Ix- PROVEMENTS IN THE SEPARATION OR OBTAINING OF AMMONIA PROM AZOTED MATTERS, AND IN THE PREPARATION OF MANURE
Year: 1863

page_text: LETTERS PATEN to
Clark, of 53, Chancery Lane, in
ounty
of Middlesex, Engineer and Patent Agent, for the Invention of "Ix-
PROVEMENTS IN THE SEPARATION OR OBTAINING OF AMMONIA PROM AZOTED
MATTERS, AND IN THE PREPARATION OF MANURE."-A communication from
abroad by Lucien IIenry Blanchard, Merchant, and Théodore Chateau,
Chemist, both of 29, Boulevart St. Martin, Paris.
Sealed the 2nd September 1863, and dated the 21st March 1863.
PROVISIONAL SPECIFICATION left by the said William Clark at the
Office of the Commissioners of Patents, with his Petition, on the
21st March 1863.
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 SEPARATION OR OBTAINING OF AMMONIA PROM
AZOTED MATTERS IN THE PREPARATION OF MANURE," to be as follows:―
This Invention consists, 1st, in causing azoted matters to be filtered through
suitable substances for retaining and settling the aminoniacal products in said
azoted matters, yet permitting the escape of the liquids after they have been
partly or entirely cleared of the azoted compounds contained therein.
2ndly, in retaining and settling or depositing partly or entirely at will the
ammoniacal compounds of azoted matters by means of phosphoric acid in a
free state or partly combined with other bases, so as to produce therefrom
acid phosphates and a salt of magnesia, forming as filtration takes place
ammoniaco-magnesian phosphate non-soluble in water, phosphoric acid freed

page_text: from the acid phosphates first applied for the retention and settling of
ammoniacal compounds in azoted matters, is prepared for trade by any
known process at a price sufficiently low to permit of its economical appli-
cation on an extensive scale. Further, free phosphoric acid or the acid
phosphates prepared for trade by any known or till now unknown process
are or may be applied in these processes. Among all acid phosphates I
choose preferably the acid phosphates of lime or bi-phosphate, and the acid
phosphate of magnesia, instead of phosphoric acid in the free state; and acid
phosphates may be substituted in this process, the solutions of neutral or basic
phosphates in mineral and vegetable acids principally in hydrochloric acid,
which solutions conjointly with the salt of magnesia, answer the same purpose
as free phosphoric acid, and consequently they act, not through the acid
solvent, but through the free phosphoric acid which arises from the dissolving
action of the mineral or vegetable acids upon the basic or neutral phosphates.
I do not limit myself to any basic or neutral phosphate, either alkaline, terreous,
alkalino-terreous, or metallic, all of them being readily dissolved in mineral
acids, but I prefer using a solution of bones or fossil phosphates (nodules
caprolites) in common hydrochloric acid. The bones I use may be either fresh
or ungelatinated, or calcined to a white state, and reduced to powder, in order
to facilitate the action of the acid. Instead of bones fresh or ungelatinated or
burnt as above, I may likewise employ the exhausted animal black from
refineries, or the refuse from the manufacture of animal black. The solution
of bone powders and in general of basic or neutral phosphates, either neutral
or artificial, is effected under ordinary pressure in a cold or hot state, or under
pressure in suitable digesters. The solution of fresh or ungelatinated bones
in muriatic acid acts very energetically in the retention or settling of ammonia
free or combined in manures. I claim the employment of phosphoric acid
and acid phosphates either in a solid, concentrated, or diluted state, and either
alone or mixed with mineral or vegetable acids. Instead of salt of magnesia I
make use of sulphate as being of a lower price, still reserving the use of any
salt of magnesia, natural or artificial, soluble or not, and capable of forming
with phosphoric acid and ammonia, ammoniaco-magnesian phosphate. As salt
of magnesia I claim the use of mother waters from salt marshes. I may
further dissolve said salts of magnesia in water or in mineral or vegetable
acids, or even mix them with phosphoric acid in the free state or with acid
phosphates, provided that the acidity of the settling products be not altered.
These latter solutions of the magnesian salts in phosphoric acid answer the
same purpose as the acid phosphate of magnesia. Acid phosphates or the
acid solutions of neutral or basic phosphates are like phosphoric acid in the

