IMPROVEMENTS IN TREATING NATURAL PHOSPHATES OF LIME FOR AGRICULTURAL PURPOSES
Year: 1863

page_text: LETTERS PATENT to Guillaume Ville, of Paris, France, Professor at the
Museum of Natural History, for the Invention of "IMPROVEMENTS IN
TREATING NATURAL PHOSPHATES OF LIME FOR AGRICULTURAL PURPOSES."
Sealed the 29th April 1864, and dated the 4th November 1863.
PROVISIONAL SPECIFICATION left by the said Guillaume Ville at the
Office of the Commissioners of Patents, with his Petition, on the 4th
November 1863.
I, GUILLAUME VILLE, of Paris, France, Professor at the Museum of Natural
History, do hereby declare the nature of the said Invention for "IMPROVE-
MENTS IN TREATING NATURAL PHOSPHATES OF LIME FOR AGRICULTURAL PURPOSES,"
to be as follows:-
These improvements consist in disaggregating by calcination, or what is
called the dry process, with the admixture of suitable salts, natural phosphates
of lime, such as apatites, phosphorolites (nodules), caprolites or bones, in order
better to appropriate the said phosphates to agricultural purposes, and at the
same time form useful manuring compounds. For this purpose the phos
phates to be treated are reduced to the pulverized state and intimately mixed

page_text: therewith either sulphate of magnesia, chloride of magnesium, double sul-
phate of potash and magnesia, or a combination of two or three of the said
salts; which latter may be employed in the more or less pure state in which
they are obtained from the mother waters in the manufacture of sea salt, and
are known in France by the name of summer salts (sels d'été). The mixture is
then calcined in a retort, reverberatory furnace, or other suitable means, so as
to cause the various parts of the mixture to act on each other, procure a
suitable disaggregation of the phosphate, and form compounds suitable for
manuring purposes. For certain varieties of phosphates, such as phospho-
rolites (nodules) containing much clay or silica, the addition of an alkaline
sulphate and calcination will suffice; but others, such as apatites, for instance,
require the adjunction of a salt of magnesia before calcination.
Instead of the above-mentioned salts others, such as potassa or its salts, soda
or its salts, barytes or its salts, magnesia or its salts, or some salts of iron, may
be made use of.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Guillaume Ville in the Great Seal Patent Office on the 4th
May 1864.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, GUILLAUME
VILLE, of Paris, France, Professor at the Museum of Natural History, send
greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Fourth day of November, 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 Guillaume Ville, Her special licence that I, the said Guillaume
Ville, my executors, administrators, and assigns, or such others as I, the
said Guillaume Ville, my executors, administrators, and assigns, should at any
time agree with, and no others, from time to time and at all times there-
after 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
TREATING NATURAL PHOSPHATES OF LIME FOR AGRICULTURAL PURPOSES," upon the
condition (amongst others) that I, the said Guillaume Ville, 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

page_text: 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 Guillaume Ville, do hereby declare the
nature of said Invention, and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following
my
statement:-
Scientific and experimental researches of the last years having sufficiently
proved the beneficial effect of phosphates for agricultural purposes, and par-
ticularly for forming part of artificial manuring compounds, various modes
have been proposed for reducing the principal natural phosphates of lime,
such as apatites, phosphorolites (nodules), coprolites, or bones to a state fit for
being readily assimilated by plants. The modes hitherto made use of for
that purpose consisted principally in treating the said phosphates either with
sulphuric acid, and producing thereby what is known in the trade as super-
phosphate of lime, or with hydrochloric acid.
My Invention consists in disintegrating or suitably altering the chemical
constitution of phosphates of lime by calcining them, or what is called the dry
process, with the addition of a suitable salt or salts, and obtaining thereby not
only the required desintegration or chemical alteration of the said phosphates,
but at the same time form compounds of highly beneficial effects for agricul-
tural purposes.
For this purpose I submit the natural phosphates of lime,
such as apatites, phosphorolites (nodules), coprolites, or bones to a suitable
calcination in a reverberatory or other suitable furnace, in crucibles, retorts,
or by any other suitable means, in combination with a salt or salts exercising
their effect on the said phosphates either, 1ly, the said salt or salts being
decomposable by heat their acid is thereby set free, and acts on the phos-
phates, destroying the compactness of these latter reduces them to a spungy
condition resembling that of pumicestone or calcined bones; or, 2ly, the salt
or salts to be made use of, not being decomposable heat, the desintegrating
of the phosphate is still obtained by the presence or by adding a sufficient
quantity of silica, this latter acting, by the effect of the calcinating heat, as an
acid, and entering into combination with the base of the salt or salts made use
of; whilst the acid of these latter acting on the phosphates procures the desinte-
gration or alteration of these latter, so as finally to give rise to the same result
as if a salt spontaneously decomposable by heat had been made use of.
The distinguishing features of my Invention thus being explained, I will.
now enter into the details thereof, and describe the modes of putting the

