IMPROVEMENTS IN THE TREATMENT OF SUBSTANCES CONTAINING PHOSPHATE OR LIME
Year: 1866

page_text: LETTERS PATENT to Charles Norrington, of Sussex House, Plymouth,
in the County of Devon, for the Invention of "IMPROVEMENTS IN THE
TREATMENT OF SUBSTANCES CONTAINING PHOSPHATE OR LIME'
Sealed the 12th April 1867, and dated the 20th December 1866.
PROVISIONAL SPECIFICATION left by the said Charles Norrington at the
Office of the Commissioners of Patents, with his Petition, on the
20th December 1866.
I, CHARLES NORRINGTON, of Sussex House, Plymouth, in the County of
Devon, do hereby declare the nature of the said Invention for "IMPROVEMENTS
IN THE TREATMENT OF SUBSTANCES CONTAINING PHOSPHATE OF LIME," to be as
follows:-
It is a well-known fact that there are many substances containing phosphate
of lime, but which on account of the presence of a large per-centage of
carbonate of lime, iron, and other matters have hitherto been considered of
little or no value, and entirely unfit for the economical manufacture of super-
phosphate of lime.
The nature and object of my Invention is to make available for the use of
manure manufacturers and others the phosphate of lime contained in these
substances by the application of hydrochloric or muriatic acid, thereby pro-
ducing a phosphate of lime of great purity. I act upon the phosphate of lime
contained in these substances in the following manner:-I apply such a
quantity of hydrochloric or muriatic acid as will be sufficient to neutralize the-

page_text: carbonate of lime and other bases, and render soluble the phosphate of
lime; water is subsequently added in sufficient quantity to wash out the
phosphate of lime which has been rendered soluble, and the phosphate of lime
held in the solution is then to be precipitated, the water run off, and the
residue evaporated, dried down, and burnt, or it may be evaporated, dried
down, or burnt without precipitation. The residue after drying or burning
will be a phosphate of lime of great purity available for the use of manure
manufactures and others.
I also claim improvements for the use of hydrochloric acid in the manufacture
of superphosphate of lime from phosphatic substances, such as coprolites,
apatite, bone ash, and phosphatic guanos, I propose to apply such a quantity
of bydrochloric acid to either of the substances before named as shall
neutralize the carbonate of lime and render soluble the phosphate of lime;
water is subsequently to be added in sufficient quantity to hold in solution the
soluble phosphate which is then to be precipitated, and the water run off,
and the superphosphate dried or burnt, or it may be dried or burnt without
adding the water or precipitating the soluble phosphate, if not burnt I prefer
drying at the heat of boiling water, viz., 212 degrees.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Charles Norrington in the Great Seal Patent Office on the
20th June 1867.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, CHARLES
NORRINGTON, of Sussex House, Plymouth, in the County of Devon, send
greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Twentieth day of December, in the year of our Lord
One thousand eight hundred and sixty-six, in the thirtieth year of Her
reign, did, for Herself, Her heirs and successors, give and grant unto me, the
said Charles Norrington, Her special licence that I, the said Charles Nor-
rington, my executors, administrators, and assigns, or such others as I, the
said Charles Norrington, 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, 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 TREATMENT OF SUBSTANCES CONTAINING PHOSPHATE OF LINE," upon

page_text: the condition (amongst others) that I, the said Charles Norrington, 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
5 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 Charles Norrington, do hereby
declare the nature of the said Invention, and in what manner the same is
O to be performed, to be particularly described and ascertained in and by the
following statement thereof, that is to say :-
First, I by my Invention render available for the purposes of manure
manufacturers, phosphorus manufacturers, and others, those mineral and
fossil substances containing phosphate of lime which although well-known,
5 yet on account of their containing too large a per-centage of carbonate of
lime, iron, silica, and other valueless substances are generally considered
of no value in the economical manufacture of superphosphate of lime, and
I do this in the manner herein-after described by using bydrochloric acid
which has also usually been considered unfit for the same manufacture,
although it possesses valuable solvent properties and is of little cost, being a
superabundant waste product of the soda manufacture.
Secondly, I according to my Invention treat in like manner coprolitic
phosphates, apatite, bone ash, phosphatic guanos, and other mineral phos-
phates, such as are already in use for the manufacture of superphosphate
of lime.
Thirdly, I according to my Invention treat phosphatic substances with
bydrochloric acid, using only sufficient for the solution and removal thereby
of the carbonate of lime present without rendering the phosphates soluble.
Having thus stated the nature of my said Invention I will proceed to
describe the manner of performing the same.
I act upon the phosphatic substances before named (and which should be
previously finely ground or pulverized) in the following manner :-I apply
such a quantity of hydrochloric acid to either of the before-named phosphatic
substances as will be sufficient to neutralize the carbonate of lime, and I mix
in an ordinary cylinder or trough (such as is generally in use by manufacturers
of superphosphate of lime) and so render soluble the phosphate of lime. The
quantity of hydrochloric acid necessary for the purpose will be regulated by
the per-centage of carbonate of lime and phosphate of lime contained in the
substance (which should have been previously ascertained by analysis) to

