IMPROVEMENTS IN THE PROCESS OF FERMENTATION IN ORDER TO PREPARE ALCOHOLIC SOLUTIONS OF COLOURING MATTERS
Year: 1884

page_text: DREIFICATION,
I JOHAN HENRI LODER of 22 Tolsteegcingel Utrecht in the Kingdom of the
Netherlands do hereby declare the nature of my Invention for IMPROVEMENTS IN
THE PROCESS OF FERMENTATION IN ORDER TO PREPARE ALCOHOLIC SOLUTIONS OF
COLOURING MATTERS to be as follows:-
By these improvements it is proposed to obtain an alcoholic solution of colouring
matters vanilline salicylaldehydine benzoylaldebydine and others by fermentation
of a glucosic solution with nitric salts such as iron nitrate or nitric acid, and with
aromatic compounds as those of phloroglucine, catechine, resorcine, orcein and of
phenylic acid. Those substances are simply mixed with the glucosic solution
before fermentation is promoted or during the fermentation. The nitric acid is
used in glucosic solutions containing albuminous matters and is boiled before.
Instead of phloroglucine and catechine, those substances are used, that, treated
with acids or with alkali are decomposed into those principles, it is advantageous
to separate the glucosic compounds of them first before using them in this
manufacture.
The substances preferred are moritannic acid quercetine, resorcine, trinitro-
resorcine, extract of archil or orceine with or without erythroglucine, mononitro-
phenols, monoamidophenols, aniline, nitric acid nitrate of potassium, or of
ammonium, tartrate of iron, sulfocyanate of potassium or of ammonium, methyl-
amine, ricinoleic linoleic acid and phosphate of calcium.
Following coloring matters may be obtained. No 1. Those produced by the use
of 5.6 grammes of resorcine, 17.3 grammes of orceine, 11.3 grammes of Saltpetre
and 10 grammes of tartaric acid-N° 2. Those produced by the use of 6.3 grammes
of trinitro resorcine and 7.8 grammes of orceine. No 3. Those produced by the
use of 9.7 grammes of orceine, 9.7 grammes of saltpetre, 7.4 grammes of moritannic
acid or of quercetine, 3 grammes of sulphocyanate of potassium, 1 gramme of
tartrate of iron and 10 grammes of tartaric acid. N° 4 Those produced by the
use of 4.3 grammes of orthomononitrophenol, 9.6 grammes of orceine 3 grammes of
sulphocyanate of potassium. 6.1 gramines of saltpetre, 10 grammes of tartaric acid
and 1 gramme of tartrate of iron-No 5 those produced by the use of 4.8 grammes
of orceine 1'.3 grammes of orthomononitrophenol, 7.4 grammes of moritannic acid
or of quercetine 9.1 grammes of sulfocyanate of potassium. 4.7 grammes of saltpetre
10 grammes of tartaric acid and gramme of tartrate of iron. The coloring
matters of Nos 1 and No 2 produced in one mash with those of No 3 No 4 or of
No 5 give complicate compounds. In producing those of No 5 those of N° 3 and
No 4 are produced of course at the same time.
The quantities given of orceine, moritannic acid or quercetine are minimum ones
for those of the saltpetre or of the nitrified principles. If extract of sorrel paste or

page_text: extract of yellow wood is used they must be increased proportionally. Quercetine
may be used instead of moritannic acid, but it is advantageous to use the same
quantity of quercetine as that of moritannic acid if the orceine is not employed
in No 3. No 4. No 5. By the orthomononitrophenol I understand that mononitro-
phenol which has been rectified by distillation with water The quantities of iron
and of tartaric acid may be diminished to /, of their weight.
The quantities of saltpetre and nitrified principles given for 1000 grammes of
sugar proposed to be transformed into alcohol are nearly maximum ones, they may
be doubled if the mash contains albuminous matter. On 100 grammes of
albuminous matter grammes of saltpetre or the corresponding quantity of nitrified
principles may be used. In that case however instead of nitrates nitric acid is
used On 1000 grammes of glucose and 100 grammes of albuminous matter is used
in that manner 10 grammes of nitric acid of a density of 1.32. This nitric acid or
the corresponding nitrified principles with 0.75 grammes of tartrate of iron on
1000 grammes of flour is boiled from 20 to 30 minutes with the mash, the other
principles are added after cooling. The orceine may also be added to the mash
6 to 12 hours after the beginning of the fermentation.
