IMPROVEMENTS IN THE MEANS OF UTILIZING REFUSE AZOTED MATTERS OF COMMERCE FOR THE MANUFACTURE OF VARIOUS CHEMICAL PRUDUCTS
Year: 1863

page_text: LETTERS PATENT to William Clark, of 53, Chancery Lane, in the
County of Middlesex, Engineer and Patent Agent, for the Invention
of "IMPROVEMENTS IN THE MEANS OF UTILIZING REFUSE AZOTED MATTERS
OF COMMERCE FOR THE MANUFACTURE OF VARIOUS CHEMICAL PRUDUCTS." —
A communication from abroad by Amédée Gélis, Chemist, and Lucien
Dusart Chamist hath of 29 Boulovart St Mantin Danie
Scaled the 1st March 1864, and dated the 9th September 1863.
PROVISIONAL SPECIFICATION left by the said William Clark at the
Office of the Commissioners of Patents, with his Petition, on the 9th
September 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
Invention for "IMPROVEMENTS IN THE MEANS OF UTILIZING REFUSE AZOTED
MATTERS OF COMMERCE FOR THE MANUFACTURE OF VARIOUS CHEMICAL PRODUCTS, to
be as follows:-
In a previous Patent granted to me, and dated November 7th 1862,
No. 301, it has been stated that alkaline sulphurets possess the remark-
able property of dissolving azoted matters of animal origin without injuring
the vegetable fibre with which they may be combined, which property has
been utilized in the preparation of manures, and the separation of cotton.
or thread from wool, silk, leather, or other substance for the various
purposes of commerce.

page_text: The object of this Invention is the novel application of this property of
alkaline sulphurets in the preparation of various known chemical products
which have never hitherto been obtained under economical and advantageous
conditions, which is effected by the novel means herein described.
The primary matters employed are, 1st, alkalino sulphurets, whatever may
be their mode of production; 2ndly, peroxide of iron; 3rdly, all kinds of
residues of commerce containing azote, consisting by preference of silk and
wool waste, hair, horn, leather, offal, old shoes, bones, and others, and the
products resulting from the treatment of these matters are, 1st, cotton
thread and vegetable fibres in general; 2ndly, ammonia and ammoniacal
salts; 3rdly, prussiates of potash or soda; 4thly, carbonates of potash or
soda; 5thly, sulphuret of iron. I will now proceed to give the details of
the process.
Description. I commence by preparing a solution of alkaline sulphuret,
which for greater clearness I will here suppose to be sulphuret of potas-
sium, although it should be understood that sulphuret of sodium will give
the same results, one or other of which may be used for the purpose.
The concentration of this solution may be varied, always however keeping
as near as possible to saturation, with a view to avoid the expense of
evaporation. This solution is heated to about 212° degroes Fahrenheit, to
which is added the matters to be treated when the latter consist of
pure azoted substances they are dissolved without leaving any residue, when
on the contrary they are mixed with cotton threal or other vegetable fibre
the latter will be preserved uninjured and deprived of animal matters, they
may then be used anew in commerce for the manufacture of paper or other
fabrics according to their state of preservation. This primary treatment
with alkaline sulphurets may be effected either in the open air or under
pressure; the dissolving properties are not the same in both cases, as in
the open air one part of the sulphuret dissolves about four times its
weight of animal matters, while under pressure the amount of matter dis-
solved would reach about 20 times in weight that of the reagent, and that
without exceeding a pressure of 5 atmospheres. The boilers employed for the
opeu air treatment may be varied in form, the most convenient however being
of conical form, and about three or four cubic yards in capacity, furnished with
a double bottom to prevent contact of the metal with the organic matter.
The boilers are about 4ths filled with the solution of alkaline sulphuret, which
is theu raised to boi ing heat, and the matter to be heated is then intro-
duced, which is contained in a net suspended from a pulley. After a cer-

