Process and Apparatus for the Simultaneous Manufacture of Phosphorus and of Alkaline Silicates by the Treatment of the Mineral Phosphates of Lime, Alumina, or Bone Ash.
Year: 1890

page_text: Date of Application, 22nd Aug., 1890
Complete Specification Loft, 1st Dec., 1900 Accepted, 21st Feb
4004
PROVISIONAL SPECIFICATION.
Process and Apparatus for the Simultaneous Manufacture of
Phosphorus and of Alkaline Silicates by the Treatment of
the Mineral Phosphates of Lime, Alumina, or Bone Ash.
I, LOUIS MARIE CHARLES FOLIE-DESJARDINS, of 17, Alleé St. Etienne,
Toulouse, Hte Garonne, France, Chemist, do hereby declare the nature of this
invention to be as follows:-
My invention has for object :-
1. The elimination of the phosphoric acid of the mineral phosphates of lime,
or of alumina, or of bone ash, for forming a simple or a complex alkaline
phosphate.
2. The elimination of the phosphoric acid of alkaline phosphate by means of
heat and of silicic acid, and, simultaneously the reduction by means of carbon, of
the liberated phosphoric acid.
These operations have not hitherto been effected industrially or chemically with
the object of obtaining
--
1, an alkaline phosphate
2, simultaneously, phosphorus and a simple or a complex alkaline silicate.
In order to enable my invention to be more readily understood, I will, after
having described the apparatus, indicate by examples the chemical reactions to
be effected, then I will illustrate the process of the operation by the aid of the
drawings annexed hereto.
The left hand
Fig. 1 shows in vertical section the gas generator, and the furnace or oven
with its regenerator. The right hand portion is a vertical section of the furnace or
oven with its regenerator on the line VIII, IX, X, XI of Fig. 2.
portion is a vertical section of the gas generator on the line I II of Fig. 6.
Fig. 2 is a cross section of the furnace or oven with the regenerator.
Fig. 3 is a cross section of the gas generator taken through the charging
opening G.
Fig. 4 is a front elevation of the gas generator.
Fig. 5 is a front elevation of the furnace or oven with its condensers.
Fig. 6 is a horizontal section of the gas generator on the line IV, V, VI, VII of
Fig. 1, and a horizontal section of the regenerator on the line XII, XIII,
XIV, XV, of Fig. 2.
Fig. 7 is a plan of the gas generator and a horizontal section of the regenerator
on the line IX, X, XVI, and XVII of Fig. 2. The apparatus comprises :-
1, a furnace or oven heated by means of carbonic oxide (CO), with a regenerator
of the waste heat.
2, retorts, varying in number arranged in the furnace or oven.
These retorts C which are of refractory earth, may, if it be thought desirable,
be provided with an internal lining of magnesite. They have a slight inclination
to allow of the outflow either of the product resulting from the mineral phosphates
or the bone ash in the first operation, or of the residual alkaline silicate from
the second operation.
The retorts are furnished with a tap hole a.
The plugs V for closing the retort and the tap hole a are furnished with an
internal lining of refractory materials surrounded by a sleeve of asbestos for
ensuring tightness of joint; they are closed by means of a pressure screw r.
Each retort is provided at its upper part at the side near the opening of the
retort, with a pipe & for allowing of the escape of gases, and formed in one piece
with it for a certain length.

page_text: 3. Brass extensions y (in the manufacture of phosphorus) fitting on the pipe x
and serving to conduct the gas into the condenser z.
4. A condenser z provided with a draught flue or chimney t communicating with
a central conduit which conveys the carbonic oxide and other uncondensed gases
into a gasometer or gas holder not shown.
5. One or more gasometers designed, in the manufacture of phosphorus, for the
reception of combustible gases which on passing from the last gasometer are
conveyed by a pipe to the burners, where they are to be utilized according to
requirement.
A is the gasometer, B the regenerator of the waste heat, D the gallery or
passage for working the gas generators, E the gallery or passage for working the
regenerators, F the door of the furnace or oven, G the charging plug, and H the
ashpit door.
Fig. 7 is a sight hole closed by a cast iron plug for enabling the conduit L to
be examined for carbonic oxide and to be cleaned from dust carried along in
suspension. I, Figs. 1 and 6 are openings provided with cast iron plugs for the
passage of false bars during the cleaning. J is a cast iron port serving for the
introduction of air and water into the gas generator.