page_text: free state compounds, which are very soluble in water; these I mix with
filtering, mineral, vegetable, or animal solid matters, which serve to contain
them, and of such nature as not to alter the settling power of the acid pro-
ducts used, and that of the salt of magnesia. Thus the non-soluble carbonates
and non-soluble bases, such as lime and other like matters, would not serve,
as they would at the same time that they saturate the phosphoric acid
diminish or even annihilate its property of combination with fixed and volatile
bases. The principal filtering matters I use for supporting the settling
products are feces and paunches of aninials; powders of peat, non-soluble non-
calcareous neutral phosphates, baked or non-baked plaster free from car-
bonates, sand, charcoal, or coal powders, waste tan cakes, and other like
matters. All these filtering materials impregnated with settling products aro
placed in an apparatus upon a double bottom, either fixed or movable,
perforated with holes for permitting the escapo of the liquids, which double
bottom may be of wickerwork or metal wirework. The filtering matters
being thus impregnated with the settling compounds of azote are superposed
upon the double bottom in the most suitable order, so that the retention and
settling of ammoniacal products may be suitably effected. The fittest arrange-
ment is to place at bottom a layer of crotels, next the sulphate of magnésia in
powder, and then another layer of dry crotels saturated with a solution of
phosphoric acid in the freo state, of acid phosphate of lime, or a hydrochloric
solution of ungelatinated bones. An arrangement far simpler and quite as
beneficial is to place on the double bottom a sufficiently thick layer of filtering
matters, and afterwards a second layer saturated with phosphoric acid holding
a salt of magnesia in solution. The amount of filtering matters and of settling.
materials of ammonia free or combined should be in proportion to the amount
of azoted elements, which are to be retained and settled. The filtering ȧppa-
ratus may be of any form and dimensions, and are provided beneath tho
double bottom with an opening for the issue of the liquids which may be
passed either into vessels tightly closed, which when filled are replaced by
others, or the liquids may be conducted directly into the sewers. The filtering
apparatus once filled with anmoniacal matters, either solid or nearly so,
accumulating by filtration, are transferred tightly closed and emptied into
suitable places of deposit. The ammoniacal waters are suitably mixed with
filtering and settling substances, and then thickened to the desired consistency
by the addition of suitable absorbing matters, which matters may be the same
as those serving to contain the settling products of ammonia. :
Should it be found that the ammoniacal products when in the depot are not
sufficiently settled, I may in this case add to them, either conjointly or

page_text: separately, phosphoric acid in the conditions above stated, or it may be
sulphate of magnesia. Instead of having the ammoniacal matters liquid or
solid filtered upon the above products, I may, according to circumstances, mix
such products directly with the ammoniacal products, either on the spot or
when in the depot.
The principal applications of the Invention may be classed as follows:-
1st, filtering fecal matters or feces while fresh, whether liquid, pasty, or
solid, and also the retention and settling of the ammoniacal compounds
contained therein. The first application to filtering the said fecal matters
ensures the following results:-1st, it allows of collecting the said matters in
the most inoffensive way since they are disinfected by the very process itself;
2ndly, it permits of enriching the manure resulting from said fecal matters as
the ammoniacal matters contained therein, at the very moment of the filtration
are arrested, fixed, and settled. I may, however, mix the settling products
directly with the fecal matters from pits, said mixture being effected in
suitable proportions either in a pit or otherwise.
2ndly, I may apply it to the filtering of fresh or stale human or animal
urines, and for depositing the ammoniacal compounds contained therein. The
retaining and settling of azote may also be obtained by immediate precipitation
or by mixing the settling products directly with the urines, the chief point
being to transform the whole amount of ammonia, free or combined with
other matters, into ammoniaco-magnesian phosphate.
3rdly, I may also apply it to the filtration of ammoniacal waters resulting
from the manufacture of lighting gas for the purpose of retaining and
settling the ammonia therein in a state of ammoniaco-magnesian phosphate.
This filtration of ammoniacal matters is most important, as it permits of
utilizing in a quick economical way for the benefit of agriculture, a most
cumbrous product by extracting the ammoniacal products therefrom in a cold
state, allowing the water to run off at same time.
4thly, I may apply it to filtering waters from sewers, dirt, and generally of
all matters, either pasty or liquid containing ammonia, either free or combined
with other matters for manufacturing manure therefrom.
5thly, I may apply it to settling the ammoniacal products in solid, pasty,
liquid, or other manures chiefly when proceeding from animal or vegetable
organic matters, which are readily putrefied for the double purpose of stopping
or preventing the loss of azote in the state of ammonia, and obviating the
ammoniacal infection which results from the fermentation of any vegetable or
animal azoted matters.