The use of iron is not only of importance for the shade of colour if catechines are
employed but also by its action during fermentation on nitrified principles and on
the sulphur contained in albuminous matters By the use of that iron with nitric
acid it is possible to obtain, in a mash prepared from grain or in a glucosic solution
'containing other albuminous matter as of peas or of the like, from orthomono-
nitrophenol or from moritannic acid other compounds like vanilline and from
monoamidophenol and aniline salicyl and benzoylaldehydine with methylic
compounds of these-Those substances may be obtained in using either on
1000 grammes of glucose 31 grammes of moritannic acid or 14 grammes of aniline
or 17 grammes of amidophenol with 15 grammes of sulfocyanate of potassium
1 gramme of tartrate of iron 16 grammes of saltpetre 10 grammes of tartaric acid
and 4.8 grammes of methylamine or 9.2 grammes of trimethylamine-Or on
1000 grammes of glucose 21 grammes of orthomononitrophenol with 15 grammes
of sulfocyanate of potassium 4.8 grammes of methylamine, 1 gramme of tartrate of
iron, 5 grammes of tartaric acid.
All those substances may be produced in one mash to obtain compounds of them
but it must be borne in mind that the quantities given of saltpetre, or nitric acid
and of nitrified principles are nearly maximum ones in the conditions mentioned.
The shade of colour of those solutions depends on the constitution of the
álbuminous matters of the mash and on that of the yeast employed, in other words
on the sulphur they contain and on the products they are decomposed into by the
action of fermentation-All mashes used to prepare alcohol may be employed.
With the moritannic acid or the quercetine may be added on 1000 grammes of
sugar, 1 gramme of trimethylamine.
It must be said that 0.75 grammes of tartrate of iron on 1000 grammes of sugar
is sufficient to produce the different substances described but if there is at the
same time 0.25 grammes of tartrate of aluminium in the mash. 0.25 grammes of
tartrate of iron will do. It is not necessary to promote the fermentation by a special
yeast, that yeast produced during the manufacture may be used.
However it is found advantageous to have for that purpose on 1000 grammes of
glucose 5 grammes of a mixture of ricinoleic and of linoleic acid and 5 grammes of
phosphate of calcium in the mash.

page_text: I, JOHAN HENRI LODER, of 33, Tolsteegcingel, Utrecht, in the Kingdom of the
Netherlands do hereby declare the nature of my Invention for "IMPROVEMENTS IN
THE PROCESS OF FERMENTATION IN ORDER TO PREPARE ALCOHOLIC SOLUTIONS
OF COLOURING MATTERS," to be as follows:-
By these improvements it is intended to obtain an alcoholic solution of colouring
matters vanilline, salicylaldehydine, benzoylaldehydine by fermentation of a sacc-
harine solution with nitric salts, nitric acid, iron salts and aromatic compounds as
those of phloroglucine, catechine, resorcine, orcein and benzole.
Those substances are simply mixed with the glucosic solutions before fermenta-
tion is promoted or during the fermentation. The nitric acid and the sulpho-
cyanic acid are used to substitute their salts.
Instead of phloroglucine and catechine those substances are used, which treated
with acids or with alkali are decomposed into those principles.
It is advantageous to separate their glucosic compounds before using those
substances in this manufacture.
The substances preferred are moritannic acid, resorcine, trinitroresorcine, extract
of archil or orcein, with or without erythroglucine, mononitrophenole, monoamido-
phenole, aniline, nitric acid, potassium nitrate, ammonium nitrate, iron tartrate,
potassium sulpho-cyanate, ammonium sulpho-cyanate, methylamine, ricinoleic acid
and calcium phosphate.
As the mash or the yeast employed contains sufficiently phosphoric acid, calcium
carbonate is used instead of calcium phosphate; for each molecule of phosphoric
acid one molecule of calcium oxide should be employed.
For the preparation of the mash any substance used for alcoholic fermentation
may be employed. But a minimum quantity of chloric salts is tolerated in the
water used in this manufacture.
The following colouring matters may be obtained in using for a mash prepared
from 1000 gr of sugar about 250 gr of yeast 20 gr of calcium carbonate and
from 0.02 to 0.2 gr: of iron oxide:
1st 10.2 gr of resorcine, 25.2 gr: of nitric acid, 10 gr: of tartaric acid and
15.3 gr of orcein.
2nd 24.5 gr of trinitroresorcine, 15.3 gr: of orcein, 6.3 gr: of nitric acid,
10 gr of tartaric acid and from 0.2 to 2 gr: of iron oxide.
3rd 7.65 gr of orcein, 25.2 gr: of nitric acid 11.9 gr: of moritannic acid,
23.6 gr of sulpho-cyanic acid and 10 gr: of tartaric acid.
4th 13.9 gr of orthomonitrophenole, 7.65 gr: of orcein, 23.6 gr: of sulpho-
cyanic acid 19.9 gr: of nitric acid and 10 gr: of tartaric acid.
