IMPROVEMENTS IN THE MANUFACTURE OF PHOSPHORUS
Year: 1854

page_text: LETTERS PATENT to Edouard Cari Mantrand, of Paris, France, Chemist,
for the Invention of "IMPROVEMENTS IN THE MANUFACTURE OF PHOSPHORUS."
Sealed the 22nd September 1854, and dated the 25th May 1854.
PROVISIONAL SPECIFICATION left by the said Edouard Cari Mantrand at
the Office of the Commissioners of Patents, with his Petition, on the
25th May 1854.
I, EDOUARD CARI MANTRAND, of. Paris, France, Chemist, do hereby declare
the nature of the said Invention for "IMPROVEMENTS IN THE MANUFACTURE OF
PHOSPHORUS to be as follows:-
"
The Invention consists in decomposing all kinds of phosphates, but moro
particularly phosphate of lime, or the residuum animal charcoal from sugar
manufactories, by means either of hydrochloric acid gns or chlorine, in order
to set free the phosphorus. For this purpose, I mix with the phosphate from
which I wish to obtain the phosphorus a certain quantity of charcoal, or any
other suitable carbonaceous matter, and having heated to a bright red heat, I
cause a current of one of the above-mentioned gases to pass through the
mixture; the following reactions take place :-
1°, for hydrochloric acid gns.-(Ph. O³, 3 Ca. O,) + 3 Cl. H. +8 C-
3 Ca. Cl. +8 Co. + 3 H. + Ph.
20, for chlorine. (Pb. O, 3 Ca. O,) + 3 El. + 8 C=3 Ca. Cl. +8 Co. + Ph..
In both instances the phosphorus is set free, and may be received in a proper
condensor. The operations are performed in retorts, ovens, or any other suitable
apparatus of freestone, or any other material not acted upon by the above-
mentioned chemical substances, and sufficiently refractory.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Edouard Cari Mantrand in the Great Seal Patent Office on
the 25th November 1854.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, EDOUARD
CARI MANTRAND, of Paris, France, Chemist, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Twenty-fifth day of May, in the year of our Lord One
thousand eight hundred and fifty-four, in the seventeenth year of Her reign,
did, for Herself, Her heirs and successors, give and grant unto me, the said
Edouard Cari Mantrand, Her special licence that I, the said Edouard Cari
Mantrand, my executors, administrators, and assigns, or such others as I, the
said Edouard Cari Mantrand, my executors, administrators, and assigns, should
at any time agree with, and no others, from time to time and at all times
thereafter 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 THE MANUFACTURE OF PHOSPHORUS," upon the condition (amongst others) that
I, the said Edouard Cari Mantrand, 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 Edouard Cari Mantrand, do hereby
declare the nature of my said Invention, and in what manner the same is to be
performed to be particularly described and ascertained in and by the following
statement:-
My Invention, which is applicable to all matters containing phosphates, but
more particularly to those containing phosphate of lime, has for its object to
obtain phosphorus with greater facility, in less time, and in larger quantities than
was possible by any other method employed till yet. The principal part of my
process is based on the chemical decomposition, which takes place when hydro-
chloric acid gas (H. Cl.) or chlorine (Cl.) is brought in contact with a proper
mixture of phosphate and carbon, the mixture being at the bright red or white
heat. Thus, for instance, when phosphate of lime is acted upon, the following
chemical decompositions will take place, viz, by employing hydrochloric acid,
Ph. 0, 3 Ca. O. + 8 C. + 3 Cl. II. 3 Ca. Cl. + 8 Co. + 3 H. + Ph., and by
employing chlorine, Ph. 0³, 3 Ca. O. + 8 C. + 3 Cl. = 3 Ca. Cl. + 8 Co. + Ph.
In both instances phosphorus and oxyde of carbon is set free, and a residuum

page_text: of chloride of calcium is left behind in the retort. My process is applicable to
all matters containing phosphates, but more particularly to those containing
phosphate of lime, such as bones, the residuum in the manufacture of glue from
bones, the animal charcoal employed in sugar refineries, the residuum of the
ordinary manufacture of phosphorus, &c. Matters containing phosphate of
lime being more particularly those to which I intend applying my process, I
will in this Specification more particularly apply to them, though the process
may also be applied to other phosphates.
The process is performed by means of ovens, muffles, retorts, or other
suitable recipients of fire-clay, or other suitable material permitting of bringing
the above-mentioned mixture of the phosphate and carbon to a bright red or
white heat, and allowing the passing (for decomposing the phosphate) a current
of hydrochloric acid gas or chlorine through the mixture without attacking the
said recipients. I prefer to employ apparatus arranged in such manner as to
allow the easy removal of any residuum formed during the process; at the same
time it will be preferable that the recipients are arranged in such manner as to
allow them to be emptied and filled at any time without interfering with the
regular course of the process. As for the arrangement of these apparatuses, I
do not intend to confine myself to the use of any of them in particular; however,
I will describe here an arrangement which I prefer using when the process is
to take place on an extensive manufacturing scale. Fig. 1 represents a plan
view of the arrangement, of which Figure 2 indicates a longitudinal vertical
section over the line A, B, of Fig. 1; whereas Fig. 3 is a vertical transverse
section of Figure 1 over the line C, D; and Fig. 4, another vertical section over
the line E, F. The same is composed of a sort of a reverberatory furnace a,
provided with one or more muffles or retorts 6, of fire-clay, or any other
suitable material, the ends of which retorts protrude on both sides beyond the
oven. At one of these ends a removable slanting tube or allonge c is luted;
the other end of which allonge passes through the cover d of a condenser or
tank e, lined with lead and partly filled with water, in which the lower end of
the allonge dips for about 1 to 1 inches. The cover d dips into a groove f,
arranged all round the border of the tank, in which groove water is contained
in such manner as to form a hydraulic closure for the tank. At the other end
of each retort b is fixed a tubo g, communicating by means of a stop-cock i,
with a main tube k, which latter communicates by means of a pipe with the
apparatus 1, for evolving the hydrochloric acid gas or chlorine, or with any
other apparatus from which these gases may be obtained. m is the fire-place
of the furnace, and n the chimney of the same. The muffles or retorts bare
to be placed in such a position as to incline towards the hinder part, in order

