Improvements in Bleaching and Disinfecting Starch and Fecula by Electrolysis.
Year: 1892

page_text: Date of Application, 19th Jan., 1892
Complete Specification Left, 10th Oct., 1892-Accepted, 3rd Dec., 1892
1
PROVISIONAL SPECIFICATION.
Improvements in Bleaching and Disinfecting Starch and Fecula
by Electrolysis.
I EUGENE HERMITE of No. 4 Rue Drouot, Paris, in the Republic of France,
Manufacturer, do hereby declare the nature of this invention to be as follows
--
This invention relates to improvements in bleaching and disinfecting starch and
fecula by electrolysis.
From investigation of the processes now in use it may be concluded that, in starch
and fecula works, the method which will give the most complete satisfaction will
be that which will permit :-
"
1°. To obviate the inconvenience of calcareous waters by precipitating the lime;
20. To easily separate the fecula from the parenchyma and albuminoïd matters;
30. To prevent the pectic and lactic ferinentations as well in the " gras or
residuums resulting from the treatment of the starches or feculas and which is
added to fresh fecula in ulterior operations (hereinafter termed slime), as in the
green or moist fecula and to facilitate the working of these slimes by rendering
the extraction of these residuums easy, without the use of sulphuric acid, from a
fecula as pure as the first fecula;
4°. To destroy the essential oils without injuring the amylaceous matter and
thus get rid of the characteristic smell of fecula from the "Oise;
"
50. To give to the fecula a whiteness similar to that of the Dutch or German
feculas of the brand B K M F, without, running the risks incurred by the use of
liquid chloride of lime or calcium;
6°. To yield as excreta:-1°. Pulps containing the greatest possible quantity of
azoted principles. 2°. Waters not susceptible of fermentation.
The rational application of the electro-chemical process permits complete
realisation of this very extensive programme.
My process is based upon the following scientific principle:
:-
If a current of electricity is passed into a watery solution of a salt, preferably
a chloride, this salt is decomposed at the same time as the water; there is formed
at the positive pole a very unstable oxygenated compound of chlorine, gifted with
a great power of oxidation and therefore of disenfection. At the negative pole, an
oxide is formed which has the power of precipitating organic matters.
This principle laid down, suppose that I have to treat a very calcareous water:―
I add thereto a small quantity of chloride of sodium (sea-salt) and submit it to
electrolysis. At the positive pole there will be formation of an oxygenated com-
pound of chlorine, whereas at the negative pole there will be formation of caustic
soda. This caustic soda reacting upon the calcareous salts of the water, will
precipitate the lime in transforming the carbonate of lime into lime and carbonate
of soda, the salts of iron into ferro-oxide and into salts of soda etc. The insoluble
lime will precipitate by standing. If, I have added to the chloride of sodium a
few traces of chloride of aluminium, I shall have in formation gelatinous alumina,
one of the best clarifiers known, which will rapidly precipitate the lime remaining
in suspension.
Besides calcareous salts, the water often contains organic matters, germs,
ferments, sulphuretted hydrogen and sulphurets, and carbonates of hydrogen. The
oxygenated compound of chlorine obtained at the negative pole will act powerfully
on these various compounds and by abandoning its oxygen thereto will transform
them either into carbonic acid, or into sulphuric acid, or into sulphates.
Thus, by adding to the water intended for the extraction of the fecula a small

page_text: "
quantity of sea salt and electrolysing it, it may be freed from its calcareous matters
which as is well known, have the inconvenience of forming with the pectose and
other organic matters contained in the fecula, insoluble compounds and charging it
with a very powerful antiseptic principle, the oxygenated compound of chlorine.
An apparatus may thus purify about 500 litres of water a minute. The first point
of the programme "suppression of the inconvenience of calcareous waters by
precipitating the lime is thus fulfilled.