5th 7.65 gr of orcein, 6.95 gr of orthomononitrophenole 23.8 gr: of moritannic
acid, 23.6 gr of sulpho-cyanic acid, 22.05 gr of nitric acid and 10 gr: of
tartaric acid.
:
The colouring matters mentioned 1st and 2nd developed in one mash with those
mentioned 3rd supply complicated compounds. A mixture of very important ones
are obtained in using of the quantities mentioned 1st with 3 of the quantities
mentioned 3rd, or in using of the quantities mentioned 1st, 1 of the quantities
mentioned 2nd and of the quantities mentioned 3rd.
The quantities given are: calculated on the understanding, that orcein is repre-
sented by the formula C, H, NO,, moritannic acid by the formula C₁, H₁, O, nitric
acid by the formula NO, H, sulpho-cyanic acid by the formula C N S H, iron

page_text: '
oxide by the formula Fe, O,, and calcium carbonate by the formula Ca C O,
and that orthomononitrophenole is that mononitrophenole, which distills over by
steam.
If extract of archil or extract of yellow wood is used the quantities should be
augmented proportionally; it is however more advantageous to employ pure orcein
and pure moritannic acid.
Quercetine may be used to clear the coloured alcoholic solutions.
All the substances mentioned in these figures are added to the mash before the
ferment, except the orcein and the moritannic acid which are added to the mash at
the moment that of the sugar has been transformed into alcohol or about 21 hours
after the beginning of the fermentation.
:
The use of iron is not only of importance for the nature of the colouring matter
if trinitroresorcine is employed but also for its action during fermentation on
nitrified principles and the sulphur contained in albuminous matters. By the use of
that iron with nitric acid it is possible to obtain in a mash prepared from grain
or in a glucosic solution containing other albuminous matters as those of pease or
the like from orthomononitrophenole or from orthomonoamidophenole and aniline,
salicyl and benzoylaldehydine with methylic compounds of these. From each of
those principles should be used 1 gr: on 100 gr: of albuminous matter of the mash.
That quantity may be augmented by using for 1000 gr: of glucose about 250 gr of
yeast 20 gr of calcium carbonate and from 0.02 to 0.2 gr: of iron oxide, either
13.9 gr of aniline or 16.35 gr: of orthomonoamidophenole with 11.8 gr: of
sulpho-cyanic acid 25.2 gr: of nitric acid and about 15 gr: of tartaric acid or
41.7 gr of orthomononitrophenole with 23.6 gr of sulpho-cyanic acid, 6.3 gr: of
nitric acid and 10 gr: of tartaric acid, or 35.7 gr: of moritannic acid with 23.6
gr:
of sulpho-cyanic acid, 25.2 gr: of nitric acid and 10 gr of tartaric acid.
All the matters mentioned above may be produced in one mash, so as to obtain
compounds of these.
To produce these compounds distinctly in one mash for each molecule of orcein
of phlorglucine of catechine of aniline of orthomonoamidophenole one molecule of
sulpho-cyanic acid and one molecule of nitric acid and for three molecules of
sulpho-cyanic acid one molecule of resorcine or one molecule of trinitroresorcine
is used.
As a further illustration the following figures in which the quantity of sulpho-
cyanic acid and that of nitric acid is augmented of the theoritical proportions, as
exposed above are given. :
For a mash prepared from 1000. gr: of sugar proposed to be transformed into
alcohol 20 gr of calcium carbonate and from. 0.02 to 0.2 gr: of iron are used.
6th 11.8 gr of sulpho-cyanic acid 25.2 gr: of nitric acid with either 22.95 gr: of
orcein or 13.9 gr: of aniline or 1635 gr of orthomonoamidophenole and from
10 to 15 gr of tartaric acid.
7th 23.6 gr of sulpho-cyanic acid 25.2 gr of nitric acid, 35.7 gr: of moritannic
acid or of a corresponding quantity of any other combination of phloroglucine and
catechine and 10 gr of tartaric acid.
8th 23.6 gr of sulpho-cyanic acid with 41.7 gr: of orthomononitrophenole,
6.3 gr of nitric acid and 10 gr of tartaric acid.
:
9th 11.8 gr of sulpho-cyanic acid. 25.2 gr: of nitric acid, 5.1 gr.: of resorcine
with either 22.95 gr of orcein or 13.9 gr: of aniline or 16.35 gr of orthomono-
amidophenole and from 10 to 15 gr: of tartaric acid.
10th 23.6 gr of sulpho-cyanic acid 25.2 gr: of nitric acid, 35.7 gr: of mori-
tannic acid or of a corresponding quantity of any other combination of catechine
and phloroglucine and 10 gr: of tartaric acid.
