IMPROVEMENTS IN THE TREATING OF FISH AND FISH RESIDUES FOR EXTRACTION OF OIL, AND CONVERTING THE RESIDUES INTO CHARCOAL AND PHOSPHATES AND AMMONIACAL SUBSTANCES
Year: 1879

page_text: LETTERS PATENT to Henri Lissagaray, of No. 11, Bessborough Gardens,
Pimlico, in the County of Middlesex, for the Invention of "IMPROVEMENTS
IN THE TREATING OF FISH AND FISH RESIDUES FOR EXTRACTION OF OIL,
AND CONVERTING THE RESIDUES INTO CHARCOAL AND PHOSPHATES AND
AMMONIACAL SUBSTANCES."
Sealed the 18th June 1880, and dated the 27th December 1879.
PROVISIONAL SPECIFICATION left by the said Henri Lissagary at the Office
of the Commissioners of Patents on the 27th December 1879.
HENRI LISSAGARAY, of No. 11, Bessborough Gardens, Pimlico, in the County of
Middlesex. "IMPROVEMENTS IN THE TREATING OF FISH AND FISH RESIDUES
FOR EXTRACTION OF OIL, AND CONVERTING THE RESIDUES INTO CHARCOAL AND
PHOSPHATES AND AMMONIACAL SUBSTANCES."
This Invention of improvements in the treating of fish and fish residues for
extraction of oil, and converting the residues into charcoal and phosphates and
ammoniacal substances, relates to the treatment of either fresh or stale fish or offal
left from cleaning.
In the case of stale or putrid fish I disinfect them by hypochlorite of soda or
other suitable disinfectant added in proper proportions.
I first boil the fish or fish residues in an open vessel of water, with one and a half
their weight of water acidulated with muriatic acid, representing 1 to 3 per cent.
of dehydrated acid to weight of fish. Then is added in the proportion of 3 to 6
per cent. of the fish a solution of hypochlorite of soda, 200 degrees by chlorometric
analysis (system Gay Lussac).
In certain cases the hypochlorite may be substituted by sulphate of soda or other
suitable salt.
The acid fixes the ammonia already free, and the chlorine as produced decomposes
the products of phosphorous and neutralises the odour. On the other hand the
muriatic acid acts simultaneously upon a portion of the tribasic phosphate of the
bones and transforms it into soluble super phosphates, and also a portion of
their carbonates, producing corresponding chlorides and a discharge of carbonic
acid gas.

page_text: .
When the disinfection is complete, the phosphorescent gases decomposed, and the
ammonia fixed, an outlet with a grating in the bottom of the vessel is opened au!
the solution run off into a suitable vessel. The oil rises to the surface and is drawn
off; the residual liquor is precipitated by milk of lime
The solid residues left in the vessel are then subjected to the following treatment
which I have discovered, and by which I suppose a change of molecular structure is
effected -It depends on treating this residue at a higher temperature than that of
boiling water in solutions such as chloride of calcium, glycerine, or even oils and
fatty substances, and the molecular modification resulting in the separation of the
oil is probably brought about by the presence of water naturally in the residues (a,
some of the liquids can be used quite dehydrated) in proximity to the higher ten-
peratures of the heated liquid. Of course the liquid with high boiling point must
be chemically inert to the nitrogenous matter and towards the oil, etc., to be
separated.
Tho residue being then, as indicated above, treated for about an hour and a half
or two hours, the bones become friable and the whole will form a thick paste. No
appreciable discharge of ammonia takes place.
The paste is then run off and subjected to pressure, and the oil is separated from
the nitrogenous and phosphated matters. The liquid employed may be used
again. The pressed cake may be washed with hot water and again pressed.
The pressed cake may then be dried and separated in any usual manner, the
nitrogenous from the phosphated portions.
After the nitrogenous and the phosphated powders have been separated, this latter
is treated in different ways, either for the direct extraction of the phosphorous or
for the preparation of a phosphoric solution.
