IMPROVEMENTS IN THE MANUFACTURE OF ARTIFICIAL MANURES
Year: 1872

page_text: LETTERS PATENT to Benjamin Tanner, of Liverpool, in the County of
Lancaster, for the Invention of "IMPROVEMENTS IN THE MANUFACTURE
OF ARTIFICIAL MANURES."
Sealed the 4th April 1873, and dated the 9th October 1872.
PROVISIONAL SPECIFICATION left by the said Benjamin Tanner at the
Office of the Commissioners of Patents, with his Petition, on the
9th October 1872.
I, BENJAMIN TANNER, of Liverpool, in the County of Lancaster, do
hereby declare the nature of the said Invention for "IMPROVEMENTS IN
THE MANUFACTURE OF ARTIFICIAL MANURES," to be as follows:-
In the preparation of artificial manures it is usual to manufacture
phosphate of lime into the well-known commercial form of "
'super-
phosphate of lime," and to intermix with it ammoniacal and other
alkaline salts, which, in practice, are to a great extent washed away
into the subsoil before they can be made use of or assimilated by the
growing crop to which they are applied.

page_text: The present Invention consists in the economical production of single,
double, and triple superphosphates having, one, two, or three alkaline
bases instead of the lime, or in addition thereto, and the production
of ammoniacal matters in combination or admixture therewith in a more
or less rapidly soluble condition, so as to produce highly concentrated
artificial manures having that varying composition and solubility of
character which any peculiarity of soil may render desirable.
For the convenience of description and reference, the following
paragraphs in which the processes embraced by this Invention are
described are numbered consecutively.
1. Solutions of any form of phosphate of lime and other mineral
phosphates are made in hydrochloric acid, phosphoric acid, water, or
mixtures thereof, by well known arrangements, which form no part
of the present Invention. These solutions are treated with silicic acid,
or sulphuric acid, or oxalic acid, or mixtures thereof, to remove any
portion of the lime present, and, by preference, the lime is thus reduced
in relation to the phosphoric acid to the proportion present in mono-
calcic, bicalcic, or tricalcic phosphate, according to the ultimate
product desired. Sulphate, silicate, or oxalate of potash or mixtures
thereof is or are then added to the liquor for the purpose of removing
all or any portion of the lime, and for substituting potash. The liquor
is separated from any insoluble salts formed by filtration, decantation,
or otherwise, and the clear liquor on evaporation yields a superphosphate
of potash, more or less intermixed with superphosphate of lime, and in
such proportions as may be desired. Any other alkaline matter may
be substituted for or used in conjunction with the potash added thereto,
by using a corresponding salt or salts of such alkaline matter, and any
form of single, double, or triple superphosphate can thus be produced,
according to the proportions of the base or bases employed.
2. A very similar result is attained by adding the base or bases to be
substituted for the lime or alkaline matter in. a caustic condition, or
in combination with any acids or elements, which during the process
of manufacture are decomposed or volatilised, such as chlorides, for
example. In such cases it is preferred to remove that quantity of lime
or other base (from the solution of phosphate) which is equivalent to
the base or bases to be added or substituted. This is done by the use
of silicic acid, sulphuric acid, oxalic acid, or mixtures thereof, in the

page_text: manner described in the paragraph of this Specification numbered 1.
The proportions may, in like manner, be balanced by making an
addition of phosphoric acid to the solution of phosphate (prepared as
before described) equivalent to the quantity of base or bases to be added.
The liquor is, by preference, separated from any insoluble matter by
filtration, decantation, or otherwise, and is then crystallised or eva-
porated to dryness, and produces any form of single, double, or triple
superphosphate, according to the proportions of the salt or salts.
employed.
3. Phosphoric acid or phosphoric and hydrochloric acids, more or less
diluted with water, are also treated in the required proportions with the
base or bases in a caustic condition, or in combination with any acids
or elements (such as chlorides), which during the process are decomposed
or volatilised, and their solutions when evaporated produce any form of
single, double, or triple superphosphate, according to the proportion in
which the base or bases has or have been added. The superphosphates
produced by the processes described in this and the two preceding
paragraphs are sometimes further concentrated by dissolving the soluble
portion in water, separating insoluble matter, and evaporating the liquor
in the manner herein-after described, and when it is desired for the
product to be richer in alkali an additional quantity of alkaline matter
is added.
4. These solutions when prepared for evaporation, as described in the
preceding paragraphs, are intermixed with shoddy, woollen waste, blood,
flesh, or other form or forms of nitrogenised matter, or mixtures thereof,
and evaporated to dryness. The quality of the product is improved by
the passage of steam or superheated steam over the surface or through
the drying mass. When the mixture has been reduced to dryness, a
single, double, or triple superphosphate is obtained, having ammoniacal
matter in a slowly soluble form intermixed therewith, the composition
of which may be varied on the same principle, according to the special
requirement of any soil or climate, but in each case enabling the
ammoniacal matter to be presented to vegetation in a slowly soluble
form.
5. The solutions of phosphate of lime and other mineral phosphates
described in the paragraph of this Specification numbered 1 are also
treated in the manner therein described (and by other well known

