IMPROVEMENTS IN GENERATING AND FIXING AMMONIA
Year: 1853

page_text: LETTERS PATENT to Charles Frederick Spieker, of New York,
in the United States of America, Professor of Chemistry, for the
PROVISIONAL SPECIFICATION left by the said Charles Frederick
Spieker at the Office of the Commissioners of Patents, with his
Petition, on the 25th July 1853.
I, CHARLES FREDERICK SPIEKER, do hereby declare the nature of
the said Invention for "IMPROVEMENTS IN GENERATING AND FIXING
AMMONIA" to be as follows:-
It is well known to chemists that ammonia consists of a combination
of nitrogen and hydrogen, and that ammonia is usually procured by
the decomposition of animal matters which are known to contain these
ingredients. The present Invention consists in obtaining animonia by
the decomposition of various other matters known to contain the
elements of which ammonia is composed, viz., hydrogen and nitrogen;

page_text: water or substances containing water is the substance I propose to employ
for obtaining the hydrogen, the nitrogen or other element of ammonia
being obtained from the atmosphere, which it is well known consists of
oxygen and nitrogen; the decomposition of the water will therefore free
the hydrogen, and the decomposition of the air will set free the nitrogen.
These decompositions are caused by some chemical agents which
will combine with the oxygen contained in the water and air, leaving
the nitrogen of the air free to combine with the dydrogen of the water,
and thereby form ammonia, which being volatile is afterwards fixed by
some other and well-known chemical agents. Supposing the ammonia
when obtained is to be employed in the manufacture of manure, silicate
of alumina or peat charcoal, either alone or in combination with other
substances which are fertilizing agents, are the substances which I
prefer to employ for absorbing or condensing the ammonia. For fixing
the ammonia when obtained I employ either the well-known acids, or
salts containing such acids, and which will readily decompose in the
presence of ammonia. In some cases I employ chalk, shells, lime, or
fossil remains in combination with the above process for obtaining am-
monia, as I have found by experiment that as these substances contain
animal remains they will greatly assist in producing the ammonia and
increasing the quantity, which circumstance may, perhaps, arise from
the fact of these substances containing remains of animal matters
which, as before mentioned, are composed to a great extent of some of
SPECIFICATION in pursuance of the conditions of the Letters Patent, 2
filed by the said Charles Frederick Spieker in the Great Seal
Patent Office, on the 25th January 1854.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I,
CHARLES FREDERICK SPIEKER, of New York, in the United States of
America, Professor of Chemistry, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Twenty-fifth day of July, in the year
of our Lord One thousand eight hundred and fifty-three, in the seven-
3

page_text: teenth year of Her reign, did, for Herself, Her heirs and successors,
give and grant unto me, the said Charles Frederick Spieker, Her
special license that I, the said Charles Frederick Spieker, my ex-
ecutors, administrators, and assigns, or such others as I, the said
Charles Frederick Spieker, my executors, administrators, and assigns,
should at any time agree with, and no others, from time to time
and at all times thercafter 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 GENERATING AND
FIXING AMMONIA," upon the condition (amongst others) that I, the
said Charles Frederick Spicker, by an instrument in writing under
my hand and seal, 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 Charles Frederick Spieker, do
hereby declare the nature of my said Invention, and in what manner
the same is to be performed, to be particularly described and ascer-
tained in and by the following statement (that is to say):
It is well known to chemists that ammonia consists of a combination
of nitrogen and hydrogen, and that ammonia is usually procured by the
decomposition of animal matters which are known to contain these.
ingredients. The present Invention consists in obtaining ammonia by
the decomposition of various other matters known to coutain the
elements of which animonia is composed, (videlicit,) hydrogen and
nitrogen. Water or any substance containing water is the substance
I propose to employ for obtaining the hydrogen, the nitrogen or other
element of ammonia being obtained from the atmosphere, which it is
well known consists of oxygen and nitrogen; the decomposition of
water will therefore free the hydrogen, and the air will supply the
nitrogen required. The decomposition of the water is caused by some
chemical agents which will combine with the oxygen contained in the
water, leaving the hydrogen of the water free to combine with the

