Improvements in the Manufacture of Manures, and New Processes for Obtaining the same.
Year: 1893

page_text: Date of Application, 15th June, 1893
Complete Specification Left. 15th Mar., 1894-Accepted, 21st Apr., 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by C. SEYBOLD, Apothecary, and F. HEEDER,
Manager, both of Wülfrath, near Elberfeld, in the Empire of Germany.]
Improvements in the Manufacture of Manures, and New Processes
for Obtaining the same.
I, HENRY EDWARD NEWTON of The Office for Patents 6, Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
It is known that the phosphoric acid occurring in the phosphates of nature, or
in the phosphates which are obtained as by-products in several branches of
manufacture, or in guano, bones, or the like, has hitherto been rendered fit for use
in agriculture by treating the said materials with mineral acids. The compound
having the formula: Ca,(PO4)2 was converted by such a treatment, either into
superphosphate, which is represented by the formula (PO4)2H.Ca, or into the so
called "precipitate" of the following composition, viz. PO,HCa.
My foreign correspondents have now found, that the aforesaid process of con-
verting materials containing phosphoric acid into soluble products fit for
agricultural purposes, can be effected in a manner far more rational and simple,
viz. by employing carbonic acid in place of the mineral acids used up to the
present time.
According to the researches of my foreign correspondents, it is also possible to
employ those phosphates, which, owing to the great amount of calcium carbonate,
or calcium oxide they contain, could not be rendered soluble by means of the
former methods, and to convert them into soluble products containing the phosphoric
acid capable of being readily assimilated by plants.
This new method, in general, consists in heating the phosphates, or substances
containing phosphates, at a temperature varying from about 50 to 120 degrees centi-
grade, in chambers, whilst a current of carbonic acid is allowed to pass continually
over the heated materials. The phosphates are treated in a comminuted state,
moistened with water, and spread in thin layers. It is likewise advantageous to
introduce steam into the above chambers. The carbonic acid necessary for the
said purposes, can be obtained from the gases arising from the furnace used for
heating the aforesaid chambers.
The reaction taking place during this operation can be illustrated by the
following equation, viz. :-
Ca,(PO) + CO2 + H₂O = 2 (PO.CaH) + CaCO,.
The so-called "precipitate" is formed in this manner. It is to be noted, that on
continuing this process for a longer period, the calcium contained in the first
produced "precipitate" is partly replaced by hydrogen, the so-called "
phosphate," having the composition (PO4),Caй, being formed in this way, which
may be represented by the following equation :-
DOCH
ՈՐՈ
super-
2 (FO,Caff) + CO2 + H2O = (PO.),CH, C₂CO..
My foreign correspondents have further found, that by means of the process
herein before described, such phosphates as contain calcium and alkali-metals, like-
wise can be prepared, riz., by adding to the wet phosphates or the like, a sufficient
quantity of potassium carbonate or sodium carbonate, or the like, or mixtures of
such carbonates. By varying the process in this manner, double salts
are

page_text: obtained; for instance, in treating the phosphate (PO4)Cas together with
potassium carbonate in the presence of water and carbonic acid, the process
proceeds in the manner represented by the following equations :-
Of course, the potassium carbonate employed in the aforesaid processes illustrated
by the above equations a and b, or in similar processes, can be replaced by mixed.
carbonates, such as, for instance, alkali-magnesium carbonate, alkali calcium,
carbonate, or the like, these mixed carbonates effecting the same result, especially
by their amount of alkali.
In order to obtain directly a manure containing nitrogen, alkali carbonates with
the addition of quicklime, or only alkali hydroxides, are employed for dissolving
organic materials containing nitrogen (such as hair, hoof, horn, leather, or wool
refuse, offal, or the like), taking the necessary steps that the nitrogen escaping in
the form of ammonia may be recovered, for instance, by introducing the latter
into acids. The finely powdered phosphates are added to the thus resulting solution,
and the mixture is then treated with carbonic acid in the chambers (drying stoves),
as above mentioned. The alkali hydroxides and quick-lime are, by the carbonic
acid of the furnace, converted into, respectively, alkali carbonate or calcium
carbonate, whilst the further process of rendering these salts soluble proceeds in
the manner above referred to.
In carrying out the process in the last-named manner, the conversion of the
phosphates, viz., the production of phosphoric acid soluble in the soil, or in water,
proceeds in a shorter time, and with greater readiness, as the particles of the
phosphates are in a more isolated state, and are affected more euergetically by the
carbonic acid and alkalies.