page_text: tain time, which varies according to the degree of concentration of the
alkaline solution, and the amount of material under treatment, the net is
removed which carries with it the undissolved cotton thread or other sub-
stance if wool rags have been treated. The matters are allowed to
drain for some time over a vessel, and then placed in a contiguous vessel,
containing a similar solution, in order to complete its action on the animal
matters which may still remain after the first treatment. On leaving this
vessel the rags are carefully washed to remove the alkaline solution with
which they are impregnated, and are then bleached with chloride of lime
after being previously treated with a weak acid; the first boiler is then
immediately recharged with a fresh quantity of woollen rags, and the ope-
ration proceeded with as before; when the sulphuret in this boiler is
saturated, that is, when at the ordinary pressure, its action upon the rags
is almost nil; the contents are then withdrawn into another boiler with a
flat bottom where evaporation is effected. When the solution has lost some
portion of its water, while still retaining a certain amount of liquid, peroxide
of iron is added in amount equivalent to the strength of the sulphuret in
the alkaline liquor (three parts of oxide of iron to two parts of sulphuret)
evaporation being continued until a small portion of the mixture when placed
on a cold surface will solidify without adhering thereto. At this moment the
heat is withdrawn and the matter thus prepared is in a suitable condition for
being distillel. This distillation is effected in an apparatus consisting either of
a large retort similar to those used in the manufacture of pyrolignoous acid
worked with a crane, or it may be a furnace containing four, five,or seven retorts
similar to those employed in gas works for the distillation of coal. In both
cases the furnaces are raised to a red heat. Under the influence of the heat
the mixture divides into two parts, the one which is liquid and volatile
becomes distilled, while the other and solid part remains as a fixed residue.
The distilled part consists of ammoniacal water and tar, the fixed part beinga
black, porous, friable mass which is easily washed, and in which will be found
amixture of prussiate and carbonate of potash or soda according to the nature
of the sulphuret employed, and of the sulphurets of iron and carbon.
Independently of the products enumerated above I also obtain an abundant
amount of gas which may be used for lighting if collected in a gasometer and
afterwards purified, or it may be used for heating purposes by passing it
through tubes under the furnace bars. In all cases the action of the heat on
the mixture of peroxide of iron andazoted matters dissolved in the alkaline
sulphurets determines the production of an important product, viz., volatile
ammonia, and as it is indispensable to coudense said product it should be

page_text: placed in retorts in communication with refrigerating apparatus. For this
purpose I use a barrel containing ascending columns in communication with
the heads of the retorts, and a worm formed of closed horizontal tubes dipping
in water, a closed tank is used for receiving the condensed products, also a
column of coke in order that the ammoniacal gas may be washed with water;
lastly there is a vessel lined with lead containing acidulated water foriemoving
the last traces of ammonia. The gases passing from this series of condensers
are then collected or consumed in the furnaces. Instead of employing a
furnace for the manufacture of the gas I use retorts such as those used for
distilling wood, the condensing apparatus being the same with the exception
of the barrel which is dispensed with. The matters to be distilled are in this
case simply placed in the retort and the operation completed, after removing
the retort from the furnace, and before allowing it to cool it is perfectlyclosed
with a luted plug; but it I employ ordinary gas retorts the matters may not
be heated direct, as it is absolutely indispensable at the termination of the
operation to subject the residue when at a red heat to the action of the air,
for this purpose I employ slicet iron vessels of similar form to the retorts, each
of which vessels is about four feet in length and closed at one end, the other
being opened and closed by means of a cover which is suitably luted. On the
top and at the end corresponding to the bottom of the vessel is an opening
of about four or five inches for the escape of vapours and gases. This opening
is closed when the operation is completed as it is only by the action of the air
that the prussiate formed may be transformed into cyanate. These vessels
are filled at the large end with an alkaline mixture which is evaporated
sufficiently to be of a solid consistency, the opening is then closed, the upper
apertures only being left open; this being done, said vessels are introduced
by means of muffles into the retorts, which are previously raised to a red heat
and then quickly closed again. The distillation is soon effected, and when
gas ceases to disengage the vessels are withdrawn from the retorts, and the
upper opening closed, other vessels kept ready for the purpose replacing those
which have been withdrawn. After being completely cooled the product
contained in the vessels is treated with water to dissolve the prussiate and
carbonate which are afterwards separated by crystallization. It will be
understood that under these conditions the whole of the prussiate becomes
crystallized, when it is mixed with an alkaline liquor. The mother waters
afterthe elimination of the prussiate areevaporated anddried ina reverberatory
furnace. The residue abandoned by the water is formed of sulphuret of irou
and carbon which is dried in-blocks, and afterwards may be roasted and so
transformed into sulphurousacid to serve in the manufactureofsulphuricacid,