K, Figs. 1 and 4 is the rose of a sprinkler serving for the rapid extinction of the
ashes resulting from the cleaning. L is a flue for carbonic oxide. M are flues for
smoke and products of combustion which pass through N underneath the roof of the
regenerator, and after passing between the tubes of the regenerator, enter the
chimney. O, (Figs. 2 and 6) are exit orifices for hot air. O, Fig. 7, are orifices
for placing the last rows of tubes into communication with the air chamber Q.
P (Fig. 6) are exit orifices for carbonic oxide. Q, Fig. 7 is an air chamber
placing the orifices O for hot air into communication with one another. R, Figs. 1,
2, 6 and 7, is an inlet for cold air into the regenerator.
S, Fig. 2, are internal baffles compelling the cold air to pass into all the rows of
tubes as indicated by the arrows. T, Figs. 1, 6 and 7, is a chimney furnished with
a register n. d, e, f, Figs. 5 and 6 are sight holes of cast iron.
The treatment of the phosphates in the first operation by means of alkaline
sulphates or carbonates may be effected by means of a reverberatory furnace
having a slightly inclined bottom or hearth. In this manner deterioration of the
retorts by the corrosive action of the carbonates, more than that of the sulphates, is
obviated.
However, if it is desired to utilize the carbonic acid or the sulphurous acid, retorts
and furnaces or ovens may be employed similar to those just described; except
that tube x of the retorts C communicates, in such a case, with a central conduit
and not with a condenser, and the carbonic acid gases or sulphurous acid gases are
conducted to apparatus which are intended to store up or else directly utilize the
same.
CHEMICAL REACTIONS-PROCESS OF THE OPERATION.
The first operation to be performed is the elimination of the phosphoric acid from
the phosphate of alumina or phosphate of lime by means of an alkaline sulphate or
carbonate, or by means of a mixture of carbonate of soda and carbonate of potash,
or by means of a sulphate of these two bases.
When operating for instance with carbonate of soda and phosphate of alumina, or
wavellite, the reaction to be produced is represented by the following equation
AT O°, PO + 4 (Na U, CO²) +
+ 3 Na O, PO³ + 4 CO².
As already stated, this reaction may be effected either in a reverberatory furnace
or in retorts of refractory earth heated by means of carbonic oxide. X is the tube
serving for the escape of the carbonic acid CO2. This gas passes by a central
conduit towards the place of storage or utilization. Thus the carbonic acid may

page_text: oven heated by means of carbonic oxide, as illustrated in Fig. 1 and Fig. 5 of the
annexed drawings.
The reaction to be produced is illustrated by the following equation in the
example I have taken.
3 Na O, PO' + 3 Si O³ + 5 C
= 3 (Na O, Si O³) + P + 5 CO.
The intimate mixture being raised to a bright red heat in the retorts, the silicic
acid attacks the base; forming an alkaline silicate and liberates the phosphoric acid.
The latter being free, is reduced by the carbon which unites with the oxygen of
the acid to form carbonic oxide (CO). The volatilized phosphorus P, passes by a
and y into the condenser z where it is collected. The carbonic oxide and the
uncondensed gases pass into the central conduit and through b into a gas holder.
The combustible gases thus collected, are then, according to the requirements of
the case, conveyed to the burners of furnaces, or preferably to furnaces for
regenerating the waste heat.
The products of the operation are therefore :-
1. Phosphorus, which is to be purified by the usual means.
2. A simple or complex alkaline silicate, such as, as in the example chosen, a
silicate of soda.
The degree of acidity of the alkaline silicate may vary at the will of the operator,
according to the use for which it is intended.
The residual silico-aluminate of soda contains sesqui-oxide of iron. This residue
may be treated by known means so as to yield a precipitate of alumina and sesqui-
oxide of iron, gelatinous silica, and a caustic alkali or an alkaline carbonate.
The separation of the sesqui-oxide of iron, from the alumina may be efficiently
effected by means of trimethylamine N (C2 H³), which precipitates the sesqui-oxide
of iron and the alumina, and then redissolves the latter."
This residue must not therefore be considered a waste product, for it is possible
to recover the greater part of the alkaline salt.
If in place of phosphate of alumina phosphate of lime, and an alkaline carbonate
are employed for instance, the addition of silica may be dispensed with, the
carbonate of lime obtained remaining in suspension in the melted material, being
insoluble in it.