In order to illustrate more in detail this new process, the following example is
Of course, the potassium carbonate employed in the aforesaid processes illustrated
by the above equations a and b, or in similar processes, can be replaced by mixed
carbonates, such as, for instance, alkali-magnesium carbonate, alkali calcium,
carbonate, or the like, these mixed carbonates effecting the same result, especially
by their amount of alkali.
In order to obtain directly a manure containing nitrogen, alkali carbonates with
the addition of quicklime, or only alkali hydroxides, are employed for dissolving
organic materials containing nitrogen (such as hair, hoof, horn, leather, or wool
refuse, offal, or the like), taking the necessary steps that the nitrogen escaping in
the form of ammonia may be recovered, for instance, by introducing the latter
into acids. The finely powdered phosphates are added to the thus resulting solution,
and the mixture is then treated with carbonic acid in the chambers (drying stoves),
as above mentioned. The alkali hydroxides and quick-lime are, by the carbonic
acid of the furnace, converted into, respectively, alkali carbonate or calcium
carbonate, whilst the further process of rendering these salts soluble proceeds in
the manner above referred to.
In carrying out the process in the last-named manner, the conversion of the
phosphates, viz., the production of phosphoric acid soluble in the soil, or in water,
proceeds in a shorter time, and with greater readiness, as the particles of the
phosphates are in a more isolated state, and are affected more euergetically by the
carbonic acid and alkalies.
In order to illustrate more in detail this new process, the following example is
FIRST EXAMPLE.
TREATMENT OF BONE DUST FOR RENDERING IT SOLUBLE.
Bone dust is impregnated with about half its weight of water, and is then spread
on plates or dishes, which are introduced into a channel drying stove. The stove
is heated by a furnace to from about 60 to 80 degrees centigrade, and the gases
from the furnace are allowed to pass directly over the heated material. The
carbonic acid contained in these gases and the water, are sufficient to render the
phosphates employed soluble.
Of course, carbonic acid produced in any other manner may likewise be employed,
TREATMENT OF BONE DUST FOR RENDERING IT SOLUBLE.
Bone dust is impregnated with about half its weight of water, and is then spread
on plates or dishes, which are introduced into a channel drying stove.
The stove
is heated by a furnace to from about 60 to 80 degrees centigrade, and the gases
from the furnace are allowed to pass directly over the heated material. The
carbonic acid contained in these gases and the water, are sufficient to render the
phosphates employed soluble.
Of course, carbonic acid produced in any other manner may likewise be employed,
with the same result.
If, during the heating, the phosphates become too dry, steam is introduced into
the stove.
After from about 12 to 24 hours (the time depending on the kind of material
used, on the temperature, and the quantity of carbonic acid and water) the
formation of " precipitate is effected, and the process can be interrupted, or

page_text: continued further. In the latter case, steam is introduced into the gases from the
furnace. The production of "superphosphates" is then completed after from
12 to 24 hours.
On employing hydroxides or carbonates of sodium or potassium, or mixtures
thereof, or mixed carbonates, such as alkali magnesium carbonate, or alkali calcium
carbonate, the process is effected in the same manner, but the time necessary for
this process is somewhat shorter.
For
The quantity of the added alkalies of course may vary within wide limits.
instance, a mixed phosphate chiefly containing the salt (PO),Ca,HK, is
obtained by mixing bone dust (20 per cent.) with about 5 per cent. of its weight of
potassium carbonate, whilst in the employment of 10 per cent. of its weight of
potassium carbonate the phosphate having the formula: (PO₁),CH,K₂ is
formed.
The temperature indicated in the above example can be increased or diminished.
The process in general proceeds slowly at temperatures varying from 30 to
60 degrees. At elevated temperatures, say, from 80 to 120 degrees," precipitate" is
chiefly produced. The precipitate is then converted into "superphosphate," by a
suitable treatment, most practically at low temperatures.
In order to produce a substance which contains much nitrogen, and has, for
instance, a composition similar to that of guano, the method described in the
following second example can be used
PRODUCTION OF A GUANO-LIKE MATERIAL CONTAINING A HIGH AMOUNT OF
NITROGEN.
500 parts of organic waste substances containing nitrogen (such as hair, hoof,
horn shavings, leather, or wool refuse, or the like) are dissolved by heating with a
solution, in water, of 50 parts of quicklime and 50 parts of potassium carbonate.
From 500 to 600 paits of bone-dust are added to the resulting solution, and the
further treatment is effected in the manner hereinbefore described, viz., the
mixture thus obtained is heated (after placing the same in thin layers) in channel
drying stoves, whilst carbonic acid is allowed to pass over the heated material, and
if it be necessary, steam is introduced into the drying rooms, or into the gases from
the furnace.