Upon examination of the albuminoïd matters contained in the parenchyma and
in the vegetation water, it will be seen that the vegetable albumen, "legumine,"
"globuline,"
vegetable fibrin, the "mucidine," vegetable gelatine and the
myosine" are all very soluble in alkaline bases. It results therefore from this
property that these matters finding themselves in presence of an electrolysed
water as above set forth, and to which has been added carbonate of soda, will
dissolve with facility. The pectate of lime, the pectine, the azoted bodies will,
under this same influence, be transformed into soluble salts; finally the "vasculose"
oxydated by the oxygen coming from the chlorated compound will change into
:soluble resinous acid, it also, into carbonate of soda as demonstrated by "Fremy."
The separation of the parenchyma and of the albuminoïd matters from the
fecula will therefore be greatly facilitated, and the second point of the programme
fulfilled. In consequence of its power of oxydation, the oxygenated compound of
chlorine constitutes a powerful antiseptic. The "anaerobies cannot live in this
oxygenated medium and the "aerobies" are attacked in their actual constitution
and destroyed by the oxygen in an identical manner to that of sulphuric acid upon
the human body.
"
The pectic and lactic fermentations can therefore no longer be produced in green
or moist fecula having been treated by electrolysed water than putrid fermenta-
tions can be produced in "eaux-vannes or fecal-waters also electrolysed. These
fermentations are prevented as well in the "slimes" or residuums ("gras") as in
the green fecula by the use of electrolysed water; my process therefore answers
well he third point of the programme, and its use will prevent the formation of the
pectates and lactates of lime which so often trouble manufacturers of glucose.
:
In presence of the alkaline carbonates, the essential oils transform into soluble
and inoderous bodies; now the electrolytic liquor contains, as we have seen, these
carbonates they will therefore saponify these oils and free the fecula from them.
Should the extraction by alkalis be incomplete, the oxygen coming from the
oxygenated compound of chlorine would act on the oils easily transforming them
by oxydation into gascous products. The destruction of the essential oils and the
deoderisation of the fecula which constitute the fourth point of the programme are
therefore again solved by the use of my process.
The sixth consists in rendering the residuary waters unfermentisable and to fix
in the pulp as much azoted matters as possible. The oxygenated compound of
-chlorine having, as previously demonstrated, destroyed the ferments, the residuary
waters will no longer be susceptible of fermentations and they may, without any
fear be utilised for irrigation; on the other hand, the azoted compounds having
been transformed into fixed salts, the chances of loss of azote will be much
.diminished.
There remains a point which I have neglected, that of the bleaching of the
fecula. The oxygenated compound of chlorine will permit this bleaching to be
easily obtained, as its oxydating power is at the same time a very energetic bleach-
ing power. It is in fact not to the chlorine, but to the oxygen which are due the
bleaching effects of the various chlorides; the oxygenated compound of chlorine
which is found in the electrolytic liquid, abandoning its oxygen with great facility,
will therefore bleach the fecula without presenting any of the dangers of the
chloride of lime, which dissolves the "granulose."
It appears to me therefore demonstrated by the above that my electro-chemical
method may meet all.. the exigencies arising in the manufacture of starch and
fecula

page_text: This treatment may be effected in any kind of electrolyser, but I particularly
recommend the apparatuses which I have already patented.
PURIFICATION OF THE WATER.
Add to the water a small quantity of sea salt and pass it through the electro-
lyser soda will be set free, as above explained, and it will precipitate the lime of
the calcareous salts. After standing for a sufficient time, the water will issue from
the vats or vessels perfectly purified. If it is desired to act rapidly add to the sea
salt a little chloride of aluminiuni, which, in the preceding operation, will give
gelatinous alumina, an excellent clarifier.
TREATMENT OF THE STARCH OR OF THE FECULA.