The first operation will thus be represented by one of the following equations:-
1. Bone ash 3 (PO 3 Ca O) + 18 (Na O, CO²) = 3 (PO³, 3 Na O) + 9.Na O
+9 Ca O, CO² + 9 CO²
-
2. Fossil phosphate of lime 3 (PO, 3 Ca O) + Ca F1) + 18 (Na O, CO²) =
3 (PO, 3 Na O) + Ca Fl + 9 Na Ò+ 9 Ca O, CO² + 9 CO².
The product of the reactions when subjected to a slight lixiviation and allowed to
rest, deposits the carbonate of lime (or as the case may be, carbonate of lime and
fluoride of calcium), and there remains a solution of tribasic phosphate of soda and
hydrated protoxide of sodium which is to be evaporated to dryness.
With the product, an intimate mixture is made with silica and carbon which is

page_text: submitted to the action of heat, as hereinbefore stated. The reactions obtained are
represented by the following equation:
3 (PO, 3 Na O) + 9 Na O + 9 Si O² + 15 C = 3 P + 9 Na² O², Si O² + 15 CO.
If desired, the acidity of the silicate may be modified by increasing the proportion
silica as before mentioned. The result is :-
1, impure phosphorus
2, an alkaline silicate
3, carbonic oxide.
As it is possible to modify the degree of acidity or of alkalinity, so is it also
possible by mixing the alkalies, to obtain complex silicates of potash and soda.
My invention comprises the manufacture of alkaline phosphates consisting in the
chemical reactions hereinbefore described, either for sale as such or for transforming
them into metaphosphates or into pyrophosphates, or into neutral tribasic
phosphates.
By my process I avoid the employment of a high temperature in manufacture of
phosphorus; I obtain two products of great commercial value, and I transform the
manufacture of phosphorus, from an unhealthy industry, into an industry without
any danger to the health of the workpeople, without inconvenience to adjacent
property or to the public health.
Dated this 22nd day of August. 1890.
L. M. C. FOLIE-DESJARDINS.
By L. W., per F. B.
COMPLETE SPECIFICATION.
Process and Apparatus for the Simultaneous Manufacture of
Phosphorus and of Alkaline Silicates by the Treatment of
the Mineral Phosphates of Lime, Alumina, or Bone Ash.
I, LOUIS MARIE CHARLES FOLIE-DESJARDINS, of 17, Allee St. Etienne,
Toulouse, H. Garonne, France, Chemist, 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 :-
My invention has for objects-Firstly the elimination of the phosphoric acid
from the mineral phosphates of lime, or of alumina, or of bone ash, for the
purpose of forming a simple or a complex alkaline phosphate and Secondly, the
elimination of the phosphoric acid from an alkaline phosphate by means of heat and
of silicic acid, and the simultaneous reduction by means of carbon, of the
liberated phosphoric acid.
These operations have not hitherto been effected industrially or chemically with
the objects 1st of obtaining an alkaline phosphate; and 2nd of obtaining
simultaneously phosphorus and a simple or a complex alkaline silicate.
To enable my invention to be more readily understood, I will after describing
the apparatus, indicate by examples the chemical reactions to be effected; and
will then describe, by the aid of the drawings filed with my Provisional Specification
the method of carrying out the process.
Referring to these drawings,
Fig. 1 shows in vertical section the gas generator, and the furnace or oven with
its recuperator. The right hand portion of this figure is a vertical section of the
furnace or oven with its recuperator on the line VIII, IX, X, XI of Fig. 2. The
left hand portion of Fig. 1 is a vertical section of the gas generator on the line I II
of Fig. 6.
Fig. 2 is a cross section of the furnace or oven with the recuperator.
Fig.
opening G.
is a cross section of the gas generator taken through the charging
Fig. 4 is a front elevation of the gas generator.
Fig. 5 is a front elevation of the furnace or oven with its condensers.

page_text: ཁྱསཔ ཁྱས
Fig. 1, and a horizontal section of the recuperator partly on the line XII, XIII,
XIV, XV of Fig. 2.
Fig. 7 is a plan of the gas generator and a horizontal section of the recuperator
on the line IX, X, XVI and XVII of Fig. 2.
The apparatus comprises-A furnace or oven heated by the combustion of
carbonic oxide (CO) and provided with a recuperator for utilizing the heat of the
escaping products of combustion. Within this furnace or oven is arranged a series
of retorts, C the number of which may be varied to suit requirement. These
retorts C which are of refractory earth, may, if desired, be provided with an
internal lining of magnesite. They have a slight inclination to allow of the
outflow either of the product resulting from the treatment of the mineral
phosphates, or the bone ash, in the first operation, or of the residual alkaline
silicate resulting from the second operation. The retorts are each furnished with a
tap hole a. The plugs V for closing the front ends of the retorts and the plugs
for closing the tap holes a are each provided with a coating of refractory material
surrounded by a sleeve of asbestos for ensuring tightness of joint. The plugs V
are each closed by means of a pressure screw r.