Naturally, the proportions mentioned in the above examples, the temperatures
indicated therein, and the duration of the process, can be varied within wide limits,
without a materially different result being caused. The nature of the invention is
not altered by such or similar modifications, as it relates to the production of
phosphoric materials soluble in the soil and in water, by treating phosphates, or
substances containing phosphates, with carbonic acid and water, and also to the
manufacture of manure containing the three most important nutritious matters
for plants, viz., nitrogen, phosphoric acid, and potassium, by carrying out the.
aforesaid process in presence of materials containing nitrogen, and of alkalies.
The technical value of these new processes especially consists, also, in that (by
means of the latter) products result which do not contain sulphuric acid, and which
therefore cannot be injurious to the plants, whilst, on the other hand, a material
containing sulphuric acul results on the employment of the method hitherto in use
for treating phosphates or the like, vi, for rendering them soluble by a treatment
with sulphuric acid.
The method herein before explained likewise is superior to the described in the
German Patent No. 65359. By means of the latter, calcium phosphates are
prepared which contain a higher amount of phosphoric acid than the original
inaterials, whilst the phosphates, in chemical regard, remain unaltered, that is to
say, not fit for being absorbed by plants, and must further be treated in order to
render the same soluble. According to the new process discovered by my foreign

page_text: correspondents, the calcium phosphates are chemically altered, the neutral calcium
phosphates being converted into mono- or di-acid calcium phosphates. The mixed
salts obtainable by an addition of alkalies, have not been utilized commercially up
to the present time, notwithstanding that they possess the great advantage that
(being more saturated compounds) they will change when in the soil into insoluble
salts, with the same ease as the aforesaid mono and di-acid phosphates.
Dated this 15th day of June 1893.
NEWTON & SON,
Agents for the Applicant.
=
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Manures, and New Processes
for Obtaining the same.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Breams Buildings,
Chancery Lane in the County of London, Patent Agent, 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:—
It is known, that the phosphoric acid occurring in the phosphates of nature or in
the phosphates which are obtained as by-products in several branches of
manufacture, or in guano, bones, or the like, has hitherto been rendered fit for use
in agriculture by treating the said materials with mineral acids. The compound
having the formula: Ca₂(PO4), was converted by such a treatment either into
superphosphate, which is represented by the formula (PO),H,Ca, or into the so-
called "precipitate" of the following composition, viz.:-PO,HCa.
My foreign correspondents have now found, that the aforesaid process of
converting materials containing phosphoric acid into soluble products fit for
agricultural purposes, can be effected in a manner far more rational and simple,
riz., by employing carbonic acid in place of the mineral acids used up to the present
time.
According to the researches of my foreign correspondents, it is also possible to
employ those phosphates which, owing to the great amount of calcium carbonate or
calcium oxide they contain, could not be rendered soluble by means of the former
methods, and to convert them into soluble products containing the phosphoric acid
capable of being readily assimilated by plants.
This new method, in general, consists in heating the phosphates, or substances
containing phosphates, at a temperature varying from about 50 to 120 degrees
centigrade, in chambers, whilst a current of carbonic acid is allowed to pass
continually over the heated materials. The phosphates are treated in a comminuted
-tate, moistened with water, and spread in thin layers. It is likewise advantageous
to introduce steam into the above chambers. The carbonic acid necessary for the
aid purposes can be obtained from the gases arising from the furnace used for
heating the aforesaid chambers.
The reaction taking place during this operation can be illustrated by the
following equation, viz. :-
2 (PO CaH) + CO2 + H2O = (PO4)2 CaH, + CaCO

page_text: Of course, carbonic acid produced in any other manner may likewise be
employed with the same result. If, during the heating, the phosphates become too
dry, steam is introduced into the stove.
After from about 12 to 24 hours-(the time depends on the kind of the material
used, on the temperature, and the quantity of carbonic acid and water), the
formation of "precipitate" is effected, and the process can be interrupted or
continued further. In the latter case, steam is introduced into the gases from the
furnace. The production of "superphosphates" is then completed after from 12 to
24 hours. On employing hydroxides, or carbonates of sodium or potassium, or
mixtures thereof, or mixed carbonates, such as alkali-magnesium carbonate, or
alkali-calcium carbonate, the process is effected in the same manner, but the time
necessary for this process is somewhat shorter.
The quantity of the added alkalies, of course may vary within wide limits.