page_text: nitrogen of the air, and thereby form ammonia, which being volatile is
condensed, and afterwards fixed by some other and well-known chemical
agents. Supposing the aumonia when obtained is to be employed in
the manufacture of manure, silicates of alumina or peat charcoal,
either alone or in combination with other substances which are fertilizing
agents, are the substances which I prefer to employ for absorbing or
condensing the ammonia. For fixing the ammonia when obtained
I employ either of the well-known acids, or salts containing such
acids, and which will readily decompose in the presence of ammonia.
In some cases I employ chalk, shells, lime, or fossil remains in com-
bination with the above process for obtaining ammonia, as I have found
by experiments that as these substances contain animal remains they
will greatly assist in producing the ammonia and increasing the
quantity thereof, which circumstance may, perhaps, arise from the fact
of these substances containing remains of animal matters which, as
before mentioned, are composed to a great extent of some of the ele-
ments which form ammonia.
In order to generate ammonia according to my improved plan I
effect the decomposition of the water, either by means of metallic iron,
or the protoxide of manganese or of iron. Cast iron as well as
wrought iron answers equally well for this purpose, but it is very
advisable to use it in thin or small fragments, so as to offer as large a
surface as possible to the air and water for oxidation. Scrap iron,
broken vessels of cast iron, or other articles made of iron will therefore
auswer the purpose. Ammonia being highly volatile must, when ob-
tained, be absorbed and condensed, for which purpose I find that for
agricultural purposes gypsum or sulphate of lime, and also the different
kinds of aluminous earths, for instance, the silicates of alumina, are the
substances to be preferred for condensing the ammonia, particularly the
aluminous earths, as they possess this quality in a high degree when
used in a finely powdered state, cither alone by themselves, or mixed
with finely ground charcoal or peat charcoal.
The silicates of alumina which I prefer to use are those generally
known as potter's or plastic clay, clay-slate, green sand, and other
matters, which contain a considerable quantity of alumina. These

page_text: matters will condense the ammonia with great facility when they are
in a finely powdered state, after having been mixed with water or
organic matter, and subjected to evaporation. Ammonia, either when
it has been generated from the direct combination of its elements as
above mentioned, or when it has been produced by the decomposition
of organic matter, may be condensed by these silicates of alumina.
The ammonia must be condensed inmediately it is formed; that is
to say, it must come in its nascent state in contact with both the con-
densing and fixing materials. The iron scraps must be well mixed
with the finely ground aluminous carth, and spread out in thin layers
on a place where a free circulation of air can take place, as the contact
of the air is of material consequence to the success of the process. The
proportion of iron to the mass of aluminous earth is of no particular
consequence, the more iron is used the better for a quick generation of
ammonia; still there is a limit, for the iron ought to be everywhere
equally covered with a thin layer of aluminous earth. The easiest way
to prepare the mixture of the substances is to lay down a layer of the
aluminous earth, previously mixed with water and some suitable acid
such as those hereafter named, to the consistence of a thin paste, lay
the iron scraps in it, and cover them up with another thin layer of
aluminous earth in a state of paste.
The mass is then left to be evaporated gently, either by the heat of
the atmosphere in summer or by very gentle artificial heat. Particular
care should be taken that the evaporation goes on slowly, and that
if the above process be carried on in the open air the rays of the sull
do not fall directly upon the mass under operation, as too great solar
heat, at least such as that of the summer sun in America, will act very
injuriously upon the success of the process, as the heat will be found to
evaporate the ammonia before it can be absorbed and fixed. The
process may be carried on in the shade by providing a simple roof of
boards open on all sides, and care should be taken to prevent rain from
falling on the mass and washing out the salts of ammonia. After the
evaporation has reduced the mass of iron, aluminous carth, water, and
acid, or other materials to dryness they should be moistened again with
water. This may be repeated a second time if there should be un-

page_text: decomposed salt of iron yet in the mixture. The mass should be again
turned over so as to expose the materials freely to contact with the air,
in order to secure the entire decomposition of the acid. After this the
operator can easily detect, by applying a test in the ordinary manner or
by the smell, the presence of a considerable quantity of ammonia in the
mixture. The easist way of testing for the ammonia is by subjecting
a handful of the aluminous earth, freed from the iron scraps, to the
action of a strong solution of caustic potash or freshly prepared hydrate
of lime, which must be well mixed with the aluminous earth, after which
a glass rod, moistened with muriatic acid diluted with a little water,
must be held over the aluminous carth, when the presence of ammonia
will be indicated by the fumes of sal-ammoniac, caused by the-gaseous
ammonia coming in contact with the muriatic acid.
scrap
If it is desirable to make the layer of aluminous earth richer in the
salt of ammonia, it is again moistened with diluted acid, and the same
process of evaporation repeated for as many times as it is judged
desirable, so that it should contain an increased proportion of ammonia.
Another layer of earth and iron is then put upon the first, and the
layers increased to any desired thickness. The pieces of
iron can
be used repeatedly till they are entirely converted into the peroxide of
iron, it being only necessary to separate them by sifting, or in auy
convenient manner, from the aluminous earth which contains the salts
of ammonia when the aluminous earth is deemed rich enough in
ammonia. The aluminous earth and iron may be laid for the evapo-
rating process upon plates of iron or flat flag stones, or upon a layer of
plaster of Paris placed on boards, or even boards alone, although the
latter will, of course, in the beginning, absorb a good deal of the salts of
ammonia. As regards the choice of acid to be used in the mixture
with the iron and aluminous earth, this is to be decided by the price of
the different acids, and their efficacy. I have produced the salt of
ammonia by this process, both by organic acids, as, for instance, acetic
acid (vinegar), as well as by inorganic acids, such as muriatic acid or
sulphuric acid; for practical purposes I would, however, prefer sulphuric
acid on account of its cheapness and its great affinity for ammonia. If
the locality is favorable, humic acid, is contained in the extract made

