontal cylinder, which brings the
liquid into contact with the gases not yet absorbed, and it thence passes
into a second cylinder in which more of the gas is absorbed. Thence it
flows into a shallow closed vat, in which it is in a thin layer and comes
in intimate contact with the ammonia. An apparatus in some respects
similar to that used in sugar refineries for cold carbonating and for
conveying carbonic acid to the saccharine liquors is employed. The

page_text: ammoniacal gas flows through a central tube into a set of radial pipes
furnished with short vertical tubes disposed like the teeth of a rack.
This apparatus works with reciprocating or vibrating motion in the
liquid, and the ammonia is then brought into multifold contact with it
and becomes rapidly absorbed. The operation is stopped as soon as
sufficient ammonia is dissolved to produce reaction in the proportion of
liquid employed. The ammonia is then set free in another vessel so that
the ammoniacal liquor may be drawn out without stopping the process.
From this vessel the solution passes into a cylinder furnished with an
agitator. In this cylinder it is brought into contact with the carbonic
acid, and it then passes into another vessel into which the carbonic acid
is brought; there will thus be a manifold contact with the carbonic acid
and rapid absorption of the latter until all the ammonia shall be con-
verted into bicarbonate and the reaction effected. When the carbonic
acid ceases to be absorbed the liquor holding the precipitated bicarbonate
in suspension is drawn off and a non-carbonated solution is poured in in
lieu thereof. The gases proceed in inverse ratio to the liquid. The
carbonic acid gas first comes into the vat, where it meets the ammoniacal
solution; the non-utilized portion of the gas passes thence into the
next cylinder, where it finds a fresh quantity of solution, and the portion
non-absorbed flows thence into the vat, into which the ammonia enters,
and there absorbs all that remains of the carbonic acid; the gaseous
ammonia which may have escaped the solution will pass into the next
two cylinders and the portion that remains passes through the coke,
where it will be treated with fresh water or with chloride solution.
All the gases will thus be absorbed, especially as they are unmixed with
inert gases.
To complete the reaction the liquid receiving the carbonic acid should
be at a low temperature. This may be managed by allowing cold water
to flow over the cylinder or by placing the vat which receives the
carbonic acid in a jacket containing chloride of calcium or a non-

page_text: instead of pumping the carbonic gas into a gas holder and forcing it
into the solution it may be forced at a pressure of say three atmospheres
into a tubular water jacketed refrigerator. The liquors issuing from the
carbonic acid apparatus and holding bicarbonate of soda in suspension
are brought into close receivers communicating with each other and
fitted with contrivances for stopping off communication at pleasure.
The liquors are left to settle for a little. The liquor will deposit
bicarbonate in the first receiver and passes into the two other receivers
to finish precipitating..
When the first receiver is filled with the deposited bicarbonate com-
munication is closed between the two others, the liquor is led into the
second receiver to act therein, and so on, the liquor which has imbibed
the bicarbonate is drawn off into a vessel for the purpose, and the
bicarbonate is dried by a turbine or otherwise, and it is cleared from
the residua of ammoniacal salt by water or a bicarbonate solution.
The bicarbonate is prepared for the market by drying it under a
gentle heat on plates fitted to the flues. By raising the temperature
carbonate is produced. Heating by ordinary or superheated steam is
preferred.
The bicarbonate is decomposed in a cylinder, the steam circulating
in a worm in a steam jacket, and an endless feed screw may be used.
The freed carbonic acid can be utilized by conveying it through a
washing or purifying vessel into a gas holder.
The residuary liquors resulting from the draining off or dripping of
the bicarbonate or from the washing contain bicarbonate in solution,
hydrochlorate of ammonia, carbonate of ammonia, and chloride of soda.
If the ammonia can be removed from the wash the ammoniacal salts
have to be collected. For this purpose more chloride of sodium is
dissolved if the proportion of hydrochlorate of ammonia is somewhat
large. The temperature having been lowered hydrochlorate of ammonia
will be precipitated in crystals (artificial refrigeration may be resorted
to). The hydrochlorate crystals are removed and an additional supply
of chloride of sodium is thrown in the liquor which will now contain
chloride, carbonate of ammonia, and bicarbonate of soda. Before sub-
jecting the liquor to the action of carbonic acid it is passed through the