page_text: sulphites, and hyposulphites. The residue of the roasting consists of oxide
of iron which serves again in the operation herein-before described; the
volatile products which have been collected in the condensing apparatus are
treated in a similar manner. The ammoniacal waters are separated from the
tar which they contain by decantation, the tar being burnt and the ammo-
niacal waters heated by the ordinary processes to transform them into
ammoniacal salts.
Hitherto I have only treated of solutions of animal matters obtained in the
open air, that is at the ordinary atmospheric temperature in these solutions,
the amount of animal matters dissolved is four times the weight of the alkaline
sulphuret. I have also stated that at a pressure of five atmospheres the
dissolving power of the reagent would be about five times greater. I may
thus readily increase the amount of animal matters to be dissolved by working
under pressure in a closed vessel. When operating on these conditions on
rags containing a mixture of wool and cotton or thread the latter substances
will only be affected when operating at the ordinary temperature, while the
vegetable fibre will also be completely cleaned. I utilize this propery in cases
where the carbonate of potash is not of very great value, and it is wished to
diminish its production, relatively increasing that of the prussiate and ammo.
viacal salts. In this manner when the solution of animal matters is obtained
the alkaline liquors are drawn off and evaporated as before with oxide of iron
only, as the proportion of alkali would be insufficient for obtaining all the
azote from the azoted matters in the form of ammonia and cyanogen, and as
one part would escape under the form of gas I mix therewith the mother
water of the alkaline carbonate produced in the preceding operation. The
evaporated product is treated in an exactly similar manuer as for the pure
solution of clkaline sulphuret. The form of the closed vessel above referred
to is similar to those employed in the manufacture of gelatine. It has been
stated that when acting under pressure the caustic and carbonated alkalics
may perform an active part, less energetic it is true than the sulphurets, but of
sufficient importance notwithstanding. This action is for the common purpose
of producing alkalide sulphuret,and ulteriorly the treatment of animal matters
by said sulphuret. In fact all the azoted substances in the order above stated
are very rich in sulphur, and the primary effect of an alkali upon them is to
determine the separation of said sulphur in the form of sulphuret, and which
is consequently the chief object of the present Invention.

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 March 1864.
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 Ninth day of September, in the year of our Lord
One thousand eight hundred and sixty-three, in the twenty-seventh 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 AZOTED MATTERS OF COMMERCE FOR THE MANUFACTURE OF
VARIOUS CHEMICAL PRODUCTS," a com". to me from abroad by Amédée Gélis,
Chemist, & Lucien Dusart, 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 instrumentin writing undermy, 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 per-
formed, 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 follow-
ing statement (that is to say):-
This Invention embraces a whole series of operations, the final result of
which is the production of the following chemical substances, viz., ammonia,
prussiates of potash or soda, carbonate of potash or soda, sulphuret cf iron, and
also of two commercial raw materials, flax and cotton. The means I employ
for producing the above result are generally speaking of two kinds, 1st, by
the action of alkaline sulphurets upon matters of auimal origin; 2ndly, by the

