IMPROVE- MENTS IN THE TREATMENT AND PREPARATION OF PHOSPHATIC MATERIALS
Year: 1871

page_text: LETTERS PATENT to Robert Irvine, of Leith, in the County of Mid
Lothian, North Britain, and Charles Neville Johnson, of the Town
and County of Newcastle-upon-Tyne, for the Invention of "IMPROVE-
MENTS IN THE TREATMENT AND PREPARATION OF PHOSPHATIC MATERIALS."
Sealed the 20th October 1871, and dated the 24th April 1871.
PROVISIONAL SPECIFICATION left by the said Robert Irvine and
Charles Neville Johnson at the Office of the Commissioners of
Patents, with their Petition, on the 24th April 1871.
We, ROBERT IRVINE, of Leith, in the County of Mid Lothian, North
Britain, and CHARLES NEVILLE JOHNSON, of the Town and County of
Newcastle-upon-Tyne, do hereby declare the nature of our said Invention
for "IMPROVEMENTS IN THE TREATMENT AND PREPARATION OF PHOSPHATIC
MATERIALS," to be as follows:-
This Invention relates to the treatment and preparation of phosphatic
materials, such, for example, as mineral phosphate of lime, commonly
known as apatite, Spanish, German, Canadian or Charles Town phosphate,

page_text: guanos, bones, bone ash, coprolites, indeed all substances containing
phosphate of lime in sufficient quantity to make their use profitable so as
to render their constituents suitable for manures or for other purposes.
We firstly dissolve any of these substances in hydrochloric (or
muriatic) acid (so as to separate the insoluble silicious matter present)
either with or without the application of heat, and having obtained a
solution of the phosphate of lime contaminated with chloride of calcium
in amount equivalent to the amount of carbonate present in the raw
material, we then either evaporate the mixed solutions until a double
compound of phosphate of lime and chloride of calcium begins to deposit
itself in the liquid. This compound we designate phosphato-chloride of
calcium. At this stage the evaporation is stopped and the thick liquid
is run into coolers where it deposits a large quantity of the above-
mentioned compound salt; this when cold we place upon drainers or
filters so as to separate the mother liquor or the portion remaining fluid.
The pasty mass so left we dry down at a temperature sufficient to cause
the acid phosphate of lime present to react upon the chloride of calcium,
in which case we obtain a compound containing a large quantity of
soluble phosphate of lime which does not materially absorb moisture
from the atmosphere. The mother liquor from this paste on being
further evaporated yields a fresh portion of the phosphate chloride, and
this we treat in a similar manner. Or we take the solution of phosphate
of lime in hydrochloric acid and add to it an equivalent quantity of
the sulphates of soda, potaslı, or ammonia, or the bi-sulphates of these
alkalies, so that the sulphuric acid present shall combine with the lime
present in the muriatic acid solution of crude phosphate, forming, as is
well known, insoluble sulphate of lime. The fluid which separates or
drains away from the precipitate so formed we evaporate down until the
chlorides formed by the double decomposition which takes place settle
down or salt out from the solution containing it. The evaporation of
the portion still fluid is carried on to dryness so as to obtain. the phos-
phoric acid combined with the alkaline bases enumerated. The portion
which salts out we either purify as is well understood to extract any
phosphates it may contain or we use it as manure according to the
amount of phosphates present.
We do not confine ourselves to the herein-before mentioned quantities
as we find that by using a smaller amount of alkaline sulphates we can
.obtain a manure which does not absorb moisture to any extent, but we

page_text: prefer as far as we can to separate as much lime as possible combined
with sulphuric acid as sulphate of lime, which substance may be
employed in addition to other applications in the manufacture of paper
to mix with rag or other pulp fibre.
In some cases we prefer to add the alkaline sulphates to the separated
phosphato-chloride before mentioned, in which case a less amount of
such salt or salts are required, and we dry down the mixture so as to
obtain a manure containing all the lime present therein, or we may
add the alkaline sulphates direct to the crude solution of phosphate
in muriatic acid, and dry down the whole mass at a gentle heat. We
thus obtain impure phosphates of soda, potash, or ammonia individually,
or all combined in the manure; these are directly applicable to the soil
as fertilizers. Or we take the solution of crude phosphate of lime in
muriatic acid, and boil it down nearly to dryness. We then add to the
mass whilst still moist an equivalent amount of alkaline sulphates
or of sulphuric acid, or of bi-sulphates of soda, potash, or ammonia, so
as to decompose the chloride of calcium, either in whole or in part.
After desiccation we obtain a valuable manure containing in addition
soluble phosphate of lime. Or to the solution of crude phosphate of
limo in muriatic acid we add sulphuric acid, in equivalent proportion,
to combine with the whole of the lime therein or in part only. We then
separate the sulphate of lime so formed, and evaporate the clear solution
to dryness, by which means we obtain an impure variety of phosphoric
Lacid, which we also make use of as manure, either by itself or combined
or mixed with such substances as are commonly used as dryers for
manures.
These products may also be applied to the mordanting of cloth, or, as
in the case of the crude phosphoric acid above referred to, it may be
employed in the manufacture of phosphorus. Or instead of proceeding
by any of the processes before mentioned, we take the solution of
phosphate of lime in hydrochloric acid before referred to and evaporate
it to complete dryness in pans or in specially constructed furnaces, and
thereafter incinerate or roast the residue so obtained until the free
phosphoric acid or acid phosphate of lime present has reacted upon the
chloride of calcium formed by the action of the hydrochloric (or
muriatic) acid upon the lime in the phosphate under treatment. By
this means we secure the reformation of tribasic or insoluble phosphate
of lime, associated with an amount of chlorides of calcium or magnesium,