page_text: Invention into practical effect. The salts which, for cheapness sake and as
giving the most satisfactory results, I prefer to make use of for operating the
required desintegration of the phosphates are, the chloride of magnesium, the
sulphate of magnesia, the sulphate of potash, and the double sulphate of
magnesia and potash, and more especially the said salts obtained from the
mother waters of the brine pits in the manufacture of sea salt. A com-
bination of any two or more of these salts, or of other salts, acting on the
phosphates in the same manner as has been explained above, may be made
use of, such, for instance, as potassa or its salts, soda or its salts, barytes or its
salts, strontia or its salts, lime or its salts, magnesia or its salts, or some salts
of iron.
And in order to make the Invention more easily understood I will now
describe more fully the modes of acting and the chemical reactions which
take place; thus, for instance, for procuring the desintegration of apatites by
means of chloride of magnesium, and more especially the chloride of mag-
nesium obtained from the mother waters of the brine pits in the manufacture
of sea salt, or what are called in France the summer salts (sels d'été), the
mode of acting is as follows:-The said apatites are reduced to a finely-
pulverized state, and after having intimately mixed therewith about twenty
per cent. more or less of the said chloride of magnesium, the whole is calcined
for about three hours to red heat in a reverberatory furnace, a crucible, retort,
or other suitable apparatus till the whole is reduced to a spongy state
resembling about pumicestone; the mixture is then removed from the
furnace or other apparatus in which the calcining had taken place, left to
cool, and after being pulverized may be made use of for manuring purposes.
The chemical reaction which during the calcination has taken place is as
follows: By the effect of the red heat the chloride of magnesium becoming
decomposed, its chlorine is set free as nascent hydrochloric acid, which acts
on the phosphate, part of the said acid forming chloride of calcium, whilst
magnesia is left behind, together with the phosphate, the chemical consti-
tution is entirely changed from what it was before calcining, and has become
readily assimilable by plants. By adding during the calcining process suitable
quantities of sulphate of soda or sulphate of potash to the mixture of apatite and
chloride of magnesium, the desintegrating effect is increased, the spungy or
pumicestone-like appearance of the mass becomes more homogenous and better
fused throughout. Sulphate of magnesia decomposed by heat may be made use of
instead of the chloride of magnesium for desintegrating the natural phosphates
of lime; or a mixture of sulphate of magnesia and sulphate of soda, or the
double sulphate of potash and magnesia obtained from the mother waters of