page_text: action of heat on the alkaline mixture of animal matters in the presence of
oxide of iron.
Action of Alkaline Sulphurets on Animal Matters.-When any azoted
matter, such as fibrin, wool, silk, leather, hair, or other similar substances, is
heated in a solution of alkaline sulphurets, especially those of potassium and
sodium, it becomes entirely dissolved without any ammonia being evolved at
twohundredandtwelvedegrees Fahrenheit,andunder the ordinary atmospheric
pressure, one part of sulphuret dissolving from four to five parts of animal
matters. When working at a higher pressure, but not exceeding five atmos-
pheres, the amount of animal matters should be twenty times at least the
weight of the sulphuret, on which conditions their dissolution is nearly instan_
taneously effected. All the substances known under the generic denomination
of albuminoid matters operate in the same manner. If, however, instead of
azoted matters liqneous materials are treated, such as flax, hemp, or cotton,
and allowed to boil together with the solution ofalkaline sulphurets, whatever
may be the duration of the experiment, no dissolution can be obtained; and
further, the materials will not have undergone the least alteration while the
fibres retain their primitive qualities. I have taken advantage of this difference
of action for separating the cotton and flax or hemp from the animal materials
contained in mixed fabrics. There are, in fact, materials known in commerce
under the denomination of" waste" for manure, such as cotton, hemp, or flax,
thread warps, in which wool, flax, and cotton threads are so incorporated as
to render it impossible to separate them advantageously by any mechanical
process.
According to this Invention I operate on such products, and obtain there-
from, first, a solution of animal matters, and secondly, a residue consisting
of flax and cotton, which after being bleached may be used again, either for
the production of paper pulp or for the manufacture of various fabrics.
Action of Heat upon the Alkaline Mixture of Animal Matters with Oxide
of Iron. After separating the cotton and other threads there remains from
the foregoing operation a solution of animal matters in the sulphurets, which
solution is utilized as follows:-The liquors thus obtained are submitted to
evaporation, which is effected without disengaging any sensible amount of
ammonia, and when the liquor has attained a syrupy condition some peroxide
of iron is added, still continuing to heat it, until on a small quantity being
dropped upon a cold body it becomes solidified without adhering thereto; the
whole is then submitted to the action of a strong heat which causes water to
distil, charged with a considerable amount of ammonia, and when the vessel
is red hot, and no more gas is disengaged, the whole is allowed to cool out of

page_text: រ
contact with the air there remains in the retort a black matter in a half
melted condition, consisting of a mixture of prussiate and carbonates of potash
or soda, according to the alkali used, and some sulphuret of iron and carbon.
The treatment of this matter by water eliminates the prussiate and carbonate
which is separated by crystallization, while the mixture of sulphuret of iron
and of carbon is dried and serves for the preparation of sulphurous acid. This
process may therefore be divided into two distinct parts, 1st, treatment of
animal matters or mixtures of same by a solution of alkaline sulphurets, 2ndly,
treatment of the solution of alkaline azoted matters for their transformation
into chemical products.
I will now proceed to give a practical description of the various
operations.
Treatment with Alkaline Sulphurets.-I have already stated that this treat-
ment may be effected at two hundred and twelve degrees Fahrenheit under
the ordinary atmospheric pressure, or at a higher pressure. When working
at the ordinary pressure, I use large boilers from four to five cubic yards in
capacity, which are about two-thirds filled with the solution of alkaline
sulphuret marking about twenty degrees. The liquor is first brought rapidly
to boiling heat, during which time a wire or other basket filled with the
material to be treated, such as rags or pure animal matters, is introduced
into the boiler. After a certain time, which varies according to the quantity
of materials under treatment, the basket is removed, carrying away with it the
matters such as cotton and other threads left undissolved, and which are
insoluble in the reagent, being replaced by another containing fresh matters,
and so on, until the sulphuret in the boiler is saturated, at which moment the
liquors are evaporated and ready for use. The rags of cotton and linen are
steeped in lye in order to extract the sulphuret with which they are impreg
nated, and are then bleached, after previous treatment, with a weak acid.
When the treatment by means of sulphurets takes place at a higher pressure
than that of the atmosphere, I make use of a large cylinder about six feet in
height, by six feet six inches in diameter. This cylinder has at its lower part
a cast-iron worm pipe, the two ends of which issuing from the boiler are
provided with cocks whereby they communicate on one side with a steam
generator and on the other with a water condenser. From this arrangement,
it results that a continuous current of steam is caused to traverse the digester
or closed vessel, which rapidly raises the temperature thereof; this digesteris,
like the boiler described in the preceding operation, about two-thirds filled
with sulphuret, and receives a basket full of the materials to be treated. The
apparatus being charged, and the cover put on, the temperature is then raised

