Year: 1896

page_text: I, LOUIS LUCIEN BILLAUDOT, of 18 Avenue Victoria, Paris, in the Republic of
France, Manufacturer, do hereby declare the nature of this invention to be as
follows:-
The improved process of manufacture of phosphorus which forms the subject of
this invention mainly consists in (1) Preparing metallic phosphuret by the reduction
of a phosphate; and (2) Separating phosphorus from such metallic phosphuret by
dissociation or displacement, i.e. by forming a compound of the metal with another
body, such as carbon, for example.
The first of these reactions viz. the preparation of a phosphuret by the reduction
of a phosphate, at a more or less raised temperature, by means of a reducing agent
(or medium), such as hydrogen or carbon, has only been feasible up to the present
time with the phosphates of Cd (Cadmium), Cr (Chrome), Cu (Copper), Fe (Iron),
Mn (Manganese), Mo (Molybdenum), Ti (Titanium), W (Tungsten), or Zn (Zinc).
Now, as a result of a number of experiments I produce phosphurets of other metals,
-chiefly of an alkaline-earthy nature, by perforining the reduction of phosphates
in electrical crucibles (no matter how basic or otherwise such phosphates may be);
which fact, however, particularly concerns tri-basic phosphate of calcium, it being
reducible to the state of phosphuret of calcium.
The second reaction, viz. the separation of the metallic phosphurets by dissociation.
may but with difficulty be performed by heat alone. It has hitherto been observed
to take place only in connection with the phosphurets of Ba (Baryum), Cu (Copper),
Mn (Manganese) and Sn (Tin), and with these it has been found to be practically
complete.
I have noticed in the course of my experiments, already referred to, in the
preparation of the metallic phosphurets in electrical crucibles, that during that
operation, phosphorus-vapours were constantly rising, and that the analysis of the
metallic phosphuret, that had been produced, showed that it was accompanied by a
carbide of that metal. This observation led me to the conclusion, which the outcome
of my enquiries fully corroborated, that the carbon, when treated in an electrical
crucible, displaces the phosphorus of the metallic phosphurets and forms carbides,
-a reaction which is of particular importance to industry, as regards both phosphuret
of calcium and phosphuret of iron, as these phosphurets, by reason of their low price,
enable phosphorus to be obtained economically.
In practice the operation may either be divided, by first manufacturing the
metallic phosphuret, as in the case of iron phosphuret, for example, which may be
prepared in a blast furnace, and then treating it in an electrical crucible; or both
stages of operation may be combined into one, as I do in treating tri-basic phosphate
of calcium. It would, moreover, be somewhat difficult, in the case of this
last-mentioned body, to separate the two operations one from the other, for, as stated
above, a loss of phosphorus is sustained in the preparation of phosphuret of calcium.

page_text: Tribasic Phosphate of Calcium + Carbon = Phosphorus +Carbide of Calcium
+ 3 CaC³
(Po*)'Ca³
+
14 C
= P³
Carbonic Oxide
+
8 Co
The phosphorus is carried off in the condition of vapour, along with the carbonic
oxide, and such vapour, as it cools, condenses in very small particles, which reinain
long in suspension in the oxide of carbon, and require somewhat bulky condensing
apparatus; it appearing that the capacity of such apparatus should be one litre per
gramine of phosphorus obtained in one hour, to obtain a satisfactory final product.
The yield in phosphorus has exceeded the 80 per cent. indicated by theory, where
the manufacture is carried on with primitive plant. By way of residue, I obtain, in
this process of manufacture, carbide of calcium, which is as pure as that which is
made from ordinary lime and coke. The motive power to be employed in this case,
which power is calculated on the assumption that the same quantity of carbide of
calcium is produced, is about 17/13 of the power necessary for the production of
carbide of calcium alone.
Dated this 18th day of July 1806
HASELTINE, LAKE & Co.,
45 Southampton Buildings, London, W.C., Agents for the Applicant.
I, LOUIS LUCIEN BILLAUDOT, of 18 Avenue Victoria, Paris, in the Republic of
France, Manufacturer, 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 :-
The improved process of manufacture of phosphorus which forms the subject of
this invention mainly consists in
(1) The preparation of metallic phosphides by the reduction in electrical crucibles
of phosphates of metals, such as alkaline earthy metals and more particularly by the
reduction of tribasic phosphate of lime (Po) Ca' and
(2) The separation also in an electric crucible, of phosphorus from metallic
phosphides, by dissociation or displacement by forming a compound of the metal with
another body, such as carbon, for example.
The first of these reductions viz. the preparation of a phosphide by the reduction
of a phosphate, at a more or less raised temperature by means of a reducing agent
such as hydrogen or carbon has only been feasible up to the present time with the
phosphates of Cd (Cadmium), Cr (Chromium), Cu (Copper), Fe (Iron), Mn
(Manganese), Mo (Molybdenum), Ti (Titanium), Tu (Wolfram), or Zn (Zine).
The invention comprises the several methods employed in the preparation of
phosphorus, or of compounds thereof, which consists in the extraction of the
phosphorus, or compounds of phosphorus, from the metallic phosphides obtained by
my process.
My invention moreover covers generally the mode of extraction of phosphorus, by
treating with carbon, in an electrical crucible, not only metallic phosphides prepared
by my process, but also any other metallic phosphides prepared by any known process.
Now as a result of a number of experiments I produce phosphides of other metals,