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
18th September 1863.
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-first day of March, in the year of our
Lord One thousand eight hundred and sixty-three, in the twenty-sixth 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 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 Inven-
tion for "IMPROVEMENTS IN THE SEPARATION OR OBTAINING OF AMMONIA FROM
AZOTED MATTERS, AND IN THE PREPARATION OF MANURE," a com³. to me from
abroad by Lucien Henry 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 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
performed, to be particularly described and ascertained in and by the following
statement (that is to say):-
This Invention consists, 1st, in causing azoted matters to be filtered through
suitable substances for retaining and settling the ammoniacal products in said
azoted matters, yet permitting the escape of the liquids after they have been
partly or entirely deprived of the azoted compounds contained therein.
2ndly, in retaining and settling or depositing partly or entirely at will the
ammoniacal compounds of, azoted matters by means of phosphoric acid in the
free state, or partly combined with the bases, so as to produce therefrom acid

page_text: phosphates and a salt of magnesia or more simply by the aid of acid phosphato
of magnesia, so as to produce as filtration takes place ammoniaco-magnesian
phosphate insoluble in water.
3rdly, I may also proceed by precipitation, pouring phosphoric acid or acid
phosphates and a salt of magnesia on to the ammoniacal matters; or acid
phosphates of magnesia may be used in order to produce ammoniaco-magnesian
phosphate above indicated, and allow it, after standing a sufficient time to bo
separated from the liquid part, which is now of no value on account of its
being deprived of the ammoniacal compounds it contained.
Raw Matters. Phosphoric acid, freed from the acid phosphates first
applied for the retention and settling of the ammoniacal compounds in azoted
matters, is prepared for trade, either by any known or the herein-described
process, at a price sufficiently low to permit of its economical application on
an extensive scale. This phosphoric acid at 40° Beaumé may be supplied at
threepence per pound instead of the regular price of 17. to 21. for a similar
quantity. Further, phosphoric acid in a free state, or the acid phosphates
prepared for trade by any known or till now unknown process, are or may be
applicable for these purposes.
I claim under this head the manufacture of phosphoric acid and its acid
derivatives in the manner described, as being its first introduction in cominerce.
Among acid phosphates I choose preferably those of lime and magnesia.
I claim especially the manufacture and application of the latter acid.
phosphate by means of which, without the addition of other ingredients, the
ammonia may be precipitated either in a fresh state or combined in any other
liquid or solid azoted matters, and consequently to instantly disinfect said
matters. As regards its preparation it may be effected either by decomposing
the acid phosphate of lime with sulphate of magnesia, or by partially saturating
the phosphoric acid produced according to this Invention with magnesia,
carbonate of magnesia, or dolomite. I do not confine myself to any particular
method of manufacturing this salt of which I claim the use and application
as being the first to render it suitable for commercial and agricultural
purposes.
Phosphoric acid in the free state, and acid phosphates, especially those of
lime and magnesia, may be substituted in this process for the solutions of
neutral or basic phosphates in mineral and vegetable acids, especially in hydro-
chloric acid, which solutions, conjointly with the salt of magnesia, fulfill the
same office as free phosphoric acid, and consequently they act in fixing the
ammonia not through the acid solvent but through the free phosphoric acid,
producing the dissolving action of the mineral or vegetable acids upon the basic