The nitrogenous powder is treated in a retort in presence of lime or a mixture of
soda and lime to extract the nitrogen under the form of ammonia, this latter being
received in the phosphoric solution and producing phosphate of ammonia. Sulphate
of ammonia would be obtained by receiving it in a sulphuric solution.
The two powders once separated may be again mixed "ad libitum" in the most
convenient proportions, in order to calcine them afterwards by any of the modes
generally used. Animal charcoal is thus obtained in which the proportions of
phosphate and carbonized matters can be varied "ad libitum." When it is intended
to carry out this last manufacture it would be well to reduce to a minimum the
action of the muriatic acid during the first period of the operation.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said Henri Lissagaray in the Great Seal Patent Office on the 26th Juno
1880.
HENRI LISSAGARAY, of No. 11, Bessborough Gardens, Pimlico, in the County of
Middlesex. "IMPROVEMENTS IN THE TREATING OF FISH AND FISH RESIDUES
FOR EXTRACTION OF OIL, AND CONVERTING THE RESIDUES INTO CHARCOAL AND
PHOSPHATES AND AMMONIACAL SUBSTANCES."
This Invention of improvements in the treating of fish and fish residues for
extraction of oil, and converting the residues into charcoal and phosphates and
ammoniacal substances, relates to the treatment of either fresh or stale fish or offal
left from cleaning.
In the case of stale or putrid fish I disinfect them by hypochlorite of soda or
other suitable disinfectant added in proper proportions.
I first boil the fish or fish residuos in an open vessel of water, with one and a half
their weight of water acidulated with muriatic acid, representing 1 to 3 per cent.
of dehydrated acid to weight of fish. Then is added in the proportion of 3 to 6
per cent. of the fish a solution of hypochlorite of soda, 20° by chlorometric analysis
(system Gay Lussac). In certain cases the hypochlorite may be substituted by
sulphite of soda or other suitable salt. The acid fixes the ammonia already free,
and the chlorine as produced decomposes the phosphuretted products and neutralizes
the odour. On the other hand the muriatic acid acts simultaneously upon a portion
of tribasic phosphate of the bones, and transforms it into soluble super-phosphates,
and reacts also upon a portion of their carbonatos, producing corresponding chlorides
and a discharge of carbonic acid gas. When the disinfection is complete, and the
phosphoretted gases having been decomposed and the ammonia fixed, an outlet with
a grating in the bottom of the vessel is opened and the solution run off into a suitable
vessel. The oil rises to the surface and is drawn off; the residual liquor is preci-
pitated by milk of lime. The solid residues left in the vessel are then subjected to
the following treatment which I have discovered, and by which I suppose a change
of molecular structure is effected :-It depends on treating this residue at a higher
temperature than that of boiling water in solutions such as chloride of calcium,
glycerine, or even oils and fatty substances, and the molecular modification resulting
in the separation of the oil is probably brought about by the presence of water naturally
in the residues (as some of the liquids can be used quite dehydrated) in proximity
to the higher temperature of the heated liquid. Of course the liquid with high
boiling point must be chemically inert to the nitrogenous matter and towards the
oil, etc., to be separated.
I namo amongst the anhydrous liquids which can make this molecular modification,
1stly. Anhydrous glycerine, which can be heated to a temperature above 100° C.,
and in the midst of which the water (of which the weight is three quarters of the
weight of the fish) is only vaporized slowly and with difficulty.
2ndly. The fatty bodies, and notably the oils which comply with all conditions,
I can thus realise a treatment which appears paradoxical. If I act on a weight of
fish residues impregnated with oily mattor, from which I would separate the oil by
an equal weight of fish oil, and bring the mixture slowly to a temperature of 115°
to 120° C,
Firstly, the proteine matter will be heated by the oil bath; secondly, the water
contained in the fish residues will only be vaporised slowly, and then only when the
temperature shall rise to the above mentioned limit. Before its total evaporation
O the water will rest there some time in presence of the proteine matter, its temperaturo
being notably above 100° C.