11th 11.8 gr: of sulpho-cyanic acid, 15.75 gr of nitric acid 12.25 gr : of trinitro-
resorcine with either 22.45 gr of orcein or 13.9 gr: of aniline or 16.35 gr: of
orthomonoamidophenole from 0.2 to 2 gr: of iron oxide and from 10 to 15
tartaric acid.
gr:
of

page_text: 12th 23.6 gr of sulpho-cyanic acid 6.3 gr: of nitric acid 24.50 gr of trinitro-
resorcine 35.7 gr: of moritannic acid or of a corresponding quantity of any other
combination of phloroglucine and catechine from 0.2 to 2 gr: of iron oxide and
10 gr: of tartaric acid.
The quantities are calculated supposing the moritannic acid to be represented by
the formula C₁s H₁0 O, and to be composed of one molecule of catechine and one
'molecule of phloroglucine that the orcein is represented by the formula C, H, NO,,
the nitric acid by the formula NO, H, the sulpho-cyanic acid by the formula
CNHS, the iron oxide by the formula Fe, O, and the calcium carbonate by the
formula Ca CO,. Different combinations are obtained by aid of what is mentioned,
6. 7. 8. 9. 10. 11 and 12thly in using in one mash either . . . and of the
one figure with ... and of any other figure. So that of the quantities
of the 9th figure and of those of the 10th figure or ½ of the quantities of the
9th figure, of those of the 10th figure, of those of the 11th figure and of the
12th figure may be used.
It should be observed, that all the substances mentioned in these figures should
be added to the mash before fermentation is promoted, except: the orcein, the
moritannic acid, the aniline, the orthomonoamidophenole and the tartaric acid,
which are added in a state of solution when a third part of the sugar has been
fermented, or about 21 hours after the moment that the ferment has been added to
the mash. The aniline and the orthomonoamidophenole are added in the form of
tartrates.
The quantities of the substances in these figures are about maximum ones for
1000 gr of sugar, 250 gr of yeast and 20 gr of calcium carbonate. They might
be doubled if 500 gr of yeast and 40 gr: of calcium carbonate are employed; in
that case the orcein, the moritannic acid, the aniline, the orthomonamidophenole
and the tartaric acid should be added to the mash at the moment that of the
sugar has been fermented about 28 hours after the adding of the ferment; but the
use of the double of the quantities mentioned is not advisable for the reason that it
is impossible to avoid absolutely the access of air during the fermentation, therefore
there should, if strong coloured solutions containing 7.5 per cent alcohol are
required, be used for each 1000 gr: of sugar 350 gr of yeast 28 gr: of calcium
carbonate of the quantities mentioned in the said figures; the orcein, the
moritannic acid, the aniline, the orthomonoamidophenole and the tartaric acid
should be added to the mash at the moment that of the sugar has been trans-
formed into alcohol or about 25 hours after the adding of the ferment to the mash.
In a mash prepared from grain or from other amylaceous matter, the same
proceedings should be followed; on the quantity of phosphoric acid contained in
the mash depend the quantities of the calcium salts and of the other substances,
which have to be added to the mash.
It is advisable to use clear mashes, these need not to be boiled.
After the fermentation those alcoholic solutions of coloured matter are treated in
the same manner as wine or beer in order to obtain clear solutions which may be
conserved.
The nature of those alcoholic solutions of colouring matters depends on the
constitution of the albuminous matters of the mash, in other words on the sulphur
they contain and on the products they are decomposed into by the action of
fermentation. That nature depends also on the nature of the pressed yeast
employed; the latter being fabricated from grain or from legumes as pease or the
like the extract of the alcoholic solutions must be different; but the nature of the
alcoholic solutions of colouring matters depends also on the yeast ferments; it is
advisable to use that yeast which contains saccharomyces ellipsoideus or apiculatus
with bacteria or fungi, which are also found on the hay, the food of the cattle; and
it is advantageous that the yeast or the mash contains a minimum quantity of
aluminium oxide to supply the iron oxide.
Those alcoholic solutions of colouring matters prepared as set forth may be
employed for the fabrication of wines, red, white or sparkling ones and by distilling

page_text: them for the fabrication of an alcohol containing aromatic principles; they may
serve to prepare vinager or also for dyeing purposes.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare that what
I claim is:
1st The alcoholic solutions of colouring matters obtained by the use of nitric
acid, trinitroresorcine, orthomononitrophenole with sulpho-cyanic acid, resorcine,
orcein, aniline, orthomonoamidophenole, phloroglucine and catechine derivatives, in
a mixture in a state of alcoholic fermentation, principally in accordance with the
specification.