An Improved Process of Fixing Atmospheric Nitrogen, and of Producing Bicarbonate and Formiate of Ammonium, Formic Acid, and other Formiates.
Year: 1893

page_text: Date of Application, 27th June, 1893-Accepted, 2nd Sept., 1893
COMPLETE SPECIFICATION.
An Improved Process of Fixing Atmospheric Nitrogen, and of
Producing Bicarbonate and Formiate of Ammonium, Formic Acid,
and other Formiates.
I PIERRE ROGATIEN Vicomte de Lambilly of 28 Rue de Strasbourg Nantes
in the Republic of France, 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 :-
This process of fixing atmospheric nitrogen rests upon the following facts which
experiment will verify.
1. If a mixture of nitrogen and hydrogen is passed through a tube charged with
porous bodies capable of absorbing gas, such as pumice stone, charcoal, bone black
or lead sponge, platinated pumice stone or carbon sponge, spongy platinum or
platinum black, etc. etc. in a cold state but preferably under the influence of a slight
rise of temperature, a certain quantity of ainmonia gas is produced.
The elements of this gas N + H3 in combining, release about 12 units of heat
and for this reason it requires but a slight influence to bring their affinity into
action.
II. If instead of passing these gases through in a dry state, they are previously
humidified by letting them pass through water, ammonia is obtained but in a larger
proportion. As the combination of ammonia gas with water discharges nearly
9 units of heat, this more abundant production is easily understood.
III. If further, we add to our mixture of nitrogen and hydrogen another gas
adapted to combine with ammonia to form a salt and releasing further units of heat,
we obtain a still more considerable fixing of nitrogen.
Thus a mixture of nitrogen, hydrogen and carbonic acid in presence of water
would give the two following reactions
2CO3 + 2N+ 2H* + H2O = CO*H (NH*) + CO*H(NH)
CO% + N + H* + HO = CO*H(NH*),
CO+N+H3 + HO = COH(NH*).
In this case only formiate of ammonium is produced. The production of these two
salts takes place and can only take place at a temperature but slightly raised,
since the bicarbonate decomposes at about 60° C. and the formiate at about 150° C.
To obtain their respective production it is necessary to operate at a temperature
lower than that of their decomposition. However if the operation is done at
higher temperatures, carbonate of ammonium CO' (NH3)2 or formiamide CHONH
can be produced which, if received in the water is transformed subsequently on
hydration, the first into bicarbonate and the second into formiate of ammonium.
Upon these principles I have founded the following process of producing
ammonia, which is performed in three operations.

page_text: formiate of calcium may serve for production of formic acid and consequently any
other desired formiate.
COROLLARY OF THE PROCESS.
As set forth at the outset a mixture of humidified nitrogen and hydrogen
produces ammonia when passed over porous materials at a slightly raised
temperature. Ammonia may therefore be manufactured by passing a mixture of
the component gases in proper theoretical proportions through an apparatus
substantially as described under the heading of "Combination of the gases."
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed I declare that what I
claim is
1. The process of fixing atmospheric nitrogen which consists in passing over
porous bodies of absorbent nature, after previous humidification, either a mixture
of nitrogen and hydrogen to produce ammonia, or the same mixture of gases with
the addition of carbonic acid gas to produce the bicarbonate and formiate of
ammonium, or the same mixture with addition of carbon monoxide in place of
carbonic acid gas for the production of formiate of ammonium.
2. The method of carrying this invention into effect consisting in causing a
mechanical circulation of the gases from a gas holder through one or more
combining apparatus back to the gas holder until the combination is complete.
3. The production of formic acid or any other formiate from formiate of
ammonium by distillation of a solution of the latter with lime to produce formiate
of calcium and subsequent conversion of the latter into formic acid or any other
formiate.
Dated this 07th ICT 1000
R. HADDAN,
Herbert Haddan & Co.,
18, Buckingham Street, Strand, London, Agent for Applicant.