page_text: apparatus wherein ammonia is introduced which it takes up in proper
quantity.
When the process is applied to distillation in which ammonia is only
scantily formed the ammonia has to be regenerated. The liquor is first
boiled to drive off the very volatile carbonate of ammonia which is
collected in the waters of condensation of a distilling or other apparatus.
The liquor is then treated with lime to free the ammonia. When it has
settled and is freed from the carbonate of lime there will remain chloride
of sodium mixed with chloride of calcium in solution, which is evaporated
till the former is precipitated, the mother water is left to cool, and
crystals of hydrated chloride of calcium will be formed.
The reaction apparatus may be connected in pairs and the saturated
solution be in continuous communication with the gases.'
To prevent loss of ammonia closed precipitating vessels, tanks, and
cylinders are used, whence the carbonate of ammonia formed therein
can be readily withdrawn. The carbonate settling tanks and the turbine
case are also closed.
Carbonate of potassa is produced by using sulphate of potassa which
is mixed with carbon and gently calcined in a reverberatory furnace, so
arranged that a reducing flame shall pass over it and produce sulphuret
of potassium. Carbonate of potassa is treated in a chamber with a
stream of carbonic acid proceeding from. fermentation so as to produce
bicarbonate of potassa which is subjected to ebullition or gently calcined
with the sulphuret of potassium, to which it gives up its superfluous
carbonic acid and gives off sulphuretted hydrogen. The necessary
equivalent of bicarbonate of potassa is regenerated with a stream of
carbonic acid for a fresh operation.
When the carbonate of soda is prepared in a distillery by means of
chloride of sodium and ammonia, then instead calcining in order to
decompose it and bring it to a state of carbonate it is treated with
sulphuret of potassium obtained as above described, and carbonates of
potassa and soda will be produced and sulphuretted hydrogen will be
disengaged. The two carbonates are separated by ordinary means.
The sulphuretted hydrogen may be utilized in various ways; for
instance it may be burnt or "still burnt," and the disengaged sulphurous

page_text: acid used to produce sulphuric acid. The sulphurous acid may also be
utilized to make bisulphite of lime for sugar refineries, and sulphite of
soda for bleaching. A half portion of the hydro-sulphuric acid produced
may be burnt, and the sulphurous acid produced is put into contact with
another equivalent portion of unburnt hydro-sulphuric acid in presence
of water so as to obtain sulphur. Or the sulphuretted hydrogen may
be passed through a set of purifiers containing a mixture of hydrated
peroxide of iron and sawdust.
To produce saltpetre nitrate of soda is dissolved and treated with
ammonia and carbonic acid in the same way as sea salt precipitates
bicarbonate of soda; nitrate of ammónia will remain in the liquor which
is treated with lime and heated so as to give off ammonia and nitrate of
lime which remains in solution. The liquor treated by sulphate of
potassa precipitates insoluble sulphate of lime and nitrate of potassa
remains in solution, which when evaporated and cooled deposits salt-
petre. Or in another process which is based on the double decom-
position of nitrate of soda and chloride of potassium under ebullition,
and in which raw potassa is refined and chloride of potassium obtained,
the raw potassa is washed, the liquors are concentrated and left to cool,
and deposit sulphate of potassa. The supernatant liquor is drawn off
into a vessel divided into compartments, in which it is extended in
shallow layers or flanged plates. In this vessel the carbonic gas of
fermentation is absorbed by the carbonates of soda and potassa which
are converted into less soluble bicarbonates and deposited on the plates.
The supernatant liquors are treated with chloride of calcium and con-
verted into. chloride. The liquors drawn off are carried to a boiler in
which the nitrate of soda is dissolved. The chloride of sodium is pre-
cipitated by ebullition and drawn off. When precipitation ceases the
boiling liquor is carried to a crystallizing vessel in which the saltpetre is
deposited by refrigeration.
The chloride of sodium is purified thus:-Pure salt is dissolved in
boiling water to saturation, and then wicker baskets containing the
chloride of sodium to be purified is immersed therein. The liquor
saturated with chloride will only dissolve the saltpetre, and the purified
salt is removed and treated with ammonia and carbonic acid to produce
bicarbonate of soda. The precipitated bicarbonates of potassa and soda

page_text: are reduced to carbonates by heat, or the decomposition may be utilized
for converting the sulphate of potassa into carbonate by the process
above described.
In distilleries or manufactories in which there are nitrate of soda and
molasses or saccharine matter the products will include saltpetre, car-
bonate of potassa, carbonate or bicarbonate of soda, alcohol, hydro-
chlorate of ammonia, and sulphites of soda and lime.