MENTS IN THE PREPARATION OF PHOSPHATES OF AMMONIA AND AMMONIACO- MAGNESIAN PHOSPHATE
Year: 1864

page_text: of Middlesex, Engineer and Patent Agent, for the invention of IMPROVE
MENTS IN THE PREPARATION OF PHOSPHATES OF AMMONIA AND AMMONIACO-
MAGNESIAN PHOSPHATE."-A communication from abroad by Emmanuel
Adrien Lesieur, of 29, Boulevart St. Martin, Paris, Engineer Chemist..
Sealed the 2nd December 1864, and dated the 6th June 1864.
PROVISIONAL SPECIFICATION left by the said William Clark at the
Office of the Commissioners of Patents, with his Petition, on the 6th
June 1864.
I, WILLIAM CLARK, of 53, Chancery Lane, in the County of Middlesex,
Engineer and Patent Agent, do hereby declare the nature of the said Inven-
tion for "IMPROVEMENTS IN THE PREPARATION OF PHOSPHATES OF AMMONIA AND
AMMONIACO-MAGNESIAN PHOSPHATE," to be as follows:-
Ammoniaco-magnesian phosphate has long been recognized as forming an
excellent manure, although it has never been made the subject of special
manufacture. The means for preventing the loss of ammonia in urine by
precipitating it in the form of ammoniaco-magnesian phosphate are also indi-
cated in Boussingault's Annals of Chemistry, published in the year 1847.
Still more recently the same result has been sought but with little success; in
the treatment of sewage products it was thought that the ammonia in the

page_text: -
liquids would be wholly precipitated in a state of ammoniaco-magnesian phos-
phate, and that the quality of the manure furnished by the solid matters
would be improved in this manner. Thus the only method hitherto employed
for the production of ammoniaco-magnesian phosphate has been to fix the
ammonia in the liquids in a solid state, as otherwise all its value would be
lost, whereas according to this Invention by means of sulphates and hydro-
chlorates of ammonia, which have a certain recognized value in commerce.
I unite the ammonia contained in these salts with phosphoric acid and
magnesia, and thus produce ammoniaco-magnesian phosphate in a pure state,
capable of direct application in agriculture. Phosphates of ammonia it is
evident will also form excellent manure, as they contain the two matters most
useful to vegetation, and that in the smallest possible compass. By reason of
the ammonia contained they-act the same as ammoniacal salts, hydrochlorate,
and sulphate, and through the phosphoric acid even better than phosphate of
lime. These matters have never hitherto been prepared with a view to their
application as manures.
Methods of manufacturing phosphates of ammonia.-I first prepare the
acid phosphate of ammonia serving to produce tho other substances, as will
be seen in the course of this description. According to the improved method of
manufacturing acid phosphate, I treat bones in any suitable condition, or it
may be nodules or coprolites, by means of hydrochloric or sulphuric acids in
the ordinary manner, and further precipitate the resulting liquors by means of
sulphate of ammonia, which second part of the operation constitutes the
novelty of the process, as acid phosphate of ammonia has never before been
prepared in this manner. By the employment of hydrochloric acid the
following reactions take place:-
1st. Pho³ 3CaO+2HCl= PhO CaO+2Ca Cl.
2ndly. Pho CaO+2Ca Cl+3(SO³ Az H³)
=3(SO³ CaO)+ Pho³ AzH³+2(HCI.AZH³).
In the first operation the tribasic phosphate of lime treated with hydro-
chloric acid produces bi-phosphate of lime and chloride of calcium; these two
products on being placed in the second operation in the presence of sulphate
In the first operation the tribasic phosphate of lime treated with hydro-
chloric acid produces bi-phosphate of lime and chloride of calcium; these two
products on being placed in the second operation in the presence of sulphate
of ammonia produce sulphate of time, which is precipitated, as also bi phos
phate and hydrochlorate of ammonia, which are separated by crystallization.
When treating bones and other substances with sulphuric acid the following
reactions take place :-