Each retort is provided at its upper part at one side and near its front end with
a pipe a to allow of the escape of gases. Each of these pipes is or may be formed
in one piece with its corresponding retort. yy are extensions preferably of brass,
for the manufacture of phosphorus ; these extensions are fitted onto the pipes a as
shown in Fig. 5 and serve to conduct the gases from the retorts into a condenser z.
This condenser is provided with a draught flue or chimney t that communicates
with a central conduit which conveys the carbonic oxide and other uncondensed
gases produced in the manufacture of phosphorus into one or more gasometers or
gasholders not shown. From the gasometer or gasholder, or from the last one
if more than one be used, the combustible gases are conveyed by a pipe to the burners
where they are to be utilized according to requirement.
A is the gas generator; B the recuperator of the waste heat; D the gallery or
passage wherein a person can stand whilst working the gas generator or gas
generators if more than one be used; E the gallery or passage for working the
recuperators, F a door near the lower end of the gas generator, G the charging
opening to said gas generator, normally closed by a plug; and H the ashpit door
of the generator. g, (Fig. 7) is a hole normally closed by a cast-iron plug. This
opening enables the conduit L to be examined for carbonic oxide and to be cleaned
from dust that has been carried along in suspension and, deposited therein.
I, (Figs. 1 and 6) are openings normally closed by cast-iron plugs and serving for
the passage of false bars during the cleaning of the gas generator. J is a cast
iron part or box serving for the introduction of air and water into the gas
generator. K (Figs. 1 and 4) is the rose of a sprinkler serving for the rapid
extinction of the ashes resulting from the cleaning. L is a flue for conducting
carbonic oxide from the gas generator to the furnace or oven containing the
retorts C. M, M are flues for smoke and products of combustion which pass
through the flues N underneath the roof of the recuperator, and after passing
between the tubes of the recuperator, enter the chimney. O, (Figs. 2 and 6) are
exit orifices for hot air from the recuperator into the furnace or oven.
0¹, 0¹,
(Fig. 7), are orifices for placing the last rows of tubes in the recuperator in com-
munication with the air chamber Q. P (Fig. 6) are exit orifices for carbonic
oxide into the furnace or oven. Q, Fig. 7, is an air chamber that places the
orifices O for hot air in communication with one another. R, (Figs. 1, 2, 6 and 7,)
is an inlet for cold air into the recuperator. S, S, (Fig. 2,) are internal baffles
that compel the cold air to pass through all the rows of tubes, as indicated by the
arrows. T, (Figs. 1, 6 & 7), is a chimney furnished with a register n. d, e, f,
Figs. 5 and 6 are sight holes normally closed by plugs. The treatment of the
phosphates in the first operation by means of alkaline sulphates or carbonates may
be effected by means of a reverberatory furnace having a slightly inclined bottom

page_text: or hearth. In this manner deterioration of the retorts by the corrosive action
of the carbonates, which is greater than that of the sulphates, can be obviated.
However, if it be desired to utilize the carbonic acid or the sulphurous acid
evolved during this operation, retorts and furnaces or ovens may be employed,
similar to those herein before described with reference to the drawings except that
the tubes of the retorts C communicate, in such a case, with a central conduit
and not with a condenser, and the gases containing carbonic acid gas or sulphurous
acid gas as the case may be, are conducted to apparatus wherein it can be either
stored up, or directly utilized as may be required.
The chemical reactions that take place in carrying out my invention are as
follows:-
The first operation to be effected is the elimination of the phosphoric acid from
the phosphate of alumina or phosphate of lime by means of an alkaline sulphate or
carbonate, or by means of a mixture of carbonate of soda and carbonate of potash,
or by means of a mixture of the sulphates of these two bases.
When operating for instance with carbonate of soda and phosphate of alumina
or wavellite, the reaction to be produced is represented by the following equation:-
P₂ O₂ Al₂ O¿ + 4 CO Na O2 + Si O₂ = Na, O, Al„ O̟ Si O₂ +
P₂ O₂ Al₂ О + 4 CO Na O2 + Si O₂ = Na, O, Al„ O̟ Si O₂ +
2
B
As already stated, this reaction may be effected either in a reverberatory furnace
or in retorts of refractory earth heated by means of carbonic oxide. When retorts
such as C (Figs. 1 and 2) are used the tubes a serve for the escape of the carbonic
acid gas (CO2), which passes by a conduit to the place where it is to be stored
or utilized. Thus the carbonic acid may serve for the treatment of the residual
silico-aluminate of soda (Na, O, A₁₂ O₂, Si O2), or for any other suitable
purpose.