page_text: that the liquid chloride of calcium or other residue may collect in this part,.
which is provided with a hole, by means of which the residues may be removed
whenever the plug o, with which the hole is closed, is removed. p is a small
tube for conducting the phosphoretted hydrogen evolved during the process
under a bell q, communicating by means of a tube 1, with a second tank s, also
lined with lead, and partly filled with water, and provided with partitions t.
The phosphoretted hydrogen evolved during the process is ignited at the end of
the tube r, under the bell q, in contact with the atmosphere, by which means
phosphoric acid will pass over in the tanks along with oxyde of carbon
formed during the process; the phosphoric acid will dissolve in the water of the
tank, from which it may be obtained afterwards by evaporation, and trans-
formed into phosphorus by deoxydizing with charcoal in retorts at a proper
degree of heat. The oxyde of carbon escapes through the pipo u.
The apparatus being thus arranged, the fire is lighted, the allonges c
removed from the retorts, and these latter filled with the mixture of phosphatic
matters and carbon; the allonges c are then fixed again in the back of the
retorts, and the joints having been carefully luted, the retorts are brought to a
bright red or white heat, when the cocks i being opened, the hydrochloric
acid gas or chlorine is allowed to pass through the mixture in the retorts,
when decomposition will at once begin, and the phosphorus along with some
phosphoretted hydrogen and oxyde of carbon will distil over. The phosphorus
will condense in the tank or condenser e, and is gathered and afterwards
purified in the ordinary manner; whereas the phosphoretted hydrogen is
decomposed in, the bell apparatus, and the oxyde of carbon escapes, as has
been already described. When the mixture in one of the retorts is sufficiently
deprived of its phosphorus, the stop-cock is turned, and the hydrochloric
acid gas or chlorine prevented from entering any further into this retort; the
chloride of calcium, forming a residuum in this latter, is permitted to flow out
by removing the plug o, after which this latter is again replaced in the hole,
and the retort being filled with a fresh quantity of the mixture of phosphate
and carbon, and the joints having been carefully luted, the cock i is again
opened as soon as the matters in the interior of the retort will have become
sufficiently heated, and hereby the hydrochloric acid gas or chlorino is allowed
to flow in the retort, when the decomposition and the evolving of phosphorus
will begin at once.
I must mention here that I prefer using hydrochloric acid gas rather than
chlorine.
For the carbon to be mixed with the phosphatic matters, I use finely
pulverized wood charcoal, the quantity of which is to be regulated according

page_text: to the atomical proportions of phosphorus contained in the phosphatic matters,
and differs consequently according to their nature; but at all events it will bo
good to use rather a little more of the carbonaceous matters, as would corre-
spond with the quantity necessary in conformity with the atomical proportions for
deoxydizing the phosphoric acid formed; these proportions generally vary from
about twenty to 50 p %% by weight of the phosphatic matters. The phosphates
are reduced as much as possible to a finely pulverized state, and they must be
thoroughly mixed with the pulverized wood charcoal; when acting on matters
containing phosphate of lime, I generally prefer mixing with them a certain
quantity of silicious sand, and a sufficient quantity of water, in order to allow of
forming the entire into small balls, which after having been dried are intro-
duced into the retorts. The reason why I introduce some silicious sand in the
mixture of phosphate and carbon is with the object, firstly, of dividing the
particles and augment the points of contact for the hydrochloric acid gas or
chlorine to act upon; and, secondly, in order to neutrålise part of the lime
from the phosphate of lime by forming silicate of lime, by which means less
hydrochloric acid is necessary for saturating the remaining lime.
Having thus described the nature of my Invention, and the manner in
which the same is to be performed, I declare that I do not confine myself to
the apparatus described, for the same may be done by a great variety of
apparatuses; but that what I claim as my Invention consists in the process
described for obtaining phosphorus, by decomposing matters containing
phosphates, and more particularly phosphates of lime, by thoroughly mixing
with them a suitable quantity of carbonaceous matters alone, or mixed with
a suitable quantity of silicious matters, and afterwards passing in suitable
apparatuses bydrochloric acid gas or chlorine through these mixtures when
the same are brought to a bright red or white heat.
In witness whereof, I, the said Edouard Cari Mantrand, have hereunto
set my hand and seal, this Twenty-second day of November, in the
year of our Lord One thousand eight hundred and fifty-four.
EDOUARD CARI MANTRAND. (L.B.)