By using water purified and with the addition of a small quantity of alkalines,
preferably carbonate of soda, the washing, the rasping and the sifting of the potato
are preserved without modification. The carbonate of soda facilitates these
operations by giving solubility to the albuminoïd matters, the pectates and the
essential oils. The electrolytic method will have its action in the refining or
operation of the fecula. In this operation water will be used with addition of
chloride of sodium and chloride of magnesium. There will also be added a certain
quantity of gelatinous magnesia obtained by the treatment of chloride of magnesium
with caustic soda. It is known that in presence of the current, the chloride of
magnesium and the water will become decomposed and firm by the union of the
chlorine the chloride and the oxygen of the water, an oxygenated compound of
chlorine unstable and therefore endowed with great oxydating power.
The hydrogen and the magnesium set free will go to the negative pole, but this
latter will decompose the water and form magnesia, whereas the hydrogen will be
set free. If I introduce into a similar liquid oxydable bodies, like those contained
in the fecula, the oxygen will combine with thein to form gaseous compounds,
whereas the chlorine will reunite with the hydrogen to make chlorhydric acid which,
finding itself in the presence of magnesia will combine with it to reform the
primitive chloride of magnesium. I have therefore a complete cycle of reactions
which will be produced so long as the electric current acts on the solution in
presence of oxydable matters; this cycle, which is perfect, is composed of four
clements the electric current, the chloride of magnesium, the water and the
oxydable matter.
Only two of these elements serve to destroy the oxydable matter: the electric
current and the water; there is a simple displacement of molecules and the chlorine
acts as vehicle to carry the arising oxygen on to the oxydable matter.
In the treatment of starches and fecula I may act in two ways: either directly
or indirectly.
Direct Process. To the water employed in the refining vats I add a sufficient
quantity of sea salt, of chloride of magnesium and of the gelatinous magnesia, then
after agitation and intimate admixture with the fecula coming from the sifting,
I pass this feculant water through the electrolyser before sending it to the
depositing planes. The current under the action of the fecula decomposes the
chloride of magnesium and gives birth to the chlorated compound the action of
which has been above explained.
"
Sent upon the planes on issuing from the electrolyser, the fecula deposits rapidly,
the Crownien movement which often slackens its deposit being destroyed by the
electrolysis and the "slimes" will be converted into a sort of cap somewhat similar
to defication scums and which will retain but very little fecula.
The waters, instead of being sent to the pulp pit, are carefully collected, because,
as I have above shown, they contain the same content in regeneratered chlorides
and consequently are fit for a new work of electrolysation. There will be added to
them a little soda which, in determining the formation of gelatinous magnesin, will
permit obtaining its rapid clarification.

page_text: Indirect Process. It consists in preparing apart an electrolytic solution, then
to use it either in the refining vats, or in the turbines by clarification or
decoloration.
Whatever may be the process employed, it is necessary before the drying to give
to the fecula a last washing containing either ammonia, or hyposulphate of soda.
This washing with water has for object to neutralise all the traces of chloride which
might be found in the fecula before the drying.
TREATMENT OF THE "SLIMES" OR RESIDUUMS ("GRAS").
If they come from fecula prepared by the electrolytic process, being sterilized
and consequently refractory to fermentation, I may without fear of modifications
treat them finally. I proceed with them in the ordinary manner, but replacing the
water by an electrolysed solution, or by passing them through the electrolyser, after
a suitable addition of chloride of magnesium.
If the slimes or residuums come from fecula treated by the usual process, it is
well to submit them firstly to a washing with water charged with carbonate of soda,
which will dissolve the calcareous lactates and pectates which have formed; then,
after this first washing they will be submitted to the electrolytic process, either
directly, or indirectly. It should however be observed that the direct treatment
gives very superior results.
Dated this Nineteenth day of January 1892.
"
COMPLETE SPECIFICATION.
Improvements in Bleaching and Disinfecting Starch and Fecula
by Electrolysis.
I EUGENE HERMITE of No. 4 Rue Drouot, Paris, in the Republic of France,
Manufacturer, do hereby declare the nature of this invention and in what manner the
same is to be performed, to be particularly described and ascertained in and by
the following statement :-
This invention relates to improvements in bleaching and disinfecting starch and
fecula by electrolysis.
