Im- PROVEMENTS IN THE MANUFACTURE OF SOLUBLE AND ASSIMILABLE SUPER- PHOSPHATES OF LIME, BY THE APPLICATION OF PHOSPHORIC ACID AND ACID PHOSPHATES.
Year: 1865

page_text: LETTERS PATENT to William Clark, of 53, Chancery Lane, in the County
of Middlesex, Engineer and Patent Agent, for the Invention of "Im-
PROVEMENTS IN THE MANUFACTURE OF SOLUBLE AND ASSIMILABLE SUPER-
PHOSPHATES OF LIME, BY THE APPLICATION OF PHOSPHORIC ACID AND ACID
PHOSPHATES. A communication from abroad by Lucien Henri Blanchard,
Merchant, and Théodoro Chateau, Chemist, both of 29, Boulevart St.
Martin, Paris.
-
Sealed tho 13th October 1865, and dated the 25th April 1865.
PROVISIONAL SPECIFICATION left by the said William Clark at the
Office of the Commissioners of Patents, with his Petition, on the 25th
April 1865.
I, WILLIAM CLARK, of 53, Chancery Lane, in the County of Middlesex,
Engineer and Patent Agent, do hereby declare the nature of the said
Invention for "IMPROVEMENTS IN THE MANUFACTURE OF SOLUBLE AND ASSIMILABLE
SUPERPHOSPHATES OF LIME, BY THE APPLICATION OF PHOSPHORIC ACID AND ACID
PHOSPHATES," to be as follows:-
Hitherto the preparation of superphosphates of lime has been effected by
the action of sulphuric acid on basic insoluble phosphates of lime, either
natural or artificial, the acid serving to deprive the tribasic phosphate of lime

page_text: of one equivalent of lime, and thus produce soluble acid phosphate of lime, the
reaction being as follows when operating on pure products:-
PhO 3CaO + ?SO® TO=PhO CaO ?HO+?(SO® CaO HO).
According to this Invention I employ phosphoric acid in the preparation
of the superphosphates above mentioned as a substitute for the sulphuric
acid hitherto employed. The reaction (in case the products are pure) will be
as follows:-
Phos 3CaO 2 (Pho³ 3HO)=3 (Pho³ CaO 2HO) + HO.
In fact acid phosphate of lime may be obtained either by withdrawing one
equivalent of lime from the basic phosphate by means of sulphuric acid, or
by the addition of two equivalents of phosphoric acid, only the result is in the
Jatter caso much superior to the former, inasmuch as three equivalents of
acid phosphate of lime are produced instead of one; but in order to attain
this result it is necessary that the phosphoric acid should be produced at a
cheap rate. It is evident that any suitable acid phosphate may be substituted
for the phosphoric acid by reason of the amount it contains of the latter. I
have found by experiments that bones ungelatinized or burnt to whiteness,
either in pieces or in a fine powder, animal black, coprolites, nodules (or
pseudo coprolites), apatites, and phosphorites of Norway, Spain, or America,
and in fact all tribasic phosphates of lime, either singly or mixed, may be
completely decomposed by means of phosphoric acid, forming, according to the
nature of the phosphate employed and the length of the operation, a greater
or less quantity of soluble phosphate. The proportion of phosphoric acid or
acid phosphate to act on the bones or mineral phosphates is determined by
the amount of tribasic phosphate of lime contained in the phosphate under
treatment. Certain mineral phosphates, especially those containing carbonates,
in addition to the acid phosphate of limo which forms, will produce tribasic
phosphate of lime. In this case I add either an excess of phosphoric acid,
or preferably a certain quantity of sulphuric acid, which in destroying the basic
phosphate assists in the more rapid solidification of the mass. It will be
understood that I may utilize as superphosphato the imperfectly washed
residues of the manufacture of phosphoric acid and its derivatives, these
residues containing soluble products of lime, magnesia, or iron.
The Invention thus consists, 1st, in the application of phosphoric acid at
any degree of dilution or concentration for the manufacture of the products
termed superphosphates, as a substitute, either wholly or in part, for the
sulphuric acid hitherto employed for this purpose.
2ndly, in the application of alkaline, alkalino-terreous, or terreous-metallic
acid phosphates, at any degree of concentration or dilution, for the manu-

page_text: facture of manures termed superphosphates of limo, said acid phosphates being
used as substitutes, either wholly or in part, for the sulphuric acid usually
employed.
3rdly, in the application of sulphuric or phosphoric acids for transforming
into acid phosphates the tribasic phosphate of lime which is formed by the
action of phosphoric acid on carbonates of natural phosphate.
4thly, in the application of a mixture in suitable proportions of phosphoric
acid or acid phosphates and sulphuric acid for acting on mineral phosphates.
5thly, in the utilization as a superphosphate of all the incompletely washed
residues in the manufacture of phosphoric acid and its derivatives, these
residues being composed almost exclusively of sulphate of lime absorbed in
acid phosphate.
I also reserve the application of these processes, either in a hot or cold.
state, without being limited to any particular mechanical or other means
for effecting the mixture of the acid with the phosphate, or for drying
or pulverizing it. I may also add to the superphosphate obtained such
organic azoted ammoniacal nitrated or mineral matters as judged convenient
for the purpose of enriching or varying the quality of manures according to
the purposes for which they are to be employed.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said William Clark in the Great Seal Patent Office on the 25th
October 1865.
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 Twenty-fifth day of April, in the year of our Lord One
thousand eight hundred and sixty-five, in the twenty-eighth year of Her reign,
did, for Herself, Her heirs and successors, give and grant unto me, the said
William Clark, Her special licence that 1, 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 thereafter during the
term therein expressed, should and lawfully might make, use, excrcise, 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
"

