IM- PROVEMENTS IN THE MEANS OF UTILIZING REFUSE AND AZOTED MATTERS OF COMMERCE
Year: 1862

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 MEANS OF UTILIZING REFUSE AND AZOTED MATTERS OF
COMMERCE."-A communication from abroad by Messieurs Amédee Gélis
and Lucien Dusart, Chemists, both of 29, Boulevart St. Martin,
Paris.
Sealed the 21st April 1863, and dated the 7th November 1862.
PROVISIONAL SPECIFICATION left by the said William Clark at the
Office of the Commissioners of Patents, with his Petition, on the 7th
November 1862.
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 MEANS OF UTILIZING REFUSE AND AZOTED MATTERS OF
COMMERCE," to be as follows:-
This Invention relates to the utilization of azoted refuse matters, such as
horn, leather, bristles, silk fibre, animal refuse, woollen rags, and all other
products belonging to that class know by chemists under the name of albumi-
noid matters. I render these matters suitable for agricultural purposes by
transforming them into soluble and assimilable products, and when treating
woollen rags I eliminate all the animal matters through canvas or otherwise,
and then apply them for the manufacture of paper. The manufacture of
manure and the production of paper pulp may be effected simultaneously or
separately, as desired.

page_text: The improvements are based on the employment of alkaline sulphurets,
especially those of potassium and sodium, which are solvents of animal matters
without injury, and which transform them into a pulverulent state by the addition
of an acid to the solution, while further they have no influence on cotton nor
On the other hand, I may employ
other ligneous materials generally.
sulphuric acid for dissolving said animal matters, which acid, when saturated
with azoted products and having lost none of its saturating power, may be
employed for the production of acid phosphate of lime.
The following is the method of operating, for example, with woollen rags:-
I place the rags in a solution of alkaline sulphuret, the wool then dissolves,
while the cotton remains unacted upon; the latter is then removed, and after
washing may be used in the manufacture of paper; I then add fresh supplies
of rags to the sulphuret, until it becomes completely saturated with animal
matters. I also dissolve in sulphuric acid woollen refuse containing little or
no cotton, or preferably, I use animal refuse from the slaughter-house, and
when the acid is saturated I add phosphate of lime in a fine powder, and on
the acid phosphate of lime being formed I add the first-named liquor, con-
sisting of sulphuret saturated with wool; at this moment is formed an alkaline
phosphate, and the albuminoid matters are precipitated in a pulverulent state.
In this manner I produce a manure which has the advantage of possessing azote
in all its conditions. In order to separate the cotton from the wool, I
may add potash and caustic soda as solvents, at same time employing the
solution of animal matters for the production of the manure, as above
described.
Motives of economy alone have guided me in the choice of the matters
herein mentioned.
The Invention consists, 1st, in the application of alkaline sulphuret to the
solution of azoted matters for the separation of the wool from the cotton; 2ndly,
in the application of potash and caustic soda for the same purpose; 3rdly,
of dissolving the azoted matters in sulphuric acid; 4thly, of utilizing said acid
when saturated with azoted matters for the production of acid phosphate of
lime; 5thly, of saturating said acid phosphate with an alkaline liquor charged
with animal matters; 6thly, of combining these several chemical actions for
the production of an improved manure suitable for application to plants, and
containing azote in the form of hydrated and alkaline phosphates of lime,
which manure from its mode of production may be obtained at a less cost than
any heretofore manufactured.

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
7th May 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 Seventh day of November, in the year of our
Lord One thousand eight hundred and sixty-two, 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 Invention for
"IMPROVEMENTS IN THE MEANS OF UTILIZING REFUSE AND AZOTED MATTERS OF
COMMERCE," a com" to me from abroad by Messieurs Amédee Gélis and Lucien
Dusart, Chemists, both of 29, Boulevart St. Martin, Paris, upon the condition
(amongst others) that I, the said William Clark, my executors or administra-
tors, 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):-
The greater number of azoted matters of animal origin are required to
undergo various transformations before they are rendered suitable for use as
manure. For example, horn, hair, wool, leather, and others are only employed
for this purpose when all other supplies fail, and then it is only in combination
with other matters that they reach the agriculturist in the form of manure.
These matters, even after long wear, still retain their organic texture, and are
in too great a state of preservation for it to be possible to produce an imme-
diate effect-as manure.
In order that they shall acquire the greatest possible