page_text: the brine pits. The particular advantage offered by the use of this latter salt
(double sulphate of potash and magnesia) is, that the compound thus obtained
not only contains the desintegrated phosphate, but at the same time suitable
quantities of potassa and magnesia, and consequently constitutes a highly-
valuable manuring compound. What has been described above in respect to
the desintegrating of apatites is equally applicable to that of phosphorolites
(nodules), coprolites, or bones. The sulphates of soda or of potash may be
made use of in the same manner, according to my process, for desintegrating
natural phosphates of lime, in case, namely, a sufficient quantity of silica be
present, in which case by the effect of the elevated temperature during cal-
cining, the silica will decompose the said sulphates, and form with their basis
alcaline silicates; whilst the sulphuric acid of the sulphates being set free
acts on and causes the proper desintegration of the phosphates. By adding
more than twenty per cent. of sulphate of potash, for instance, with the phos-
phate, together with a suitable quantity of chloride of magnesium, or sulphate
of magnesia, the compound will melt and frit into a sort of vitrous mass.
For certain descriptions of phosphates of lime, such, for instance, as phos-
phorolites, containing much clay or silica, the addition of an alkaline sulphate
and suitable calcination will be sufficient for obtaining the proper desintegra-
tion or alteration of the phosphate; whilst other phosphates, such as apatites,
for instance, require the addition of a salt of magnesia before calcining them.
In most cases a cherry or sometimes even a dark-red heat will be a sufficiently
high temperature for calcination and obtaining the proper reaction of the salt or
salts on the phosphate, though this depends, of course, on the nature of the
phosphate to be treated.
From what has been described above it will be further conspicuous that
what forms one of the main or leading features of my Invention, particularly
if the salts obtained from brine pits for the manufacture of sea salt are made
use of, is, that the desintegrating of the phosphates is obtained by means of a
calcination at a suitable degree of heat of the said phosphates in combination
with a salt or salts, which, whilst procuring the proper desintegration of the
phosphates, at the same time leaves in the fused mass not only the desinte-
grated or assimilable phosphate, but also suitable salts of potash, soda,
magnesia, or others (according to the salts employed), and thus gives rise to
bighly valuable manuring compounds. As already stated, the salts extracted
from the brine pits or mother waters in the manufacture of sea salt are those I
prefer to make use of; I also intend to make use of these latter salts for
forming valuable manuring compounds, by simply mixing them with the
phosphates of lime, these latter having been either previously desintegrated

page_text: or not by means of my above-described processes, or merely reduced to a
finely-pulverized state or impalpable powder. It is to be understood that the
manuring compounds obtained by my processes are to be employed in a
finely-pulverized state. I also wish to add here, that I do not intend to
restrict myself to any exact proportions in which the salt or salts are to be
used in combination with the phosphates, as these proportions must neces-
sarily vary according to the nature of the salt or salts, or of the phosphates;
neither to the degree of heat to which the compounds are to be submitted
during calcination, or to the apparatuses in which this latter operation may
be effected.
My improved modes of treating natural phosphates of lime not only have
for their object to change the physical character of these latter, but more
especially to alter their chemical constitution, and render them better assi-
milable by plants than in their natural state. In natural phosphates of lime
their degree of solubility is not always a reliable measure of their useful effect
for manuring purposes, and very often phosphates of equal solubility exert a
very different useful effect on vegetation. The principal object of my pro-
cesses is to bring the said phosphates to a state in which they are readily
assimilable by plants.
Having thus described and particularly ascertained the nature of my
Invention, and the manner in which the same is or may be put into effect, I
wish it to be understood that I do not intend to restrict or restrain myself to
the exact processes above described, as many variations may be made there-
from without deviating from the main features or principles of the Invention;
but what I consider to be novel and original, and therefore claim as the
Invention secured to me by the herein-before in part recited Letters Patent,
is, for the purpose of desintegrating or rendering more readily assimilable by
plants, and consequently better suitable for manuring purposes:-
1ly, submitting natural phosphates of lime, such as apatites, phosphorolites
(nodules), coprolites, or bones to a suitable calcination in combination with
either chloride of magnesium, sulphate of magnesia, sulphate of potash, or
double sulphate of magnesia and potassa, salts obtained from the mother
-waters of brine pits in the manufacture of sea salt, or any two or three of
these salts, the desintegration of the said phosphates taking place during the
said calcination, either by means of the acid of the salt or salts acting directly
ou the phosphates, or by means of the base of the salt or salts being acted
upon by the silica present or added purposely, the acid of the salt or salts
becoming liberated effects the required desintegration of the phosphates.
2ly, obtaining the desintegrating of the said phosphates by calcining them:

page_text: in combination with one or more salts others than those just mentioned, but
acting on the phosphates in a similar manner to these latter.
In witness whereof, I, the said Guillaume Ville, have hereunto set my
hand and seal, this Thirtieth day of April, in the year of our Lord
One thousand eight hundred and sixty-four.
Witness,
A. G. BRADE.
G. VILLE. (L.S.)