From investigation of the processes now in use it may be concluded that, in
starch and fecula works, the method which will give the most complete satisfaction
will be that which will permit :-
1°. To obviate the inconvenience of calcareous waters by precipitating the
:lime;
.
#
2°. To easily separate the fecula from the parenchyma and albuminoïd matters;
3°. To prevent the pectic and lactic fermentations as well in the
12
gras or
residuums resulting from the treatment of the starches or feculas and which is
added to fresh fecula in ulterior operations (hereinafter termed slime) as in the
green or moist fecula and to facilitate the working of these slimes by rendering the
extraction of these residuums easy, without the use of sulphuric acid, from a fecula
as pure as the first fecula;
4°. To destroy the essential oils without injuring the amylaceous matter and
thus get rid of the characteristic smell of fecula from the "Oise ;
5°. To give to the fecula a whiteness similar to that of the Dutch or German
feculas of the brand BK M F, without running the risks incurred by the use of
liquid chloride of lime or calcium ;
6°. To yield as excreta:-1°. Pulps containing the greatest possible quantity of
azoted principles. 2°. Waters not susceptible of fermentation.

page_text: The rational application of the electro-chemical process permits complete
realisation of this very extensive programme.
My process is based upon the following scientific principle.
If a current of electricity is passed into a watery solution of a salt, preferably a
chloride, this salt is decomposed at the same time as the water there is formed at
the positive pole a very unstable oxygenated compound of chlorine, gifted with a
great power of oxidation and therefore of disinfection. At the negative pole, an
oxide is formed which has the power of precipitating organic matters.
This principle laid down, suppose that I have to treat a very calcareous water.
I add thereto a small quantity of chloride of sodium (sea salt) and submit it to
electrolysis. At the positive pole there will be formation of an oxygenated
compound of chlorine, whereas at the negative pole there will be formation of
caustic soda. This caustic soda reacting upon the calcareous salts of the water,
will precipitate the lime in transforming the carbonate of lime into lime and
carbonate of soda, the salts of iron into ferro-oxide and into salts of soda etc. The
insoluble lime will precipitate by standing. If, I have added to the chloride of
sodium a few traces of chloride of aluminium, I shall have in formation gelatinous
alumina, one of the best clarifiers known, which will rapidly precipitate the lime
remaining in suspension.
Besides calcareous salts, the water often contains organic matters, gerins,
ferments, sulphuretted hydrogen and sulphurets, and carburets of hydrogen. The
oxygenated compound of chlorine obtained at the negative pole will act powerfully
on these various compounds and by abandoning its oxygen thereto will transform
them either into carbonic acid, or into sulphuric acid, or into sulphates.
Thus, by adding to the water intended for the extraction of the fecula a small
quantity of sea-salt and electrolysing it, it may be freed from its calcareous matters
which as is well known, have the inconvenience of forming with the pectose and
other organic matters contained in the fecula, insoluble compounds and charging it
with a very powerful antiseptic principle, the oxygenated compound of chlorine.
An apparatus may thus purify about 500 litres of water a minute. The first point
of the programme
suppression of the inconvenience of calcareous waters by
precipitating the lime" is thus fulfilled.
66
66
Upon examination of the albuminoïd matters contained in the parenchyma and
in the vegetation water, it will be seen that the vegetable albumin, "legumine,"
globulin,” vegetable fibrin, the mucidine, vegetable gelatine and the myosine are
all very soluble in alkaline bases. It results therefore from this property that
these matters finding themselves in presence of an electrolysed water as above set
forth, and to which has been added carbonate of soda, will dissolve with facility.
The pectate of lime, the pectine, the azoted bodies will, under this same influence,
be transformed into soluble salts; finally the "vasculose" oxydated by the oxygen
coming from the chlorated compound will change into soluble resinous acid, which
is also soluble in carbonate of soda as demonstrated by "Fremy."