For instance, a mixed phosphate, chiefly containing the salt (PO), Ca, H.K, is
obtained by mixing bone dust (20 per cent.) with about 5 per cent. of its weight of
potassium carbonate, whilst in the employment of 10 per cent. of its weight of
potassium carbonate the phosphate having the formula :-(PO₁),CaH,K, is
formed.
"
The temperature indicated in the above example can be increased or diminished.
The process in general proceeds slowly at temperatures varying from 30 to
60 degrees. At elevated temperatures, say from 80 to 120 degrees, "precipitate
is chiefly produced. The precipitate is then converted into "superphosphate" by
a suitable treatment, most practically at low temperatures.
In order to produce a substance which contains much nitrogen, and has, for
instance, a composition similar to that of guano, the method described in the
following second example can be used.
PRODUCTION OF GUANO-LIKE
MATERIAL CONTAINING A HIGH AMOUNT OF
NITROGEN.
500 parts of organic waste substances containing nitrogen (such as hair, hoof,
horn-shavings, leather or wool refuse, or the like) are dissolved by heating with a
solution in water of 50 parts of quick-lime and 50 parts of potassium carbonate.
From 500 to 600 parts of bone-dust are added to the resulting solution, and the
further treatment is effected in the manner herein before described, viz., the mixture
thus obtained is heated (after placing the same in thin layers) in channel drying-
stoves, whilst carbonic acid is allowed to pass over the heated material, and, if it
be necessary, steam is introduced into the drying-rooms, or into the gases froin the
furnace.
Naturally, the proportions mentioned in the above examples, the temperatures
indicated therein, and the duration of the process, can be varied within wide limits,
without a materially different result being caused. The nature of the invention is
not altered by such or similar modifications, as it relates to the production of
phosphoric materials, soluble in the soil and in water, by treating phosphates, or
Substances containing phosphates, with carbonic acid and water, and also to the
manufacture of manure containing the three most important nutritious matters for
plants, viz., nitrogen, phosphoric acid, and potassium, by carrying out the aforesaid
process in presence of materials containing nitrogen, and of alkalies.
The technical value of these new processes especially consists, also, in that
products result, which do not contain sulphuric acid, and which therefore cannot be
injurious to the plants, whilst, on the other hand, a material containing sulphuric
acid does result on the employment of the method hitherto in use for treating
phosphates or the like, viz., for rendering them soluble by a treatment with
sulphuric acid.

page_text: The method herein before explained likewise is superior to that described in the-
German Patent No. 65,359.
By means of the latter, calcium phosphates are prepared, which contain a
higher amount of phosphoric acid than the original materials, whilst the phosphates,.
in chemical regard, remain unaltered, that is to say, not fit for being absorbed by
plants, and must further be treated, in order to render the same soluble.
According to the new process discovered by my foreign correspondents, the
calcium phosphates are chemically altered, the neutral calcium phosphates being-
converted into mono- or di-acid calcium phosphates.
The mixed salts obtainable by an addition of alkalies have not been utilized
commercially up to the present time, notwithstanding that they possess the great
advantage that (being more saturated compounds) they will not change, when in
the soil, into insoluble salts with the same ease as the aforesaid mono- and di-acid
phosphates.
Having now particularly described and ascertained the nature of this inven--
tion and in what manner the same is to be performed, as communicated to me from
abroad, I declare that what I claim is :-
:-
1. The improved process for converting insoluble phosphates into soluble.
phosphates, or phosphates containing the phosphoric acid capable of being readily
assimilated by plants, which process chiefly consists in treating phosphates or
substances containing phosphates, with carbonic acid.
.
2. The production of materials capable of being used for the manufacture of
manure or the like, which process consists in allowing carbonic acid or gaseous
mixtures containing carbonic acid, and, if desirable, steam to pass over comminuted
and moistened natural or artificial phosphates, or substances containing phosphates,
in or without the presence of alkaline hydroxides, or alkaline carbonates, or mixed
alkali calcium or alkali magnesium carbonate, whilst the said mass is heated at from.
about 50 to 120 degrees centigrade.
3. The process for producing artificial manure, which process consists in
moistening with liquids resulting from a treatment of animal offal with alkalies,.
comminuted natural or artificial phosphates, or mixtures prepared from phosphates
and alkaline hydroxides, alkaline carbonates, or alkali-calcium- or alkali-
magnesium-carbonate, and subsequently heating the resulting mass at from about
50 to 120 degrees centigrade, whilst a current of carbonic acid, or a gaseous
mixture containing carbon dioxide, is allowed to pass over the heated mass.
4. As products of manufacture, the artificial manure, and the materials therefor,.
produced by the process herein before defined.
Dated this 15th day of March 1804
NEWTON & SON,
Agents for the Applicant..