3'
The calcined product obtained according to the preceding reaction is composed
of silico-aluminate of soda and tribasic phosphate of soda (PŎ Na O₂); it is porous
and can be easily lixiviated.
When subjected to lixiviation, the tribasic alkaline phosphate is dissolved out,
and the solution thus obtained is evaporated to dryness and the residue pulverized.
The residue of the lixiviation is a silico-aluminate of soda (Na, O, Al₂ O₂, Si O₂).
The second operation has for its object to eliminate from the alkaline phosphate
thus obtained, the phosphoric anhydride P, O and to reduce the same to obtain
phosphorus. For this purpose the alkaline phosphate is intimately mixed with
silicic acid and carbon and the mixture is subjected to the action of heat in the
retorts C of a furnace or oven heated by means of carbonic oxide, as hereinbefore
described with reference to Figs. 1 and 5 of the drawings. The reaction to be
produced is indicated by the following equation in the example I have taken.
4 PO Na O3 + 3 S1 O₂ + 10 C = 3 Si Na O₁ + 4 P + 10 CO.
By raising the intimate mixture to a bright red heat in the retorts, the silicic
acid attacks the base, forming an alkaline silicate and liberates the phosphoric
anhydride which being thus free, is reduced by the carbon which unites with the
oxygen of the anhydride to form carbonic oxide (CO). The volatilized phos-
phorus (P) passes by the pipes x and y into the condenser z, where it is collected.
The carbonic oxide and the uncondensed gases pass by the flue or chimney t into
the central conduit and thence into a gasholder. The combustible gases thus
collected, can afterwards according to the requirements of the case, be conveyed
to the burners of furnaces, or preferably to furnaces for regenerating waste heat.
The products of the operation are therefore :-
1. Phosphorus, which is to be purified by the usual means.
2. A simple or complex alkaline silicate, such as in the example taken, a
silicate of soda. The degree of acidity of the alkaline silicate may be varied at
the will of the operator, according to the use for which it is intended.

page_text: 5, carbonic oxide.
As it is possible to modify the degree of acidity or of alkalinity, so is it also
possible by using a mixture of alkalies, to obtain complex silicates of potash and
soda.
Alkaline phosphates produced according to the chemical reactions hereinbefore
described, may be manufactured either for sale as such, or for conversion into
metaphosphates or into pyrophosphates, or into neutral tribasic phosphates.
By my process I avoid the employment of a high temperature in the manu-
facture of phosphorus; I obtain two products of great commercial value, and I
transform the manufacture of phosphorus from an unhealthy industry, into an
industry without any danger to the health of the workpeople, without detriment
to adjacent property or to the public health.
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is:
1. The herein described process for the simultaneous manufacture of phosphorus
and an alkaline silicate from mineral phosphate of lime, or of alumina, or from
bone ash by the following operations
:-
(a) By heating a mixture of the phosphate with one or more alkaline
sulphates or carbonates and with or without addition of silicic acid, or
a flux, in a reverberatory furnace, or in retorts within a regenerative gas
furnace, lixiviating the resulting calcined mass with water and evaporating
the solution to obtain the alkaline phosphate therein; and
(6) Heating a mixture of the alkaline phosphate thus obtained with silicic
acid and carbon, with or without addition of an alkali in a retort or retorts
within a regenerative gas furnace and thereby effecting the simultaneous

page_text: production of phosphorus and a simple or complex alkaline silicate, the
acidity or alkalinity of the latter compound being dependent upon the
amount of silicic acid, or alkali employed in the mixture substantially as
herein set forth.
2. For carrying out the process described in claim 1, apparatus comprising a
gas generator, a device such as a recuperator for utilizing the waste heat, a furnace
with retorts C having exit pipes and extensions y, a chimney communicating
with the said extensions and with a central conduit, and one or more gasometers
and with or without the condenser z, the whole arranged substantially as herein-
before described and illustrated in the drawings.
1000
L. M. C. FOLIE-DESJARDINS.
By L. W., per F. B.
L. M. C. FOLIE-DESJARDINS.
By L. W., per F. B.