page_text: amount of value they require to be placed in conditions the most favorable for
their ready assimilation, which with animal matters can only be effected by
rendering them soluble, or at least reducing them to a state of disagregation,
so that their various elements shall become decomposed by exposure to air or
damp. Pulverization by mechanical means but imperfectly fulfils this latter
condition, although it allows, it is true, of a more equal distribution of the
manure over the land, but it does not, however, destroy its organic texture in
the least, and neither renders it more soluble, putrescent, or assimilable... A.
point on which all agriculturists seem to agree and admit generally is, that
manure to possess great strength and at same time great continuity of action
should contain azote in various conditions. If the azote in a manure consists
entirely of ammonia, its action will be very energetic at first, but soon ceases;
if, on the contrary, it is contained in a substance such as leather, horn, or wool
its effect will be developed with certainty but with extreme slowness, in pro-
por ion to its disagregation and gradual transformation.
Guided by these considerations, I have endeavoured to produce in the
manufactory, by means of suitable agents, the various changes that azoted
matters undergo when decaying in the ground, and so produce manure in
which said azoted matters exist in all the various stages of decomposition:
This result I have attained by studying the action of various solvents on
different substances of animal origin, which led me to consider the entirely
different way in which sulphuric acid on the one hand and alkaline sulphurets
on the other hand act in presence of azoted matters in the preparation of
manure.
Before speaking of the preparation of the manure, I will give some details
relative to the action of the alkaline sulphurets and sulphuric acid on horn,
hair, wool, leather, and other animal substances.
"ACTION OF ALKALINE SULPHURETS ON ANIMAL MATTERS."
The researches of Mulder on the sulphuretted nature of proteic bodies, with
which are classed all the azoted matters herein enumerated, having established
a relation between them and the alkaline sulphurets, induced me to examine
in what manner these bodies act in relation to each other, which proves that
alkaline sulphurets, and especially those of potassium and sodium, are those
most suitable to be used as solvents of animal matters. When properly treated
the solution is obtained without a sensible alteration of the matters, as, if an acid
be added to the solution, the substance dissolved is precipitated in an insoluble
state without diminution in weight, and disengages but little ammonia. The
manner in which the alkaline sulphurets act is thus entirely confined to this

page_text: species of body, and should not be confounded with that of caustic alkalies. It
is well known in fact that potash and soda in acting on azoted matters
completely change them and disengage ammonia, while the, albuminous matter
is wholly or partially (according to the length of the treatment) transformed
into soluble products which are incapable of precipitation in acids. I will
now consider this action of alkaline sulphurets as a solution pure and simple.
The product precipitated by the acids consists of a pulverulent substance of
various colors according to the matters employed; although insoluble in water
it dissolves in alkalies like coagulated albumen and gluten, it also readily
ferments and becomes putrid on exposure to air or damp, and constitutes
without other preparation a manure of the first order, which may in certain
cases be applied direct. Alkaline sulphurets, even when in the form of weak
solutions, will dissolve a large quantity of. wool, horn, or leather (one part of
this sulphuret will dissolve from 4 to 5 parts of these substances), they will not
however act on ligneous matters, thread, or cotton, which may be boiled for a
length of time together with these bodies without changing them in the least.
This difference in the action I have utilized to allow of the employment in the
preparation of manure of wool residues of the least commercial value, 'so
that by producing excellent results I obtain a residue consisting of a first-class
article of much greater value than the original material. Rags containing
hardly 50 per cent. of animal matters are sold as wool waste, the remaining part
consisting of thread or cotton, which it is impossible to separate by sorting, as
they form part of the fabrics either as a warp, canvas or lining, nor can they
be sold as pure wool waste suitable for remanufacture, nor as rags for the manu-
facture of paper. According to this Invention, which is based on the
employment of alkaline sulphurets, the separation of the wool in the above
condition is readily effected, a ligneous matter being also obtained after the
operation which is purer than the best assorted rags.
"ACTION OF SULPHURIC ACID ON AZOTED MATTERS."
Sulphuric acid acts on azoted matters in a manner entirely different to
that of the alkaline sulphurets. In both cases a solution is obtained, but the
results of the chemical action are entirely different, the products of the action
of sulphuric acid are soluble in water even after the elimintation of the acid,
and disengage but a small amount of ammonia in cold alkalies. Sulphuric acid
will dissolve at the ordinary pressure about twice its weight of azoted matters
and much more when acting under slight pressure. Without pronouncing on
the real nature of the substances produced under these circumstances, I believe
them to consist of the same bodies as are produced during their putrefaction;