page_text: or neutral phosphates. I do not limit myself to any basic or neutral phosphato
either of an alkaline, terreous, alkalino-terreous, or metallic nature, all of them
being readily dissolved in mineral acids, but I prefer using a solution of bones,
fossil phosphates (nodules coprolites), in common bydrochloric acid. The
bones I use may be either fresh or ungelatined, or calcined to a white heat,
and reduced to powder in order to facilitate the action of the acid. Instead
of bones fresh or ungelatined, or burnt, as above I may likewise employ the
exhausted animal black from refineries, or the refuse from the manufacture of
animal black.
:
The dissolution of bone powders, and in general of basic or neutral phos-
phates, either neutral or artificial, is effected under ordinary pressure in the
cold or hot state, or under pressure in suitable digesters. The dissolution of
fresh or ungelatined bones in muriatic acid acts very energetically in the
retention or settling of ammonia, free or combined in manures.
I claim the employment of phosphoric acid and acid phosphates either in a
solid, concentrated, or diluted state, and either alone or mixed with mineral or
vegetable acids. As regards the salt of magnesia, I use the sulphate, as being
of a lower price, still reserving the use of any salt of magnesia, natural or
artificial, soluble or not, and capable of forming with phosphoric acid and
ammonia ammoniaco-magnesian phosphate. As salts of magnesia I also
claim the use of the magnesian mother waters from salt marshes. I may
further dissolve said salts of magnesia in water or in mineral or vegetable
acids, or even mix or dissolve them with phosphoric acid in the free state, or
with acid phosphates, provided that the acidity of the settling products be not.
altered. These latter solutions of the magnesian salts in phosphoric acid
answer the same purpose as the acid phosphate of magnesia.
Use of Raw Matters.-Application by way of filtration. Acid phosphates
or the acid solutions of neutral or basic phosphates are like phosphoric acid in
the free state, compounds which are very soluble in water; these I mix with
filtering mineral, vegetable, or animal solid matters, which serve as supports
to them, and are of such nature as not to alter the settling power of the acid
products used, and that of the salt of magnesia. Thus the insoluble carbonates
and insoluble bases, such as lime and other like matters, cannot serve as
supports, as they would at the same time they saturate the phosphoric acid
diminish or even annihilate its property of combination with the fixed and
volatile bases. The principal filtering matters I use for supporting the settling
products are, feces and paunches from animals, powdered peat, insoluble
non-calcareous neutral phosphates, baked or unbaked plaster (free from
carbonates) sand, charcoal, coal dust, waste tan cakes, and other like matters.