page_text: means for attaining the same results), so as to remove a greater
proportion of the lime or other base than is therein described, or
solutions of phosphoric acid, more or less perfectly purified, are inter-
mixed with shoddy, woollen waste, blood, flesh, or other form or forms
of nitrogenised matter, or mixtures thereof, and evaporated to dryness.
The quality of the product is improved by the passage of steam or
superbeated steam over the surface of or through the drying mass. The
product obtained on evaporation is a slowly soluble form of ammoniacal
matter which I distinguish as "ammonio-phosphate."
6. Phosphoric acid or solutions of phosphate of lime and other mineral
phosphates in hydrochloric acid, phosphoric acid, water, or mixtures.
thereof (prepared as herein-before described) is or are intermixed with
ammonia (either in the form of chloride or carbonate, or in a caustic
condition) and with sulphate or bi-sulphate of lime. The materials aro
intermixed in such proportions that for every equivalent of phosphoric
acid present there shall also be present one, two, or three equivalents
of lime, or any intermediate quantity, but preferably one or two
equivalents; and also for every equivalent of sulphuric acid there shall
be, by preference, one equivalent of ammonia present. The lime salts
employed may be dissolved in hydrochloric acid or other convenient
solvent before such intermixture, or such acid or other solvent may be
added after intermixture. The mixture may be conveniently effected
in a vessel having rotating arms or other agitating arrangements, with or
without the application of heat, until the decomposition is effected.
The mixture is then passed through a filtering arrangement to remove
any insoluble matter, and the clear liquor evaporated, or the mixture
may be evaporated to dryness without the separation of the insoluble
matter. The dry residuo thus obtained may be subjected to further
application of heat (preferably in the form of steam or superheated
steam, or any mixture thereof with hot air) till acid fumes cease to come
off, controlling and stopping the decomposition at any stage that may
be desired. The product will be a superphosphate of lime having
ammonia in a rapidly soluble form intermixed therewith, and which
can be further concentrated in the manner described in the paragraph
of this Specification numbered 3, or a superphosphate of lime may be
formed, and the ammoniacal salt separated as a bye product.
7. When it is desired to separate any portion of the ammoniacal salt
formed in the manner described in the paragraph of this Specification

page_text: numbered 6, the liquor which has been prepared for evaporation is
concentrated in the usual manner sufficiently to enable the ammoniacal
salt to crystallise out, and the liquor thus more or less fully deprived of
such ammoniacal salt is evaporated to dryness, yielding a product
similar to that described in the said paragraph numbered 6, but less
rich in ammonia.
8. The several forms of superphosphate produced by the processes
herein described may be intermixed with phosphoric acid after they
have been manufactured, or phosphoric acid is added to the liquor, or
the relative proportion of phosphoric acid increased by other means
prior to or during the evaporation of the several liquors, and by adopting
this course of procedure any superphosphate may be phosphated and
rendered more powerful as a manure, and, on evaporation to dryness,
obtained in as dry a condition as ordinary superphosphate of lime.
9. It is preferred to carry out the evaporation of the several liquors
(prepared in the manner described in the preceding paragraphs) by the
use of steam or hot air, or mixtures thereof, and although the same
results may be obtained by evaporation under the direct action of fire
in the ordinary manner, still the steam excrcises a softening influence
upon the heat, and the action is safer and in every way more
satisfactory.
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Benjamin Tanner in the Great Seal Patent Office
on the 7th April 1873.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, BENJAMIN
TANNER, of Liverpool, in the County of Lancaster, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Ninth day of October, in the year
of our Lord One thousand eight hundred and seventy-two, in the thirty-
sixth year of Her reign, did, for Herself, Her heirs and successors,
give and grant unto me, the said Benjamin Tanner, Her special licence
that I, the said Benjamin Tanner, my executors, administrators, and
assigns, or such others as I, the said Benjamin Tanner, my executors,
administrators, and assigns, should at any time agree with, and no others,