"
The separation of the parenchyma and of the albuminoid matters from the
fecula will therefore be greatly facilitated, and the second point of the programme
fulfilled. In consequence of its power of oxydation, the oxygenated compound of
chlorine constitutes a powerful antiseptic. The "anaerobies cannot live in this
oxygenated medium and the "aerobies" are attacked in their actual constitution
and destroyed by the oxygen in an identical manner to that of sulphuric acid upon
the human body.
The pectic and lactic fermentations can therefore no longer be produced in
green or moist fecula having been treated by electrolysed water than putrid
fermentations can be produced in "eaux-vannes or fecal-waters also electrolysed.
These fermentations are prevented as well in the "slimes" or residuums ("Gras")
as in the green fecula by the use of electrolysed water; my process therefore
answers well the third point of the programme, and its use will prevent the
formation of the pectates and lactates of lime which so often trouble manufacturers
of glucose,

page_text: :
In presence of the alkaline carbonates, the essential oils transform into soluble
and inoderous bodies; now the electrolytic liquor contains, as we have seen, these
carbonates they will therefore saponify these oils and free the fecula from them.
Should the extraction by alkalis be incomplete, the oxygen coming from the
oxygenated compound of chlorine would act on the oils easily transforming them
by oxydation into gaseous products. The destruction of the essential oils and the
deoderisation of the fecula which constitute the fourth point of the programme are
therefore again solved by the use of my process.
The sixth consists in rendering the residuary waters unfermentisable and to fix
in the pulp as much azoted matters as possible. The oxygenated compound of
chlorine having, as previously demonstrated, destroyed the ferments, the residuary
waters will no longer be susceptible of fermentations and they may, without any
fear be utilised for irrigation; on the other hand, the azoted compounds having
been transformed into fixed salts, the chances of loss of azote will be much
diminished.
There remains a point which I have neglected, that of the bleaching of the
fecula. The oxygenated compound of chlorine will permit this bleaching to be
easily obtained, as its oxydating power is at the same time a very energetic
bleaching power. It is in fact not to the chlorine, but to the oxygen which are due
the bleaching effects of the various chlorides; the oxygenated compound of
chlorine which is found in the electrolytic liquid, abandoning its oxygen with great
facility, will therefore bleach the fecula without presenting any of the dangers of
the chloride of lime, which dissolves the "granulose."
It appears to me therefore demonstrated by the above that my electro-
chemical method may meet all the exigences arising in the manufacture of starch
and fecula.
This treatment may be effected in any kind of electrolyser, but I particularly
recommend the apparatuses which I have already patented.
PURIFICATION OF THE WATER.
Add to the water a small quantity of sea salt and pass it through the
electrolyser soda will be set free, as above explained, and it will precipitate
the lime of the calcareous salts. After standing for a sufficient time, the water
will issue from the vats or vessels perfectly purified. If it is desired to act rapidly
add to the sea salt a little chloride of aluminium, which, in the preceding operation,
will give gelatinous alumina, an excellent clarifier.
TREATMENT OF THE STARCH OR OF THE FECULA.
By using water purified and with the addition of a small quantity of alkaline
salts, preferably carbonate of soda, the ordinary processes of washing, rasping and
sifting of the potato are preserved without modification. The carbonate of soda
facilitates these operations by giving solubility to the albuminoïd matters, the
pectates and the essential oils. In the refining or purification of the fecula water
will be used with addition of chloride of sodium and chloride of magnesium. There
will also be added a certain quantity of gelatinous magnesia obtained by the treat-
ment of chloride of magnesium with caustic soda. It is known that in presence
of the current, the chloride of magnesium and the water will become decomposed
and form by the union of the chlorine the chloride and the oxygen of the water, an
oxygenated compound of chlorine unstable and therefore endowed with great
oxydating power.