page_text: All these filtering materials impregnated with settling products are placed in
an apparatus upon a stationary or movable double bottom, perforated with
holes for permitting the escape of the liquids, which double bottom may be
replaced by wicker or wire work, perforated sheet iron, or otherwise. The
filtering matters being thus impregnated with the settling compounds of
azote, are superposed upon the double bottom in the most suitable order, so
that the retention and settling of ammoniacal products may be properly
effected. The fittest arrangement is to place at bottom a layer of crotels, next
the sulphate of magnesia in crystals, and then another layer of dry crotels
saturated with a solution of phosphoric acid in a free state, or of acid phosphate
of lime, or a hydrochloric solution of ungelatined bones. An arrangement far
simpler and quite as beneficial, is to place a layer of dry crotels on the double
bottom, and afterwards a second layer saturated with acid phosphate of
magnesia, by which the use of sulphate of magnesia in crystals is dispensed
with. The amount of filtering matters, and of the settling materials of the
ammonia, whether free or combined, should be in proportion to the amount of
azoted elements which are to be retained and settled.
The filtering apparatus may be of any form and dimensions; they are
provided beneath the double bottom with an opening for the issue of the liquids
which may be run either into tightly closed casks, which when filled are
replaced by others or conveyed directly into the sewers.
The filtering
apparatus, when filled with ammoniacal matters, either solid or nearly so,
accumulating by filtration, are removed after being tightly closed and emptied
into suitable places of deposit. The ammoniacal matters are suitably mixed
with the filtering and settling substances, and then dried or thickened to the
desired consistency by the addition of suitable absorbent matters, which
matters may be the same as those serving to contain the settling products of
ammonia. Should it be found that the ammoniacal products when in the
depot are not sufficiently settled, I may in this case add to them either con-
jointly or separately, phosphoric acid in the three states above indicated, or it
may be acid phosphate of magnesia.
Application by means of precipitation.-Instead of having the ammoniacal
matters, liquid or solid, filtered upon the above products, I may according to
circumstances mix such products directly with the ammoniacal products either
on the spot, or when in the depot. Thus with regard to fecal matters in cess-
pools, urines, and water from gasworks, for example, it would be of advantage
to treat said azoted matters by precipitation. In cases where they are intro-
duced into suitable receivers, and treated in a cold state by means of acid
phosphate of magnesia, said salt fixes the ammonia in the form of ammoniaco-

page_text: magnesian phosphate. After allowing the mixture to rest, the solid part is
separated from the liquid which is now of no value, and may be decanted and
conveyed into the sewers.
The herein-described processes may be applied as follows:-1st, for filtering
fecal matters or feces, while fresh, whether liquid, pasty, or solid, and to the
retention and settling of the ammoniacal compounds contained therein. This
first application to filtering fecal matters produces the two following results :-
1st, it allows of collecting said matters in the most inoffensive way, since these
are disinfected by the very process itself; 2ndly, it permits of enriching the
manure resulting from said fecal matters, as the ammoniacal matters contained
therein are at the very moment of their filtration retained, fixed, and settled;
2ndly, said fecal matters may also be precipitated by employing acid phosphate
of magnesia, the operation being effected either in the pits or cesspools, or on the
raw undisinfected matters after being conveyed to the depot, the separation of
the liquid from the solid part is quickened by the use of chloride of manganese
or other coagulating agent; 3rdly, I may also apply it in the filtering or preci-
pitation of fresh or stale human or animal urines, or the ammoniacal waters
resulting from the manufacture of lighting gas with a view to extract the
ammoniacal or azoted compounds contained in a cold state in the form of
ammoniaco-magnesian phosphate.
The treatment of gas water and urines by precipitation, that is, by the
employment of acid phosphate of magnesia is most important, as it permits of
utilizing for the benefit of agriculture, a most cumbrous product in a quick
economical manner by extracting the ammoniacal products therefrom in a
cold state, and after allowing them to remain some hours the water is run off:
4thly, I may also apply it to filtering waters from sewers, mud, and generally
to all matters either pasty or liquid containing ammoniacal or azoted com-
pounds; 5thly, for treating, especially by precipitation, fatty water and acids
resulting from the manufacture of gelatine and glue, sour water from starch,
putrid water used in retting textile fabrics, and generally of all liquids con-
taining azoted matters, which are easily putrefied. I may also in order to
facilitate the precipitation or enrich the precipitato add ammoniacal waters
(gas water or urine) to said liquids, and then operate on the mixture; 6thly,
I may apply it to settling the ammoniacal products in solid, pasty, liquid,
or other manures, chiefly when consisting of animal or vegetable organic
matters, which are readily putrefied for the double purpose of arresting or
preventing the loss of azote in the state of ammonia, and for obviating tho
ammoniacal infection which always results from the fermentation of any
vegetable or animal azoted matters, especially the former. -