page_text: equivalent to the carbonates of those metals present in the raw material
acted upon by the hydrochloric (or muriatic) acid in the first and well-
known portion of this process. We then remove a portion of these
chlorides from the insoluble phosphates by means of either hot or cold
water, or we add an equivalent quantity of phosphoric acid or acid
phosphate of lime, sufficient to decompose the chlorides present; this
may be added either to the solution of phosphates in hydrochloric (or
muriatic) acid, as it is first formed from the raw material, or be added
to the phosphates already rendered insoluble by incineration, and still
retaining chlorides of calcium or magnesium. Having obtained nearly
pure tribasic phosphates of lime or magnesia, we either use them by
themselves or decompose them with sulphuric acid, and so form a
compound containing soluble phosphate of lime or magnesia, suitable
for use as fertilizing agents and containing a high per-centage of soluble
phosphates.
The hydrochloric acid vapor given off during the above-mentioned
processes may be conducted into suitable condensers, and recovered for
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Robert Irvine and Charles Neville Johnson in 2
the Great Seal Patent Office on the 24th October 1871.
TO ALL TO WHOM THESE PRESENTS SHALL COME, we, ROBERT
IRVINE, of Leith, in the County of Mid Lothian, North Britain, and
CHARLES NEVILLE JOHNSON, of the Town and County of Newcastle-
upon-Tyne, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Twenty-fourth day of April, in the year
of our Lord One thousand eight hundred and seventy-one, in the thirty-
fourth year of Her reign, did, for Herself, Her heirs and successors, give
and grant unto us, the said Robert Irvine and Charles Neville Johnson,
Her special license, that we, the said Robert Irvine and Charles Neville
Johnson, our executors, administrators, and assigns, or such others as we,
the said Robert Irvine and Charles Neville Johnson, our exccutors,
administrators, or assigns, should at any time agree with, and no others,
from time to time and at all times thereafter during the term therein;

page_text: 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
TREATMENT AND PREPARATION OF PHOSPHATIC MATERIALS," upon the condition
(amongst others) that we, the said Robert Irvine and Charles Neville
Jolinson, our executors or administrators, by an instrument in writing
under our hand and scal, or under the hand and seal of one of us,
should particularly describe and ascertain the nature of the said Inven-
tion, 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 Robert Irvine, on behalf of myself
and of the said Charles Neville Johnson, do hereby declare the nature
of the said Invention, and in what manner the same is to be performed,
to be particularly described and ascertained in and by the following
statement, that is to say :-
Our said Invention relates to the treatment and preparation of
phosphatic materials, such, for example, as mineral phosphate of lime,
commonly known as apatite, Spanish, German, Canadian, or Charles
Town phosphate, guanos, bones, bone ash, coprolites, indeed all sub-
stances containing phosphate of lime in sufficient quantity to make their
use profitable.
We firstly dissolve any of these substances in hydrochloric or muriatic
acid, so as to separate the insoluble silicious matter present) either with
or without the application of heat, and having obtained a solution of
the phosphate of lime contaminated with chloride of calcium in amount
equivalent to the amount of carbonate present in the raw material, we
then either evaporate the mixed solutions until a double compound of
phosphate of lime and chloride of calcium begins to deposit itself in
the liquid. This compound we designate phosphato-chloride of calcium.
At this stage the evaporation is stopped and the thick liquid is run
into coolers, where it deposits a large quantity of the above-mentioned
compound salt; this when cold we place upon drainers or filters so as to
separate the mother liquid or the portion remaining fluid. The pasty
mass so left we dry down at a temperature sufficient to cause the acid
phosphate of lime present to react upon the chloride of calcium, in which
case we obtain a compound containing a large quantity of soluble phos-
phate of lime, which does not materially absorb moisture from the atmo-