page_text: chiefly of an alkaline earthy nature, by performing the reduction of phosphates in
electrical crucibles (no matter how basic or otherwise such phosphates may be). I
reduce for example, tribasic phosphate of lime directly in an electrical crucible by
means of carbon, and obtain phosphides of calcium according to the following
equation
(PO) Ca +8 C = P²Ca³ + 8 CO
and similarly I reduce phosphate of alumina in an electric crucible by means of
carbon, and obtain phosphide of aluminium in accordance with the formula:
Where the two operations, viz. the reduction to phosphide of the phosphate of lime
in an electrical crucible by means of carbon, and the separation of the phosphorus
from the phosphide in the same crucible, and likewise by carbon, have been carried
out successively and without any interruption-as will generally be the case-and
where no base has been added in excess, the general formula of the reaction will be:-
If instead of directly obtaining phosphorus from phosphides prepared in an
electrical crucible, it be desired to extract phosphoretted hydrogen, PH,, all that will
be necessary is to submit such phosphides to the action of water either plain or
acidulated.
Then, from this bydrogen phosphide, phosphorus may be produced in the usual
manner by dissociation, the acids and salts of the phosphorus, by oxidation, and
readily decomposable phosphides, by the action of heat.
And lastly, with the phosphides prepared in the electrical oven, other phosphides,
readily decomposable by heat, may be obtained by double decomposition, such, for
example, as tin and copper phosphides; the formula being :-
As I have already pointed out, my method of treatment of metallic phosphides in
an electrical crucible by means of carbon, with a view to direct extraction of
phosphorus, is applicable to all phosphides including all those hitherto obtained by
any known process.
Thus iron phosphide, which is now produced in a blast-furnace, according to the
following formula:-

page_text: when treated with carbon in an electrical crucible, will yield either of these two
reactions:
Having now particularly described and ascertained the nature of my said invention
and in what manner the same is to be performed, I declare that what I claim is :-
1. The process for the preparation of phosphorus, as hereinabove specified, consisting
in the treatment of phosphates of metals-such as the metals of the alkaline earths, and
more particularly tribasic phosphate of lime-with carbon in an electrical crucible,
with a view to obtaining the corresponding metallic phosphides; and in the treatment
of these several metallic phosphides with carbon in an electrical crucible for the
purpose of separating the phosphorus from such phosphides..
2. In a process such as is referred to in the first claim, the various modes of
extraction of phosphorus in the form of combinations,-phosphoric acid or compounds
thereof, consisting in the treatment by any known means or metallic phosphides
obtained by the reduction of the corresponding phosphates with carbon in an electrical
crucible, substantially as described.
3. The process of preparation of phosphorus in accordance with the first claim,
consisting in the reduction with carbon, in an electrical crucible, of tri-calcic
phosphate, (PO4) Ca³, to calcium phosphide, PCa³, and in separating the phosphorus
from the phosphide, which leads to the formation of calcium carbide, Cat, as a
residue, by causing carbon to act upon such calcium phosphide in an electrical
crucible, substantially as described.
4. The process of manufacture of phosphorus in accordance with the first claim,
consisting in the treatment with carbon, in an electrical crucible oven, of a metallic
phosphide prepared either by the reduction of the corresponding phosphate in an
electrical oven, or by any known method, substantially as described.
d this 17th day of April 1897.
HASELTINE, LAKE & Co..
45 Southampton Buildings, London, W.C., Agents for the Applicant.