The hydrogen and the magnesium set free will go to the negative pole, but this
latter will decompose the water and form magnesia, whereas the hydrogen will be
set free. If I introduce into a similar liquid oxydable bodies, like those contained
in the fecula, the oxygen will combine with them to form gascous compounds,
whereas the chlorine will reunite with the hydrogen to make chlorhydric acid

page_text: which, finding itself in the presence of magnesia will combine with it to reform the
primitive chloride of magnesium. I have therefore a complete cycle of reactions
which will be produced so long as the electric current acts on the solution in presence
of oxydable matters; this cycle, which is perfect, is composed of four elements:
the electric current, the chloride of magnesium, the water and the oxydable
matter.
Only two of these elements serve to destroy the oxydable matter, the electric
current and the water; there is a simple displacement of molecules and the chlorine
acts as vehicle to carry the arising oxygen on to the oxydable matter.
In the treatment of starches and fecula I may act in two ways: either directly
or indirectly.
Direct Process. To the water employed in the refining vats I add a sufficient
quantity of sea salt, of chloride of magnesium and of the gelatinous magnesia,
then after agitation and intimate admixture with the fecula coming from the sifting,
I pass this feculant water through the electrolyser before sending it to the
depositing planes. The current under the action of the fecula decomposes the
chloride of magnesium and gives birth to the chlorated compound the action of
which has been above explained.
"
Sent upon the planes on issuing from the electrolyser, the fecula deposits rapidly,
the "Crownien movement which often slackeus its deposit being destroyed by the
electrolysis and the "slimes" will be converted into a sort of cap somewhat similar
to defecation scums and which will retain but very little fecula.
The waters, instead of being sent to the pulp pit, are carefully collected, because,
as I have above shown, they contain the same content in regenerated chlorides and
cousequently are fit for a new work of electrolysation. There will be added to
them a little soda which, in determining the formation of gelatinous magnesia, will
permit obtaining its rapid clarification."
Indirect Process. It consists in preparing apart an electrolytic solution, then to
use it either in the refining vats, or in the turbines by clarification or decoloration.
Whatever may be the process employed, it is necessary before the drying to give
to the fecula a last washing containing either ammonia, or hyposulphite of soda.
This washing with water has for object to neutralise all the traces of chlorine which
might be found in the fecula before the drying.
By way of example of the solution to be used in my process I give the
following :-
a sumerent gentinous magnesia to keep the solution enteral and erectory
the liquor holds 2 grammes of chlorine per litre.
Of this solution thus prepared use 1 litre to every 4 kilogrammes of fecula
calculated dry.
This proportion may vary according to the fecula between 1 litre to 4 kilogrammes
and 1 litre for 6 kilogrammes of fecula.
TREATMENT OF THE 66
"
SLIMES" OR RESIDUUMS" ("GRAS").
If they come from fecula prepared by the electrolytic process, being sterilized
and consequently refractory to fermentation, I may without fear of modifications
treat them finally. I proceed with them in the ordinary manner, but replacing the
water by an electrolysed solution, or by passing them through the electrolyser after
a suitable addition of chloride of magnesium.
If the slimes or residuums come from fecula treated by the usual process, it is
well to submit them firstly to a washing with water charged with carbonate of soda,
which will dissolve the calcareous lactates and pectates which have formed; then,
after this first washing they will be submitted to the electrolytic process, either

page_text: directly, or indirectly. It should however be observed that the direct treatment
gives very superior results.
Having now particularly described and ascertained the nature of my said inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is :-
My process of bleaching and disinfection of starches and fecula by electrolysis
of the water used in this manufacture, in presence of one or of several chlorides
(such as chloride of sodium, of magnesium etc.) this electrolysis being effected
either upon the water in mixture with the fecula or starch in the course of the
manufacture, or previously upon the water which, thus prepared, is to serve for the
treatment of the starches and fecula, substantially as above set forth.
Dated this Tenth day of October 1892.