page_text: bi-phosphate is added hydrochlorate of ammonia and magnesia, the whole
being put in ebullition; in this manner ammoniaco-magnesian phosphate may
be obtained by precipitation, and also chloride of calcium, which remains in
solution and may be easily separated. This reaction, which is new, is repre-
sented by the following formula:-
Phos CaO+HCI AzH³+2MgO=Pho³(2MgO AzH³)+Ca Cl.
The chloride of calcium obtained may serve to regenerate the bydrochlorate
of ammonia necessary for a second operation by its reaction on rich car-
bonate of ammonia produced by the distillation of water from gasworks and
others :-
Ca Cl+AzH CO2 CaO CO+AzH³ HCl.
The second method of manufacturing ammoniaco-magnesian phosphate
has also the advantage over the first method of only requiring an expenditure
of two equivalents of acid; the sulphuric acid necessary for making the
bi-sulphate of lime, which is equivalent to the hydrochloric acid of the bydro-
chlorate of ammonia being retained in the chloride of calcium. The first
process always requires an expenditure of three equivalents of acid, as in
both cases three equivalents of sulphate of lime are produced.
This Invention thus consists in the manufacture of phosphates of ammonia
and ammoniaco-magnesian phosphates in the manner herein described. As
regards the phosphate of ammonia, its manufacture has never been attempted
nor proposed by the means described, that is, producing acid phosphate by the
reaction of sulphate of ammonia on bi-phosphate of lime. The production of
ammoniaco-magnesian phosphate, according to the first method described is
new, as distinguished, first, by the employment of bi-phosphate of ammonia,
the method of producing which is itself also new; and, secondly, in the direct
combination produced between the bi-phosphate of ammonia and magnesia.
As regards the second method of manufacturing ammoniaco-magnesian
phosphate it also differs from any method heretofore practised. Thus it has
ouly been proposed hitherto to utilize the ammonia from urine or contained
in water from gas or other works in a state of carbonate, or hydrosulphate in
small proportions, whereas according to this Invention I operate on an ammo-
niacal salt in the manufactured state, as found in commerce, that is, I treat
the hydrochlorate for the purpose, as before mentioned, of preventing the loss
of one-third the equivalent of acid.
Lastly, the final reaction in this, as in the preceding instance, consists in the
employment of free or carburetted magnesia, thereby permitting the whole of
the ammonia in the salt employed to be precipitated, while the magnesian salts

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said William Clark in the Great Seal Patent Office on the
5th December 1864.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, WILLIAM
CLARK, of 53, Chancery Lane, in the County of Middlesex, Engineer and
Patent Agent, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Sixth day of June, in the year of our Lord
One thousand eight hundred and sixty-four, in the twenty-seventh year of
Her reign, did, for Herself, Her heirs and successors, give and grant unto
me, the said William Clark, Her special licence that I, the said William
Clark, my executors, administrators, and assigns, or such others as I, the
said William Clark, 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 "IMPROVE-
MENTS IN THE PREPARATION OF PROSPHATES OF AMMONIA AND AMMONIACO-
MAGNESIAN PHOSPHATE," a communication to me from abroad by Emmanuel
Adrien Lesieur, of 29, Boulevart St. Martin, Paris, Engineer Chemist, upon
the condition (amongst others) that I, the said William Clark, 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 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 William Clark, do hereby declare
the nature of the said Invention, and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following
statement, that is to say :-
Ammoniaco-magnesian phosphate has long been recognised as forming an
excellent manure, although it has never been made the subject of special

page_text: manufacture. Some of the processes described in the course of the present
Specification differ entirely from anything that has been done hitherto, and
relate more particularly to the special preparation of this product.
Phosphates of ammonia it is evident will also form excellent manure, as
they contain the two matters most useful to vegetation, and that in the
smallest possible compass. By reason of the ammonia contained they act the
same as ammoniacal salts, hydrochlorate and sulphate, and through the
phosphoric acid even better than phosphate of lime. These matters have
never hitherto been prepared with a view to their application as manures.
Methods of manufacturing phosphates of ammonia.-I first prepare the
acid phosphate of ammonia serving to produce the other substances, as will
be seen in the course of this description. According to the improved method
of manufacturing acid phosphate, I treat bones in any suitable condition, or it
may be nodules or coprolites, by means of hydrochloric or sulphuric acids in
the ordinary manner, and further precipitate the resulting liquors by means of
sulphate of ammonia, which second part of the operation constitutes the
novelty of the process, as acid phosphate of ammonia has never before been
prepared in this manner. By the employment of bydrochloric acid, the
following reactions take place :-
1st. Pho 3CaO+2HCI-PhO' CaO+2CaCl.
2ndly. Pho CaO+2CaCl+3(SO³ AzH³)
=3(SO CaO)+PhO AzH³+2(HCI Az H³).
In the first operation the tribasic phosphate of lime treated with hydro-
chloric acid produces bi-phosphate of lime and chloride of calcium; these two
products on being placed in the second operation in the presence of sul-
phate of ammonia produce sulphate of lime which is precipitated, and also
bi-phosphate and hydrochlorate of ammonia which are separated by crystal-
lization. When treating bones and other substances with sulphuric acid, the
following reactions take place:-
1st. PhO 3CaO+2SO*=PLO CaO+2(SO® CaO).
2ndly. PhO CaO+SO® AzH*=PhO*AzH*+SO® CaO.
In the first operation the action of the sulphuric acid on tribasic phosphate
of lime produces an insoluble sulphate of lime and bi-phosphate of lime;
this bi-phosphate of limo separated from the sulphate is then treated with
sulphate of ammonia to obtain bi-phosphate of ammonia and phosphate of lime.
Bi-phosphate of ammonia obtained by either of the foregoing methods may be
sold in that form as manure, or it may be previously transformed into neutral
phosphate or tribasic phosphate by saturating it in caustic ammonia or car-