The result is that the molecular modification will be accomplished, and the proteine
matters after a simple washing separate themselves, so to speak, spontaneously, not

page_text: only from the added oil, but also from that naturally contained in the fish, an
which will be separated together with the former or added oil.
I have supposed the liquid employed to be anhydrous, because it is under the
conditions that one can demonstrate absolutely the fact of great importance to
known, that is, that the molecular modification and the separation of the oil whic
results are accomplished slowly by the action of the water which the fish residue
contained naturally. But these liquids may be employed equally hydrated, so tha
their boiling point is notably above 100° C., and that their presence sufficiently
retards the vaporization of the water contained in the proteine matters so that th
molecular modification can be accomplished.
In practice then I tako glycerino concentrated as it is found in commerce, and i
is possible to achieve the molecular modification of the proteine matters in the mids
of the glycerine, even with the temperature below the boiling point, and consequently
without production of steam.
These facts enable me to foresco, and experience confirms it, that the glycerine
and the oil may be replaced by a solution of certain salts in a certain state of
concentration, as their boiling point is passing 100° C.
Amongst the solutions fulfilling these conditions I name, -
3. The solution of chlorido of calcium, so concentrated that its boiling point
attains 130° C.
Whatever the liquid employed to determine the molecular modification (always
in an open vessel at atmospheric pressure), the treatment is managed successively,
firstly, the dis-aggregation produced by the chlorhydric acid; secondly, the heating
by the liquid used and the action on the water, the bones become friable and
crumble under slight pressure. When the treatment is finished they should form
with proteine matter a thick soup. Care should be taken that there is no sensible
loss of ammonia, whatever the temperature of the mixture, and this should be
assured by keeping a slip of reddened litmus paper above the vessel, the color of
which should not change to bluc.
The treatment with the hydro chloric acid and the hypo chlorite or the sulphate
of soda having lasted about half an hour, the second treatment with the liquid will
last above an hour and a half or two hours. At the end of this time the magma
should be led by a pipe to a filter press; under the pressure the liquid and the oil
separate from the proteine matters and phosphates
The liquid after separation from the oil can be used again.
The cake left in the press can be washed with hot water and again pressed, if
required; it is then dessicated, and may be pulverized.
Separation of the nitrogenous matter and the phosphates may be separated by
any of the means used for separating particles of different densities.
The first operation with the acid may be prolonged, if desired, taking care to
supply fresh acid as the first charge is absorbed by the carbonates of the bones and
the equivalent of lime which the tribasic phosphate loses in passing to super plos-
phate; but if this method is employed the free acid before saturation, which is not
instantaneous, should never exceed 3% of the fish residue; too energetic action is
thus avoided.
After separation of the phosphate powder and the nitrogenous powder, the first
may be treated in several ways, either for extracting the phosphorus directly or for
preparing phosphoric solution.
The nitrogenous powder is treated in a retort with dry lime to extract the
nitrogen as aminonia, this being gathered in a solution of phosphoric acid for
phosphate of ammonia, or in sulphuric acid for sulphate of ammonia to b:
fabricated.
After these operations the two powders may be again mixed in any proportion,
and calcined by any of the well known methods, and animal charcoal is obtained in
which the proportions of phosphate and carbon can be varied as desired.
If this latter process of making animal charcoal is desired, the action of the acil
used in the first part of the treatment should be reduced to a minimum.

page_text: Having now described and particularly set forth the nature of the said Invention,
and the manner of carrying the same into effect, I would have it understood that
what I claim is,―
1. The use of liquids, as described, with high boiling points for extracting oils
from fish or fish residues, in the manner substantially as described.
2. The preparation of phosphates and ammoniacal products from fish or fish
residues, in the manner substantially as described.
3. The preparation and manufacture of fish or animal charcoal from fish or fish
residues, in the manner substantially as described.
In witness whereof, I, the said Henri Lissagaray, have hereunto set my hand
and seal, this Twenty fourth day of June, in the year of our Lord One
thousand eight hundred and eighty.
HAMT
HENRI LISSAGARAY. (L.S.)