page_text: to three atmospheres, at which moment the current of steam is cut off and
the pressure diminishes, and when it has fallen to one and a half or two
atmospheres, the discharge of the liquors may be effected as the dissolution of
the animal matters will be complete. The discharge of the solution is readily
effected by means of a tube provided with a cock at the lower part of the
apparatus, which cock being opened, the liquid escapes into a receiver under
the action of the pressure still existing in the apparatus, whereby the latter
is emptied almost in an instant; the rags are then taken out, and treated in
the usual way.
Treatment of the Solution of Alkaline Azoted Matters.-The liquors
charged with animal matters are subjected to evaporation, peroxide of iron
being added at the moment they have attained such a state of concentration
that the oxide shall not fall to the bottom of the boiler, but remain in the
mixture. The water still continues to be drawn out until if a part of the
mass be laid upon a cold body it would become solid, although not adhering
.thereto, at which moment the matters may be withdrawn and submitted to
calcination in a distilling apparatus. This apparatus may consist either of a
large retort operated by means of a crane, and similar to those used in the
manufacture of pyroligneous acid, or it may be a five or seven retort furnace
similar to those used in gas works for distilling coal. As the action of fire on
the matters determines the production of a principal substance, viz., ammonia,
which is volatile, this product must indispensably be condensed; for this
purpose I use a barrel receiving the ascending columns, which communicate
with the heads of the retorts, also a refrigerator formed of horizontal tubes
and à closed receiver of the condensed products; there is, further, a coke
column for washing with water the gas charged with ammonia; and, lastly, a
bottle lined with lead, containing the acidulated water for removing the last
traces of ammonia. The gases usuing from this series of condensers are either
collected or burnt in the furnace.
.
. Instead of using furnaces,such as those employed in the manufacture of gas,
they may be retorts such as are used. for distilling wood, in which case the
condensing apparatus is the same, the barrel only being dispensed with. The
matters to be distilled are in this case placed in the retort, and on the termi-
nation of the operation, after removing the retort from the furnace, and before
it has become cool, its mouth is tightly closed with a luted plug. When using
retorts such as those in gas works, the matters cannot be heated directly as it
is absolutely necessary at the end of the operation to completely secure the
red hot residue against the action of the air. For this purpose sheet iron

page_text: cases or vessels are used of the same form as the retort, each case being about
four feet in length, closed permanently at one end and open at the other, which
is closed when required by a luted cover. On the top and extreme end
corresponding to the bottom of the case an opening is made about four or
five inches in diameter for the escape of vapours and gases; this opening is
closed when the operation is over as the prussiate generated should not by the
action of the air become transformed into cyanate. These cases are filled
through the large opening with the alkaline mixture evaporated to a solid
consistence,said opening is then stopped, the upper orifice only being left open,
after which the sheet iron cases are introduced by means of tackles into the
retorts, previously raised to a red heat, which latter are immediately and quickly
closed. The distillation is readily effected, and when gas no longer disengages
the cases are removed from the retorts, and the upper opening is tightly closed,
said cases being replaced by others kept ready for the purpose. After com-
pletely cooling, the product in the cases is treated with water to dissolve the
prussiate and carbonate, the separation of which is effected by crystallization.
The mother waters after elimination of the prussiate are evaporated and dried
in a reverberatory furnace. The mixture of sulphuret of iron and carbon is
placed in a heap and dried, which on its combustion may be used for the
production of sulphurous acid, the residue of the calcination consists of oxide
of iron, which is again utilized as before explained, the ammoniacal waters are
also treated in the usual way for the preparation of ammoniacal salts.
Although I have mentioned gas retorts as being of a suitable form for the
calcining apparatus such may be varied as judged suitable, in fact this part of
the process is but of secondary importance and may be modified according to
requirements. In conclusion, the above series of operations comprise the
production of cotton and linen rags, ammonia, and ammoniacal salts, alkaline
prussiates and carbonates, and lastly sulphuret of iron. It has been also
stated that by applying pressure, I may employ caustic carbonated alkalies,
and that these bodies may be substituted for the alkaline sulphurets, but to a
limited extent only,as their action is less energeticthan that of the sulphurets;
and they have besides the disadvantage of setting at liberty a certain amount
of ammonia, I therefore claim their application together with the sulphurets.
Having described the nature of this Invention and the manner of per-
forming the same, I declare that what I claim as the Invention to be pro-
tected by the herein-before in part recited Letters Patent is, the exclusive
right of preparing the various chemical substances in the manner herein-
before described, and also the application for paper-making or spinning

page_text: purposes of the cotton and other threads or fibres obtained by this im-
proved treatment of mixed rags all as herein-before described.
In witness whereof, I, the said William Clark, have hereunto set my
hand and seal, this Seventh day of March, in the year of our Lord
One thousand eight hundred and sixty-four.
Witness,
JAMES DAISH,
53, Chancery Lane,
London.
LANA.
(4.8.)