page_text: froin turf or inuick, may be also employed, either alone by itself, or
together with-sulphuric acid, or if the process is carried on near the
sea shore, the use of sea water for the oxidation of the iron in combina-
tion with an acid will be found of great advantage. If strong acids like
muriatic or sulphuric are used, they must be previously highly diluted
Of sulphuric acid of commercial strength I use generally
with water.
about two to three ounces to a gallon of water.
In the place of the metallic iron for generating ammonia, the
sulphate of iron, or the protoxide of iron; or the protoxide of
manganese may be used with success. Any of the proto-salts of iron
will produce this effect, but for practical purposes I prefer either
the proto-chlorate or the proto-sulphate of iron, generally the latter."
Of the green copperas of commerce I dissolve about one pound of
copperas in
a gallon of water, and this solution I mix with the
aluminous carth to about the consistence of a paste, and spread it out
in thin layers, and treat it in the manner as described above when
metallic iron is used; at the same time I cause a free acid to be
present. Sulphuric or muriatic acid T find the most adapted for
practical purposes, particularly the latter. Instead of sulphuric acid I
propose to use humic acid in combination with copperas; the solution
of copperas may be used by itself, or in combination with hydrate or
carbonate of lime, for the purpose of decomposing it faster. I mix with
it either slacked lime, or better finely ground carbonate of lime, two
pounds of the latter to one gallon of the above-described copperas
solution, with which the aluminous earth is mixed. Chalk, finely
ground, answers very well for supplying the carbonate of lime.
During the process of the repetition of evaporation free acids in diluted
form, as mentioned above, are added to the mixture of aluminous earth,
copperas solution, and lime, and here the addition of humic acid has
O proved very effective, and has been found to produce very good and
important results.
In the choice of the lime itself I have discovered that if finely ground
coral or coralline oyster shells, or shells of a similar kind, either in
their fresh state, or even when they are found as fossil shells in mineral
5 deposits, are used, the quantity of ammonia produced is very much

page_text: increased, which effect is likewise produced by the fossiliferous limeston
of the different geological formations, which are sometimes filled with
animal or other remains or shells in a fossil state.
The explanation of this consider to exist in assuming that by the
action of the proto-sulphate of iron upon the shells or fossiliferous lime-
stone, the particles of the latter are so fully decomposed and separated
that any organic remains which they yet contain are set free, and may
serve to increase the amount of ammonia being produced. I would
here observe that ammonia produced by any of the well known methods,
either from organic remains or otherwise, may be absorbed, condensed,
and fixed in the manner above described by means of aluminous carths
and salts or acids.
The salts of ammonia made thus by the above-described processes
may now be washed out from the aluminous earth in which they are
contained, or if they are used for agricultural purposes (for which this
process is intended) the aluminous earth itself is to be used as a
fertilizer.
I claim, First, the generation or manufacture of ammonia from its
elements obtained from the air and the decomposition of water. I also
claim the use of highly oxidizable metals or salts for this purpose, as
above explained.
Second. I claim the use and application of gypsum or aluminous
earths, as above set forth, for condensing and absorbing ammonia, and
also the use of acids or salts in combination with the aluminous carths
for fixing the ammonia.
Third. I claim the use and application for the purposes herein set
forth of shells, corals, fossiliferous limestone, and fossil animal remains.
In witness whereof, I, the said Charles Frederick Spieker, have
hereunto set my hand and scal, this Second day of January, in
the year of our Lord One thousand eight hundred and fifty-four..
CHARLES FREDERICK SPIEKER.
(L.S.)