page_text: which the acid is to be applied. I use as much of hydrochloric acid as shall
be sufficient to neutralize all the carbonate of lime present, and further to
dissolve the phosphate of lime; this may be determined in the first instance
by observing when all effervescence ceases, and in the next place by taking
a portion of the powder operated on, boiling it in water, filtering, and then
ascertaining whether on further digestion of the insoluble residue in hydro-
chloric acid any further solution takes place, which may be determined by
testing with ammonia or carbonate of soda which will precipitate the acid
phosphate if any be present. By this application of hydrochloric acid the
carbonate of lime will have become changed into chloride of calcium, and the
phosphate will have been converted into a soluble phosphate of lime. The
acid having been allowed some hours to act upon the phosphatic material, the
mixture is to be thrown into a tank or deep trough, the size of which must
depend upon the quantity of the mixture to be acted upon by the second part
of the process, and should be capacious enough to hold a sufficient quantity
of water to thoroughly wash the mixture by agitation, and hold in solution
the soluble phosphate of lime. The mixture should be washed with successive
quantities of water until the soluble phosphate is removed in solution. The
solution having been allowed to become clear by subsidence or by filtration
is to be run into any convenient tank, and the process of precipitating the
soluble phosphate may then be proceeded with. I take lime or soda (caustic
or the common crystallized carbonate of soda or washing soda), but by
preference I use lime in the state of lime water or milk of lime, and pour
into the tank containing the phosphate of lime in solution as much as will
precipitate all the phosphate of lime. The quantity necessary for that purpose
may be ascertained by testing with litmus paper a sample of the liquid
filtered off from the precipitated phosphate until (after successive additions
of the milk of lime) the solution ceases to give an acid reaction; the
precipitate may now be allowed to settle and the liquor run off as waste. The
precipitate is to be washed by agitation or stirring, again allowed to settle,
and the water run off as before until the chloride of calcium is removed;
the precipitate. is then dried by artifical heat at about the heat of boiling
water, it may conveniently be spread on a metal plate heated underneath
by steam. The precipitate when dried is a very superior phosphate of lime
readily soluble in dilute acids, but practically equal in its fertilizing effects in
the soil (without addition of acid) to soluble phosphate.
I treat phosphates containing a large proportion of carbonate of lime by
adding to the substances in fine powder sufficient quantity of bydrochloric acid
for the solution of the carbonate without dissolving the phosphate, which may
-

page_text: be judged of by observing closely when all effervescence from the evolution of
carbonic acid ceases. The solution obtained by settling being run off into a
tank should have any acidity present neutralized by the addition of finely
pulverized phosphate of lime so as to prevent the possibility of any phosphate
being carried off in solution by the employment of an excess of acid in the
first part of the operation; after the settlement of the liquid is this tank
the clear solution may be run off as waste matter, leaving the insoluble phos-
phate of lime, from which adhering chloride of calcium may be removed by
wasbing with water.
Having thus described the nature of my said Invention, and the manner of
performing the same, I would have it understood that I do not confine myself
to the apparatus described; but what I claim is,―
First, the treatment of substances containing a phosphate of lime with
hydrochloric acid so as to dissolve both the carbonate and phosphate of
lime, then precipitating the phosphate of lime free from impurities in a
highly concentrated form, and subsequently drying it by heat as described.
Also I claim the treatment of phosphatic substances with hydrochloric
acid, using only sufficient for the solution, and removal thereby of the carbonate
of lime present without rendering the phosphate soluble, as described.
In witness whereof, I, the said Charles Norrington, have hereunto set
my band and seal, this Seventeenth day of June, in the year of our
Lord One thousand eight hundred and sixty-seven.
A
CHARLES NORRINGTON. (L.D.)