page_text: proportions.
These transforma
are represented by the following formula:-
1st, Pho AzH+AzH-Pho³ 2AzF³
or Pho³ AzH³+CO AzH³= PhO' 2AzH³+CO².
2ndly. Pho AzH³+2 AzH³= PhO³ 3 AzH³
or Phos AzH+2(CO2 AzH³)= PhO³ 3 AzH³+2 CO².
I also employ raw ammoniacal liquids for saturating the bi-phosphate of
ammonia, the origin of which liquids are indicated in the following paragraph.
I also directly prepare bibasic phosphate of ammonia by a novel process,
which consists in saturating the bi-phosphate of lime until it becomes slightly
alkaline with waters rich in carbonate, and hydrosulphate of ammonia
resulting from the distillation of waste waters, gas condensing water, or that
produced by the calcination of animal matters; in fact, ammoniacal waters
obtained from any source whatever, phosphate of ammonia never having been
before manufactured from these raw ammoniacal liquids.
Ammoniaco-magnesian phosphate.-Instead of using biphosphate of
ammonia in the above form, or after having transformed it into neutral or
tribasic phosphate, I may make it serve in the preparation of ammoniaco-
magnesian phosphate. If hydrochloric acid be employed for dissolving the
bones after precipitating it with sulphate of ammonia, a liquor results com-
posed of bi-phosphate and hydrochlorate of ammonia, which liquor I boil or
place in contact in a cold state with magnesia; the latter directly combines
with the bi-phosphate of ammonia, and produces- ammoniaco-magnesian
phosphate, which is precipitated (there should be two equivalents of magnesia
for one of phosphate of ammonia), this reaction being new and never before
practised. The reaction is expressed by the following formula :-
Phos AzH+2(HCI AzH³)+2 MgO= PhO'(2 MgO AzH³)+2(H³Az H³).
The hydrochlorate of ammonia which remains inert during the reaction may
be recovered from the liquor in which is deposited the ammoniaco-magnesian
phosphate. Carbonate of magnesia may also be substituted for the magnesia,
when it will stand thus:-
Pho AzH+2(HCI AZH)+2(CO' MgO)=Ph0°(2 MgO AZH°)
+2(HCI AZH³)+2CO².
When the preparation of bi-phosphate of ammonia is effected by the
employment of sulphuric acid, the liquid does not contain any other salt. The
following are the reactions:-

page_text: The neutral and tribasic phosphate of ammonia of which I have described
the preparation, treated with magnesia the same as acid phosphate, also
produce ammoniaco-magnesian phosphate, the excess of ammonia they con-
tain being set at liberty. The following are the formulæ representing the
reactions :-
Pho 2 AzH³+2MgO=Pho³ (2 MgO AzH³)+AzH³
Pho³ 2AzH³+2Mg0=Pho³ (2 MgO AzH³)+2 AzH³.
By employing carbonate of magnesia instead of magnesia, similar reactions
may be obtained. I also claim the preparation of ammoniaco-magnesian
phosphate by means of phosphates of ammonia obtained by the ordinary
processes, treating them with magnesia or its carbonate, such process being
entirely new. I also prepare ammoniaco-magnesian phosphate according to
a second process by a similar reaction to that forming the base of the first.
Thus, in the same way as the reaction produced between the magnesia &
phosphates of ammonia a reaction also takes place between the ammonia and
the bibasic neutral phosphate of magnesia.
The bibasic phosphate of magnesia, which is almost insoluble in water, if
simply agitated in a liquor containing carbonato hydrosulphate of ammonia or
free ammonia, absorbs the base (one equivalent of bibasic magnesian phos-
phate combines with one equivalent of ammonia) and produces by means of
reactions never before indicated ammoniaco-magnesian phosphate. The
following reactions may be produced either in a heated or cold state:-
Pho 2 MgO+AzH³-Pho (2 MgO AzH³); PhO 2 MgO+AzH³ CO²
Pho (2 MgO AzH³+CO PhO 2 MgO+AzH³ HS
=Pho³ (2 MgO AZH³ +HS.
I also apply the above principle to the treatment of waste waters from gas
works, or resulting from the distillation of animal matters, or any other liquids
containing ammonia in either of the three conditions before indicated. The
quantity of phosphate of magnesia being suitably proportioned the aminonia
is totally absorbed, the water which floats on the insoluble ammoniaco-magne-
sian phosphate containing no further traces of it. From the foregoing it will
be seen that the same treatment is also applicable to the complex products of
night soil, and that the bibasic phosphate of magnesia by absorbing the whole
of the ammonia contained in the liquid part produces ammoniaco-magnesian
phosphate which becomes precipitated and unites with the solid matter
forming when dried a much richer product. I also employ the bibasic phos-
phate of magnesia in the treatment of stable and other manures or fertilizing
matters which have a tendency to become deprived of ammonia by fermenta-
tion; this body absorbs the ammonia by transforming it into ammoniaco-