page_text: there will be found, for example, leucine, tyrosine, sugar, gelatine, and others,
all of which bodies present the azote in a new form essentially assimmible. The
sulphuric acid acting on the azoted matter by reason of the catalytic action,
neither forms any combination nor loses any of its saturating power, as it acts on
carbonates, phosphates, and other acids as if in a state of purity. However, the
sulphuric solution thus obtained may not be employed direct on account of its
acidity, and I utilize it in this state for the preparation of acid phosphate or
superphosphate of lime, which salt is very useful to vegetation, it is sufficient for
this purpose to add to the sulphuric solution calcined bones, coprolites, or
apatite finely pulverized. From the foregoing it will be observed that I
thus obtain separately two liquors, the one alkaline, and the other acid; the
first mentioned, obtained by means of the sulphurets, contains azote in an
organic matter, which is still insoluble in pure water, but entirely disorganized
and suitable for subjection to the influence of exterior agents; the second,
which is produced by the sulphuric acid, contains azote in a more advanced
state of change, no longer consisting of ammonia, and forming part of a matter
which is soluble in water. I have thus united 'in these liquors all the modi-
fications that the azoted matters can undergo by their decomposition; it is then
only necessary to mix them, in order to form a manure. I would add that
besides the azoted compounds which are of such great utility there will be found
all the elements entering into the composition of a vegetable, namely, the
organic matters lime, phosphoric acid, potash, soda, and other matters.
The acidity of the one liquor saturates the alkalinity for the other, and
produces for result a manure which is easily pulverized and suitable for
transportation wherever required. The manufacture of the manure thus
comprises four operations which I will now enumerate, viz.,-
1st, the solution of azoted matters in alkaline sulphurets; 2ndly, the solution
of the same matters in sulphuric acid; 3rdly, the saturation of the sulphuric
acid by means of the phosphate of lime; and, 4thly, the saturation of
the acid phosphate of lime previously formed by the solution of the same
animal matters in alkaline sulphurets; I will now give a practical description
of each operation separately.
"SOLUTION BY MEANS OF SULPHURETS."
This operation may be effected either in the open air at the atmospheric

page_text: as twenty times the weight of the sulphuret employed. The boiler I use;
which may be of any suitable form, is of a capacity of from three to four cubic
yards; it is furnished in the interior with a double bottom, which prevents
contact of the matters with the part heated by the furnace, a cock being
placed at the lower part to facilitate the withdrawal of the matters. The
boiler is about half filled with a solution of alkaline sulphate of variable
strength, and the rags introduced; the apparatus is then luted, and the escape
pipe for the little ammonia which may be produced being connected with the
receiver; the contents are then heated to ebullition. After a greater or less
period of time, which varies according to the concentration of the liquors, and
the quantities of material under treatment, those rags which remain undis-
solved are removed and placed in a boiler, similar to the one above described,
containing a fresh solution. Any wool or silk remaining disappears com-
pletely in this second operation, and there only remains to wash the rags in
order to extract the sulphuret with which they are impregnated, and after
being dried and sorted they may be used in the manufacture of paper, and
constitute a new source of materials for this branch of manufacture. The
first boiler is immediately charged with a fresh quantity of woollen rags, and
the operation repeated as before. When the sulphuret in the first boiler is
saturated, that is, when its action on the wool is terminated, the liquors are
withdrawn and serve for future use.
Having thus described the method of operation in the open air, if it is
desired to proceed under pressure, the quantity of rags to be introduced into
the boiler being previously determined, to which is added water, so that they
shall be about three-fourths immersed, the sulphuret is then added in quantity
about equal to one-tenth of the wool contained in the rags, as near as can be
calculated; after heating them from one to two hours the solution of the wool
will be complete; the cotton is then separated from the liquor, which is
reserved for a purpose herein-after mentioned. I have mentioned wool rags,
although the treatment of other products, such as leather, horn, or hair, will
be the same, as also for those animal substances which are introduced
without preparation or the previous elimentation of the fat, and products of
superior value, such as horsehair, hoofs, or bones, which disappear and fall
to powder in the mixture, and do not require treating by any ulterior mecha-
nical operation. I have also stated that caustic or carbonated or earthy
alkalies, as also certain salts of alkaline nature, may also be employed, although
they act less energetically than the sulphurets; at same time this action, what-
ever may be its result, assists the common purpose of producing an alkaline
sulphuret, which ultimately acts on the organic matters. In fact, all these