page_text: sphere. The mother liquid from this paste on being further evaporated
yields a fresh portion of the phosphato-chloride, and this we treat in u
similar manner. Or we take the solution of phosphate of lime in hydro-
chloric acid and add to it an equivalent quantity of the sulphates of
soda, potash or ammonia, or the bi-sulphates of these alkalies, so that
the sulphuric acid present shall combine with the lime present in the
muriatic acid, solution of crude phosphate forming as is well known
insoluble sulphate of lime. The fluid which separates or drains away
from the precipitate so formed we evaporate down until the chlorides
formed by the double decomposition which takes place settle down or
salt out from the solution containing it. The evaporation of the portion
still fluid is carried on to dryness, so as to obtain the phosphoric acid
combined with the alkaline bases enumerated. The portion which salts
out we either purify as is well understood to extract any phosphate
it may contain or we use it as manure according to the amount of
phosphates present.
We do not confine ourselves to the herein-before mentioned quantities,
as we find that by using a smaller amount of alkaline sulphates we can
obtain a manure which does not absorb moisture to any extent, but we
prefer as far as we can to separate as much lime as possible combined
with sulphuric acid as sulphate of lime, which substance may be
employed in addition to other applications in the manufacture of paper
to mix with rag or other pulp fibre.
In some cases we prefer to add the alkaline sulphates to the separated
phosphato-chloride before mentioned, in which case a less amount of
such salt or salts are required, and we dry down the mixture so as to
obtain a manure containing all the lime present therein, or we may add
the alkaline sulphates direct to the crude solution of phosphate in
muriatic acid, and dry down the whole mass at a gentle heat. We thus
obtain pure phosphates of soda, potash, or ammonia individually, or all a
combined in the manure, these are directly applicable to the soil as
fertilizers. Or we take the solution of crude phosphate of lime in
muriatic acid and boil it down nearly to dryness. We then add to the
mass whilst still moist an equivalent amount of alkaline sulphates, or
of sulphuric acid, or of bi-sulphates of soda, potash, or ammonia, so as to a
decompose the chloride of calcium either in whole or in part. After
desiccation we obtain a valuable manure containing in addition soluble
phosphate of lime. Or to the solution of crude phosphate of lime in

page_text: muriatic acid we add sulphuric acid in equivalent proportion to combine
with the whole of the lime therein or in part only. We then separate the
sulphate of lime so formed and evaporate the clear solution to dryness,
by which means we obtain an impure variety of phosphoric acid which wo
also make use of as manure either by itself or combined or mixed with
such substances as are commonly used as dryers for manures.
These products may also be applied to the mordanting of cloth, or, as
in the case of the crude phosphoric acid above referred to, it may be
employed in the manufacture of phosphorus.
Or instead of proceeding by any of the processes before mentioned we
take the solution of phosphate of lime in hydrochloric acid before
referred to and evaporate it to complete dryness in pans or in specially
constructed furnaces, and thereafter incinerate or roast the residue so
obtained until the free phosphoric acid or acid phosphate of lime present
has reacted upon the chloride of calcium formed by the action of the
hydrochloric (or muriatic) acid upon the lime in the phosphate under
treatment. By this means we secure the re-formation of tribasic or
insoluble phosphate of lime associated with an amount of chlorides of
calcium or magnesium equivalent to the carbonates of those metals
present in the raw material acted upon by the hydrochloric or muriatic
acid in the first and well-known portion of this process. We then
remove a portion of these chlorides from the insoluble phosphates by
means of either hot or cold water, or we add an equivalent quantity of
phosphoric acid, or acid phosphate of lime, sufficient to decompose the
chlorides present; this may be added either to the solution of phosphates
in hydrochloric or muriatic acid as it is first formed from the raw
material, or be added to the phosphates already rendered insoluble by
incineration and still retaining chlorides of calcium or magnesium.
Having obtained nearly pure tribasic phosphates of lime or magnesia we
either use them by themselves or decompose them with sulphuric acid,
and so form a compound containing soluble phosphate of lime or
magnesia suitable for use as fertilizing agents and containing a high
per-centage of soluble phosphates.
The hydrochloric acid gas given off during the above-mentioned
processes may be conducted into suitable condensers and recovered for
use in again acting on the before-mentioned raw materials.
Having now described and particularly ascertained the nature of our
said Invention, and the manner in which the same is or may be used or

page_text: carried into effect, we would observe in conclusion that what we consider
to be novel and original, and therefore claim as the Invention secured to
us by the herein-before in part recited Letters Patent is,―
First. The treatment of phosphate materials so as to obtain what we
have called phosphato-chloride of calcium, in the manner and for the
purpose herein described.
Second. The production of sulphate of lime and of soluble phosphates
by effecting the decomposition of a solution of phosphate of lime in
hydrochloric acid by means of soluble sulphates, in the manner and for
the purpose herein-before described.
Third. The production of sulphate of lime and of phosphoric acid by
effecting the decomposition of a solution of phosphate of lime in hydro-
chloric acid by means of sulphuric acid, and the employment of the
sulphate of lime and of the phosphoric acid then obtained in the manner
and for the purpose hicrein described.
Fourth. Effecting the decomposition of chloride of calcium or of the
chloride of magnesium, and salting as herein-before described by sub-
mitting the same to the action of phosphate of lime or of phosphoric
acid at an clevated temperature in the manner and for the purposes
herein described.
In witness whereof, I, the said Robert Irvine, have to this.our
Specification set my hand and seal, the Twentieth day of
October One thousand eight hundred and seventy-onc.