page_text: 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 "IMPROVEMENTS IN THE MANU-
FACTURE OF ARTIFICIAL MANURES," upon the condition (amongst others)
that I, the said Benjamin Tanner, 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 Offico within six
calendar months next and immediately after the date of the said Letters
Patcut.
NOW KNOW YE, that I, the said Benjamin Tanner, do hereby declare
the nature of my 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 :—
In the preparation of artificial manures it is usual to manufacture
phosphate of lime into the well known commercial form of "Super-
phosphate of Lime," and to intermix with it ammoniacal and other
alkaline salts, which in practise are to a great extent washed away into
the subsoil before they can be made use of or assimilated by the growing
crop to which they are applied.
The present Invention consists in the economical production of single,
double, and triple superphosphates, having one, two, or three alkaline
bases instead of the lime, or in addition thereto, and the production of
ammoniacal matters in combination or admixture therewith in a more
or less rapidly soluble condition, so as to produce highly concentrated
artificial manures having that varying composition and solubility of
character which any peculiarity of soil may render desirable.
For the convenience of description and reference, the following para-
graphs in which the processes embraced by this Invention are described,
are numbered consecutively.
1. Solutions of any form of phosphate of lime or other mineral
phosphates are made in hydrochloric acid, phosphoric acid, or water, or
mixtures thereof, by well known arrangements which form no part of
the present Invention. These solutions are treated with silicic acid, or
sulphuric acid, or oxalic acid, or mixtures thereof, to remove any

page_text: portion of the lime present, and by preference the lime is thus reduced
in relation to the phosphoric acid to the proportions prosent in mono-
calcic, bicalcic, or tricalcic phosphate, according to the ultimate product
desired. Take for example a solution made from a phosphate of lime
containing five per cent. of lime over and above the quantity required to
form tricalcic phosphate, then in working a solution of one ton of such
phosphate, one hundredweight of lime which is in excess will have to
be removed to make the solution contain lime and phosphoric acid in
the same proportion as in tricalcic phosphate. This is accomplished by
mixing with the said solution one hundred and cighty pounds of silicic
acid, or one hundred and sixty pounds of anhydrous sulphuric acid
(in any more or less dilute condition), or two hundred and fifty-two
pounds of crystallized oxalic acid (by preference in solution), or any pro-
portional mixture thereof, in the manner herein-after described. If it be
desired to have the lime and phosphoric acid in the proportions existing
in bicalcic or monocalcic phosphate then an additional quantity of the
above-named acid or acids will have to be employed for the purpose of
removing the excess of lime, that is to say, for every twenty-eight pounds
of lime to be removed from the solution, forty-five pounds of silicic acid
or forty pounds of anhydrous sulphuric acid (in any more or less dilute
condition), or sixty-three pounds of crystallized oxalic acid (preferably
in solution), or any proportional mixtures thereof, will be necessary. In
those cases in which the solution does not contain more lime than is
desired, as, for example, when the solution has been effected by or
conjointly with phosphoric acid, the above treatment is not necessary.
Having the solution in the desired condition, sulphate, silicate, or
oxalate of potash, or any mixtures thereof, is or are then added (by pre-
ference in solution) to the liquor for the purpose of substituting potash
for all or any portion of the lime.
The quantity will vary according to the composition of the product
desired, and as the potash which is thus added carries with it an equiva-
lent quantity of sulphuric acid, or silicic acid, or oxalic acid, which
remove lime also in equivalent proportion to the potash added, it is
obvious that the substitution of the potash for lime can be carried out
to any extent the manufacturer may desire. On the same principle any
other alkalies may be substituted for or used in conjunction with the
potash by using a corresponding salt or corresponding salts of such
alkalies, varying the proportions according to the composition of the