page_text: OF SOLUBLE AND ASSIMILABLE SUPERPHOSPHATES OF LIME, BY THE APPLICATION OF
PHOSPHORIC ACID AND ACID PHOSPHATES," a communication to me from abroad by
Lucien Henri Blanchard, Merchant, and Théodore Chateau, Chemist, both of
29, Boulevart St. Martin, Paris, 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 bands and scals, 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):
:-
Hitherto the preparation of superphosphates of lime has been effected by
the action of sulphuric acid on basic insoluble phosphates of lime, either
natural or artificial, the acid serving to deprive the tribasic phosphate of lime
of one equivalent of lime, and thus produce soluble acid phosphate of lime,
the reaction being as follows when operating on pure products:-
PhO 5 3CaO+?(SO* HO)=PhO* CaO ?HO+?(SO3 CaO IO).
According to this Invention I employ phosphoric acid in the preparation of
superphosphates above mentioned as a substitute for the sulphuric acid
hitherto employed. The reaction, in case the products are pure, will be as
follows:-
PLO 53CaO+2(PLO 3HO)=3(Pho³ CaO 2 HO) + HO.
In fact acid phosphate of lime may be obtained either by withdrawing ono
equivalent of lime from the basic phosphate by means of sulphuric acid, or
by the addition of two equivalents of phosphoric acid, only the result is in
the latter case much superior to the former, inasmuch as three equivalents of
acid phosphate of lime are produced instead of one.
It is evident that any
suitable acid phosphate may be substituted for the phosphoric acid by reason
of the amount it contains of the latter. I have found by experiments that
bones, raw, ungelatinized, or burnt to whiteness, either in pieces or in a fine
powder, animal black, coprolites, nodules (or pseudo coprolites), apatites, and
phosphorites of Norway, Spain, or America, and in fact all tribasic phosphates
of lime, either singly or mixed, may be completely decomposed by means
of phosphoric acid, forming according to the nature of the phosphate
employed and the length of the operation, a greater or less quantity of soluble
phosphates. The proportion of the phosphoric acid or acid phosphate to act

page_text: on the bones or mineral phosphates is determined by the amount of tribasic
phosphate of lime contained in the phosphate under treatment. Certain
mineral phosphates, especially those containing carbonates, in addition to the
acid phosphate of lime which forms, will produce either tribasic phosphato of
lime or neutral phosphates of lime. In this case I add either an excess of
phosphoric acid, or preferably a certain quantity of sulphuric or other
mineral acid, which in destroying the basic or neutral phosphate assists in
the more rapid solidification of the mass. With a view to still further enrich
the superphosphates with soluble phosphates, I may also add a certain amount
of phosphoric acid to the superphosphates prepared according to this Inven-
tion. I also reserve the right of enriching any other superphosphates, however
prepared, by the addition of phosphoric acid in the manner described.
Further with a view to enrich the superphosphates with soluble phosphates
while still retaining the ammonia, I reserve the right of adding a certain
quantity of phosphate of ammonia to the superphosphate, the proportion
being determined by the richness of quality desired. I also reserve the right
of adding phosphates of soda or potash to the superphosphate if desired.
Having described the nature of this Invention, and the manner of perform-
ing the same, I would remark that these processes may be applied either in a
hot or cold state without being limited to any particular mechanical or other
means for effecting the mixture of the acid with the phosphate, or for drying
or pulverizing it; and I declare that what I claim as the Invention to be
protected by the herein-before in part recited Letters Patent to be,-
First, the application of phosphoric acid at any degree of dilation or concen-
tration for the manufacture of the products termed superphosphates, as a
substitute, either wholly or in part, for the sulphuric acid hitherto employed for
this purpose.
Secondly, I claim the application of alkaline, alkalino-terreous, terreous, or
metallic acid phosphates, at any degree of concentration or dilution, for the
manufacture of manures termed superphates of lime, said acid phos-
phates being used as substitutes, either wholly or in part, for the sulphuric
acid usually employed.
Thirdly, I claim the application of sulphuric or other mineral acid or phos-
phoric acid for transforming into acid phosphate the tribasic or neutral
phosphates of lime which are formed by the action of phosphoric acid on
carbonates of natural phosphate.
Fourthly, I claim the application of a mixture in suitable proportions of
phosphoric acid or acid phosphates and sulphuric or other mineral acids for
acting on mineral phosphates.

page_text: Fifthly, I claim adding to any superphosphate a certain quantity of phos-
phoric acid in order to enrich it in soluble phosphate.
Sixthly, I claim adding to any superphosphate a greater or less quantity of
phosphate of ammonia in order to enrich it in soluble phosphate, and in
volatile or fixed alkalies.
In witness, I, the said William Clark, have hereunto set my hand and
seal, this Twenty-fourth day of October, in the year of our Lord One
thousand eight hundred and sixty-five.
Witness,
JAMES DAISHI,
53, Chancery Lane,
London.
W. CLARK. (L.S.)