page_text: azoted substances are very rich in sulphur, and the immediate effect of an
alkali is to determine the separation of the most part of the sulphur under
the form of a sulphuret. This interesting reaction has been placed beyond
a doubt by the experiments of Mulder, and is moreover easily demonstrated.
"SOLUTION BY MEANS OF SULPHURIC ACID."
In this case I also effect the dissolution of the animal matters, either in the
open air, or under pressure amounting to several atmospheres, in cases where
it is wished to increase the amount of azoted products to a very great extent;
but whatever may be the mode of operation the form of the apparatus is
quite immaterial, it being simply necessary to line the boiler with lead; or
copper vessels may be used instead. The vessel employed in the open air
operation is lined with lead, and heated with steam or by fire direct; the acid
is then poured in with water and the azoted matters introduced a little at a
time; the whole is then heated, and the operation proceeded with until the
acid will no longer dissolve the organic matter. When acting under pressure
the quantity of azoted matters to be dissolved is previously determined, and
the water added together with the desired amount of acid. I have before
stated that in this manner I may increase from 8 (eight) to 10 (ten) times
the amount of matters to be dissolved, the pressure employed at same time
not exceeding 5 (five) atmospheres.
"FORMATION OF ACID PHOSPHATE OF LIME."
The phosphate of lime in a fine powder is added in small proportions to the
animalized sulphuric solution while still hot, care being taken to intimately
mix them together. The action will be rapid under these conditions, and the
phosphate will be transformed in a little time, while the amount of sulphuric
acid in the mixture being known it is easy to ascertain that of the phosphate
of lime which should be added.
66
TRANSFORMATION OF THE ACID PHOSPHATE."
This latter part of the operation has for object to reneutralize the product
obtained in the preceding operation. This is effected by adding to the mass
the alkaline solution produced in the first operation, which forms an alkaline
phosphate, hydrated phosphate of lime, and a deposit of azoted matter held in
solution in the sulphuret. The facility with which the alkaline sulphuret
effects the separation of the wool from the cotton, and which can alone be
obtained in the manner described, permits of the production of a manure very
rich in azote, & not containing any other substance than the wool preci-

page_text: pitated. An acid should then, be added (sulphuric acid, for example), to the
alkaline solution in order to regenerate the sulphate of soda contained. The
deposit of azoted matters may then be readily collected. I may also in the
latter point of view employ sulphuric acid charged with animal matters in
solution in order to saturate the alkaline sulphuret.
Lastly, the sanction which the use of superphosphate of lime has received
in practical agriculture has induced me to give a distinct and commercial
value to the production of acid phosphate by an acid charged with animal
matters. For example, in the treatment of the refuse of slaughter-houses or
horse-flesh, this improved process may be employed for regenerating this
unhealthy business. Thus in a closed vessel of large size I place sulphuric
acid in the proportion of about 5 (five) parts for ever hundred of material, to
which I add the liquid obtained after the process of boiling meat for the
extraction of the fat and separating the bones therefrom. When the apparatus
is filled I heat it for one or two hours according the size of the vessel and the
quantity of matters introduced, and when the operation is terminated the
whole of the flesh will be found dissolved and a liquor obtained, which is
run off into a receiver or large wooden vat containing phosphate reduced to
powder, and stirred up by an attendant, and the phosphate is then attacked by
the acid, which has lost none of its saturating properties, and when the
mixture is completed the whole is állowed to stand, and on cooling becomes
solid, and may be then placed in drying apparatus. It will be seen that the
product obtained is very rich in azote, the strength of which may be increased
more or less according to circumstances. Thus the proportion of 5 (five)
parts of acid per hundred parts of azoted matters may be still diminished,
although more often it should be increased in order to have a greater quantity
of phosphate in the manure. Although I have stated sulphuric acid as being
the solvent, phosphoric and bydrochloric acids may be used for the same
purpose. The product thus prepared I designate under the name of animalized
superphosphate.
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, the employment of alkaline sulphurets, and especially those of
sodium and potassium, for dissolving the azoted matters either in the open air
or under pressure, and also the separation, by means of this agent, of wool from
cotton or other thread in certain cases.
Secondly, I claim the commercial application of the solubility of said azoted

page_text: matters in sulphuric acid either in the open air or under pressure, and the
employment of said acid while saturated with azoted matters for the pro-
duction of acid phosphate of lime.
Thirdly, I claim the saturation of said acid phosphate of lime with animalized
alkaline sulphurets, and also the combination of these reactions, in order to
produce manure containing azote in various forms, alkaline phosphates, and
hydrated phosphate of lime.
Fourthly, I claim the direct application of animalized superphosphate
obtained by the action of the acid saturated with azoted matters on the phos-
phates, in the manner and for the purposes herein specified.
In witness whereof, I, the said William Clark, have hereunto set my
hand and seal, this Sixth day of May, in the year of our Lord One
thousand eight hundred and sixty-three.
Witness,
W. G. E. SwINNOCK,
53, Chancery Lane,
London.
W. CLARK. (L.S.)