page_text: product desired and the relative combining proportions of the salt or
salts employed.
The required quantity of the before-named acid or acids and salt or
salts necessary for the production of the desired form of superphosphate
may be added to the solution of the phosphate in one or more operations,
and if desired the salt or salts may be previously mixed with the acid or
acids employed.
The mixture is conveniently effected in a vat or tub fitted with re-
volving arms or other arrangements for keeping the mixture gently
agitated, and the liquor is freed from the lime, salt, or salts either by
filtration, decantation, or otherwise. The solution thus obtained is
evaporated and treated in the manner detailed in the paragraph hereof,
numbered 6, and yields any form of single, double, or triple superphos-
phate varying in composition according to the relative proportions in
which the salt or salts has or have been employed.
2. A very similar result is attained by adding the base or bases to be
substituted for the lime or alkaline matter in a caustic condition or in
combination with any acids or clements which during the process of
manufacture are decomposed or volatilised, such as chlorides for example.
In such case it is preferred to remove from the solution of phosphate
(in which the lime and phosphoric acid has previously been brought into
the proportions existing in monacalcic, bicalcic, or tricalcic phosphate)
that quantity of lime or other base which is cquivalent to the base or
bases to be substituted or added. This is done by the use of silicic acid,
sulphuric acid, oxalic acid, or mixtures thereof in the manner described
in the paragraph of this Specification numbered 1. The proportions
may in like manner be balanced by making an addition of phosphoric
acid to the solution of phosphate (prepared as before described) equiva-
lent to the quantity of base or bases to be added.
The liquor is by preference separated from any insoluble matter by
filtration, decantation, or otherwise, and is then crystallized or evapo-
rated to dryness in the manner described in the paragraph hereof
numbered 6 and produces any form of single, double, or triple super-
phosphate according to the proportions of the salt or salts employed.
3. Phosphoric acid or phosphoric and hydrochloric acids more or less
diluted with water are also treated in the required proportions with the

page_text: base or bases in a caustic condition or in combination with any acids or
elements (such as chlorides) which during the process are decomposed
or volatilised, and their solutions when evaporated in the manner
described in the paragraph hereof numbered 6 produce any form of
single, double, or triple superphosphate, according to the proportion in
which the base or bases bas or have been added. The superphosphates
produced by the processes described in this and the two preceding para-
graphs are sometimes further concentrated by dissolving the soluble
portion in water, separating insoluble matter, and evaporating the liquor
in the manner herein-after described, and when it is desired for the
product to be richer in alkali an additional quantity of alkaline matter
is added.
4. These solutions when prepared for evaporation, as described in the
preceding paragraphs, are intermixed with shoddy, woollen waste, blood,
flesh, or some other form or forms of nitrogenised matter or mixtures
thereof, and evaporated to dryness. The quality of the product is im-
proved by the passage of steam or superheated steam over the surface
or through the drying mass. When the mixture has been reduced to
dryness a single, double, or triple superphosphate is obtained having
ammoniacal matter in a slowly soluble form intermixed therewith, the
composition of which may be varied on the same principle, according
to the special requirement of any soil or climate; but in each case
enabling the ammoniacal matter to be presented to vegetation in a
slowly soluble form.
5. The solutions of phosphate of lime and other mineral phosphates
described in the paragraph of this Specification numbered 1 are also
treated in the manner therein described (and by other well-known
means for attaining the same results), so as to remove a greater pro-
portion of the lime or other base than is therein described, or solutions
of phosphoric acid, more or less perfectly purified, are intermixed with
shoddy, woollen waste, blood, flesh, or some other form or forms of
nitrogenised matter or mixtures thereof and evaporated to dryness.
The quality of the product is improved by the passage of steam or
superheated steam over the surface cf or through the drying mass. The
product obtained on evaporation is a slowly soluble form of ammoniacal
matter which I distinguish as "ammonio-phosphate."
6. Phosphoric acid or solutions of phosphate of lime and other
mineral phosphates in hydrochloric acid, phosphoric acid, water, or.