page_text: Having described the nature of this Invention, and the manner of performing
the same, I declare that what I claim as the Invention to be protected by the
herein-before in part recited Letters Patent is,-
First, filtering vegetable, mineral, animal, or ammoniacal matters in a liquid
or pasty state through suitable materials for retaining and settling the ammo-
niacal products contained therein, which filtration permits of eliminating the
liquid portion when free from its ammoniacal compounds, and of securing the
solid part which serves when enriched in the formation of manures.
Secondly, I claim retaining and fixing or settling the animonia, whether free
or combined from all kinds of animal, vegetable, or mineral azoted matters,
by means of phosphoric acid in the free state, or acid phosphates and salts of
magnesia, or it may be simply by the use of acid phosphate of magnesia, so as
to produce, as filtration is taking place, ammoniaco-magnesian phosphate
insoluble in water, and serving as a manure.
Thirdly, I claim the precipitation in a cold state of ammoniacal products
contained in all kinds of azoted matters by using principally acid phosphate of
magnesia, afterwards proceeding in the manner herein described for obtaining
manure therewith.
Fourthly, I claim the exclusive right of manufacturing phosphoric acid in
a free state, acid phosphates, and especially acid phosphate of magnesia, as
being the first to introduce these products, especially in the manufacture of
manure, which may be produced at a sufficiently cheap rate to permit of its
application on a vast scale.
Fifthly, I claim dissolving basic or neutral phosphates, whether alkaline,
alcalino-terreous, terreous or metallic, artificial, or natural, on mineral or
vegetable acids, and using such acid solution conjointly with a salt of magnesia,
for the purpose of retaining and extracting the ammonia from azoted matters,
experience having demonstrated that these solutions act through the medium
of the phosphoric acid caused by the dissolving action of mineral or vegetable
acids on basic or neutral phosphates.
Sixthly, I claim dissolving bones, either fresh, ungelatined, or calcined to a
white state, or the spent black from refineries in common muriatic acid, which
solution may be effected under the ordinary or other pressure, still reserving
the use of phosphoric acid, or acid phosphates for the same purpose, either
alone, concentrated, diluted, or mixed with mineral or vegetable acids, and
also the use of salts of magnesia in the solid state, or dissolved in water or
acids. I do not limit myself to any peculiar form or dimensions of the filtering
apparatus described, nor to the proportions of the filtering and settling materials,
as said matters may be used in the manner deemed most suitable, and arranged
3

page_text: in such order as to more or less completely retain and deposit the azote
contained to serve as a manure.
Seventhly, I claim applying the above processes to filtering fresh fecal
matters or feces, and retaining and settling the ammoniacal compounds con-
tained therein.
Eighthly, I claim the application of said processes to the treatment of fecal
matters when in the pits or at the depots, which is effected in this case by
precipitation, employing the acid phosphate of magnesia, and any suitable
coagulating agent for facilitating the separation of the solid part from the
liquid.
Ninthly, I claim the application of the same processes for the treatment of
all kinds of urines, gas waters, and generally of all kinds of ammoniacal liquids,
extracting the ammonia when cold, and either in a free state or combined
with other matters in said liquids, the method pursued being that of precipi-
tation or the employment of acid phosphate of magnesia in order to obtain
manure therefrom.
Tenthly, I claim applying the same processes to filtering sewer waters, mud,
and generally all kinds of semi-fluid products containing ammoniacal com-
pounds.
Eleventhly, I claim applying the same processes to settling ammoniacal
compounds in manures of a readily putrescible kind, for the double purpose
of preventing the loss of ammonia, and consequently of all causes of infection
in these matters.
In witness whereof, I, the said William Clark, have hereunto set my
hand and seal, this Eighteenth day of September, in the year of our
Lord One thousand eight hundred and sixty-three.
Witness,
W. G. E. SWINNOCK,
53, Chancery Lane,
London.
W. CLARK. (LS.)