page_text: inagnesian phosphate, the material treated thus preserving all its azote. The
bibasic neutral phosphate of magnesia serving for the preparation of ammo-
niaco-magnesian phosphate may be obtained in various ways.
1st, I precipitate the salts of magnesia, sulphate, and chloride, or the mother
water from salt marshes (which are rich in magnesian salts), by means of
bibasic phosphate of potash or soda. This method of preparation is well known
with the exception of its application to the mother waters of salt marshes,
which is new, although it has never served as a base for any manufacture.
2ndly, I prepare phosphate of magnesia, which is in this case mixed with
phosphate of lime, by saturating biphosphate of lime in solution with caustic
or carbonated magnesia until the liquor becomes slightly alkaline.
The whole of the acid phosphate of lime is extracted, the precipitate
obtained, consisting of a mixture of phosphate of magnesia and bibasic phos-
phate of lime; this method of preparing bibasic phosphate of magnesia being
entirely new. The following is the formula of reaction:-
2(PhO*CaO)+2MgO=PhO ?MgO+PhO ?CaO or 2(PhO CaO)
+2(CO*MgO)=PhO 2MgO+PhO 2CaO+2CO.
I also employ dolomite, either calcined or not, in the saturation. In this
case the precipitate only contains one-third of phosphoric acid in the form of
phosphate of magnesia.
Lastly, I also manufacture phosphate of magnesia by saturating phosphoric
acid or acid phosphate of magnesia as used in commerce, the first with two
equivalents of magnesia, and the second with one equivalent only of this base.
In these two cases the liquor being rendered slightly alkaline, all the phos-
phoric acid is precipitated in the form of bibasic phosphate of magnesia; the
magnesia may also be replaced by its carbonate. I also employ dolomite
either in a natural condition or calcined for the saturation of the phosphoric
acid, or I may use acid phosphate of magnesia, in which case the product
obtained is accompanied with phosphate of lime, which methods of manu-
facture are entirely new.
Having described the nature of this Invention and the manner of perform-
ing the same, I declare that what I claim as the Invention to be protected by
the herein-before in part recited Letters Patent is,
The preparation of acid phosphate of ammonia by means of biphosphate of
lime and sulphate of ammonia.
The preparation of bibasic and tribasic phosphates of ammonia by the
saturation of acid phosphate of ammonia obtained in the manner described
by means of ammonia or its carbonate, or it it may be raw products (rich
in carbonate and hydrosulphate of ammonia); also by the distillation of

page_text: ammoniacal waters from various sources, such as gaswater and those resulting
from the calcination of animal matters.
The direct preparation of bibasic phosphate of ammonia by means of acid
phosphate of lime and the raw products resulting from the distillation of the
ammoniacal waters above-mentioned. The preparation of ammoniaco-mag-
nesian phosphato by means of phosphates of ammonia prepared according to
this Invention, or by the ordinary processes (and magnesia or its carbonate.
The preparation of ammoniaco-magnesian phosphate by means of bibasic
neutral phosphate of magnesia and ammoniacal waters of any suitable
nature.
The application of the above principle, that is to say, the treatment with
bibasic phosphate of magnesia, 1st, to the complex products of night soil,
by which a much richer dry product may be obtained; 2ndly, to stable and
other manures liable to disengage ammonia so as to preserve the whole of the
azote with which they are enriched.
The preparation of bibasic phosphate of magnesia employed in the second
mode of preparing the ammoniaco-magnesian phosphate and its two appli-
cations by means, first, of the bibasic phosphates of potash or soda and
magnesian salts, chloride, or sulphate, or the mother waters from salt
marshes; secondly, of bi-phosphate of lime, magnesia, or its carbonate; or,
lastly, dolomite either natural or calcined; thirdly, of phosphoric acid or acid
phosphate of magnesia used in commerce, and magnesia, its carbonate, or
dolomite either natural or calcined.
In witness whereof, I, the said William Clark, have hereunto set my
hand and seal, this Fifth day of December, in the year of our Lord
One thousand eight hundred and sixty-four.
Witness,
JAMES DAISH,
53, Chancery Lane,
London.
W. CLARK. (L.S.)