page_text: mixtures thereof (prepared as herein-before described) is or are inter-
mixed with ammonia (either in the form of chloride or carbonate, or
in a caustic condition) and with sulphate or bi-sulphate of lime. The
materials are intermixed in such proportions that for every equivalent
of phosphoric acid present there shall also be present one, two, or three
equivalents of lime, or any intermediate quantity, but preferably one
or two equivalents, and also for every equivalent of sulphuric acid
there shall be by preference one equivalent of ammonia present, that
is to say, for every seventy-one pounds of phosphoric acid present
there shall also be twenty-eight, or fifty-six, or eighty-four pounds
of lime, or any intermediate quantity (but preferably twenty-eight or fifty-
six pounds), and also for every forty pounds of anhydrous sulphuric acid
there shall be (preferably) seventeen pounds of ammonia present. The
lime salts employed may be dissolved in hydrochloric acid or other
convenient solvent before such intermixture, or such acid or other
solvent may be added after intermixture. The mixture may be con-
veniently effected in a vessel having rotating aruns or other agitating
arrangements with or without the application of heat, until the decom-
position is effected. The mixture is then passed through a filtering
arrangement to remove any insoluble matter, and the clear liquid
evaporated; or the mixture may be evaporated to dryness without
the separation of the insoluble matter. The dry residue thus obtained
may be subjected to further application of heat, preferably in the form
of steam or superheated steam, or any mixture thereof with bot air,
having regard to the conditions specified in the paragraph hereof
numbered 9, till acid fumes cease to come off controlling and stopping.
the decomposition at any stage that may be desired. The product
will be a superphosphate of lime having ammonia in a rapidly soluble
form intermixed therewith, and which can be further concentrated in
the manner described in the paragraph of this Specification numbered 3,
or a superphosphate of lime may be formed and the ammoniacal salt
separated as a bye product.
7. When it is desired to separate any portion of the ammoniacal salt
formed in the manner described in the paragraph of this Specification
numbered 6, the liquor which has been prepared for evaporation is con- :
centrated in the usual manner sufficiently to enable the ammoniacal salt
to crystallize out, and the liquor thus more or less fully deprived of such
ammoniacal salt is evaporated to dryness, yielding a product similar to

page_text: that described in the said paragraph, numbered 6, but less rich in
ammonia.
8. The several forms of superphosphate produced by the processes
herein described may be intermixed with phosphoric acid after they have
been manufactured, or phosphoric acid is added to the liquor, or the
relative proportion of phosphoric acid increased by other means prior to
or during the evaporation of the several liquors, and by adopting this
course of procedure any superphosphate may be phosphated and rendered
more powerful as a manure, and on evaporation to dryness obtained in as
dry a condition as ordinary superphosphate of lime.
9. It is preferred to carry out the evaporation of the several liquors
(prepared in the manner described in the preceding paragraphs) by the
use of steam, or hot air, or mixtures thereof, and although the same
results may be obtained by evaporation under the direct action of fire in
the ordinary manner, still the steam exercises a softening influence on
the heat, and the action is safer and in every way more satisfactory. It
may be observed that in the evaporation and subsequent drying in any
of the processes herein-before mentioned it is preferred that it should be
done at a temperature neither exceeding 280° Fahrenheit when dry heat
is used nor exceeding 450° Fahrenheit when superheated steam is
employed.
When any mixture of steam and hot air is employed the temperature
is regulated according to the proportion in which they are mixed, that is
to say, as the temperature is increased so the proportion of steam is also
increased. It should be observed that the proportions employed for the
purposes of my said Invention are not in all cases precisely such as are
herein-before mentioned, as such proportions may, as will be well under-
stood by persons conversant with the manufacture of analogous chemical
products, in some instances, according to the state of the materials used
in regard to the admixture of impurities or foreign matters, be varied
without departing from the principles of my said Invention.
Having thus declared and ascertained the nature of my said Inven-
tion, and in what manner the same is to be performed, I would
observe in conclusion that what I consider novel and original, and there-
fore claim as constituting the Invention secured to me by the said
herein-before in part recited Letters Patent is, the manufacture of
artificial manures by means of the processes and treatment of the

page_text: several substances herein mentioned, substantially as hercin-before set
forth and described, or any mere modifications thereof.
In witness whereof, I, the said Benjamin Tanner, have hereunto
set my hand and seal, this Third day of April, in the year of our
Lord One thousand eight hundred and seventy-three.
Witness to the signature of the
said Benjamin Tanner,
HENRY TANNER.
BENJAMIN TANNER. (L.s.)