Improved Process for Converting Wood, Wood Shavings, Woody Fibre, Sawdust and other Substances into Dextrine, Glucose and Alcohol.
Year: 1899

page_text: Date of Application, 12th Jun³, 1859
Complete Specification Left. 1st Sept. 1899-Accepted. 30th Dec
1800
PROVISIONAL SPECIFICATION.
Improved Process for Converting Wood, Wood Shavings, Woody
Fibre, Sawdust and other Substances into Dextrine, Glucose and
Alcohol.
We, PAUL MAGNIER, of 30, Rue Solferino, Billancourt (Seine), and l'IERRE
ARMAND BRANGLER, of Aux Estrees par la Crèche, (Deux Sèvres), both in the
Republic of France, Chemist and Manufacturer respectively, do hereby declare
the nature of this invention to be as follows;-
---
The present invention has for its object an improved process for obtaining
dextrine, glucose and ethylic alcohol by an inexpensive treatment of wood,
woody fibre, shavings and the like.
Various attempts have previously been made to convert cellulose, wood, and
other like woody materials into glucose and as final result ethylic alcohol.
It is sufficient to recall on this subject numerous academic works which have
seen daylight and which nevertheless have up to now been so little satisfactory
that the processes described in the works in question have never been capable
of being exploited industrially.
It is precisely this problem of a possible industrial exploitation for the econo-
mical conversion of cellulose into glucose and alcohol which we consider we have
discovered but not in its entirety, that is to say it is not pretended that this
improved process is a complete innovation in all its phases, but that it is char-
acterised by certain electro-galvanic improvements or the use of any electric
metallic element as will be hereinafter specified.
The following is the method of carrying out our process:―
In the event of hard wood and other raw material being used in which the
cellulose is accompanied by a considerable quantity of foreign matter, we com-
mence by freeing the cellulose of such substances by the following preliminary
treatment.
The wood reduced to small fragments (shavings, sawdust, pulp or the like) is
subjected at the temperature of boiling point to the action of hypochlorite of
calcium and hydrate of lime in water. It is maintained at boiling point for an
hour or two according to the nature of the woody substance to be treated. At
the end of the operation a little sulphuric acid is added until the liquid is
slightly acid.
The material thus treated, or the raw material itself if it is not advisable to
subject it to this preliminary treatment, is treated at a temperature of 100° C.
with water acidulated by a mixture of about 2% (calculated on the raw materials
subjected to the treatment) of sulphuric and phosphoric acids. When the mate-
rial is deemed to be sufficiently attacked and disintegrated and when the presence
of dextrine in the liquid is ascertained, the liquid and pasty substances are
introduced in a digester where they are heated to about 150°-160° C. for some

page_text: time, it being of course evident that the higher the temperature, the shorter
the operation.
The liquid is then neutralised by introducing into the apparatus itself the
necessary quantity of carbonate of calcium or barium and if it be only desired to
obtain dextro-glucose, there is added to the substance for the purpose of bleach-
ing it, water charged with sulphuric acid and a little zine which transforms the
sulphurous anhydride into hydrosulphurous acid when the apparatus whilst
closed is again heated for some time.
If instead of glucose alone, it is intended to ultimately produce alcohol and the
brown colour of the liquid may be disregarded it is useless of course to make use
of the action of hydrosulphurous acid.
It is then sufficient to pass a voltaic current into the liquid in order to render
the major part of the introverted substances capable of fermentation and to mix
with the cellulose wort a little wort containing albuminoid substances (beetroot,
grain or the like) in order to obtain a maximum return.
The current may be produced by immersing in the liquid a metallic element
or couple such as zinc and copper for instance which even in a neutral liquid but
the temperature of which exceeds 100° C.) furnishes a sufficient voltaic current,
or even by utilising for the same purpose an external voltaic current (batteries,
dynamo or the like), this second mode of operation having the advantage of avoid-
ing the use of a temperature superior to 120-140° C whilst yielding the same
result.
In all the foregoing description it has only been a question of converting cellu-
lose substances (woody fibre shavings and the like). It is evident that electro-
lysis under pressure which forms the essential principle of the process herein before
described may be applied to all non fermentable products capable of being thereby
converted into fermentable sugar and consequently into ethylic alcohol, without
leparting from the scope of the present invention.
Dated this 10th day of June 1899
W. P. THOMPSON & Co.,
Of 6, Lord Street, Liverpool, Agents for the Applicants.
Improved Process for Converting Wood, Wood Shavings, Woody
Fibre, Sawdust and other Substances into Dextrine, Glucose and
Alcohol.
We, PAUL MAGNIER, of 30, Rue Solferino, Billancourt (Seine), and PIERRE
ARMAND BRANGIER, of Aux Estrees par la Crèche (Deux Sèvres), both in the
Republic of France, Chemist and Manufacturer respectively, 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:-
The present invention has for its object an improved process for obtaining
dextrine, glucose and ethylic alcohol by an inexpensive treatment of wood,
woody fibre, shavings and the like.
Various attempts have previously been made to convert cellulose, wood, and
other like woody materials into glucose and as final result ethylic alcohol.
It is sufficient to recall on this subject numerous academic works which have
seen daylight, and which nevertheless have up to now been so little satisfactory
that the processes described in the works in question have never been capable
of being exploited industrially.

page_text: It is precisely this problem of a possible industrial exploitation for the econo-
mical conversion of cellulose into glucose and alcohol which we consider we have
discovered but not in its entirety, that is to say it is not pretended that this
improved process is a complete innovation in all its phases, but that it is char-
acterised by certain electro-galvanic improvements or the use of any electric
metallic element as will be hereinafter specified.
The following is the method of carrying out our process: -
In the event of hard wood and other raw material being used in which the
cellulose is accompanied by a considerable quantity of foreign matter, we com-
mence by freeing the cellulose of such substances by the following preliminary
treatment.
The wood reduced to small fragments (shavings, sawdust, pulp or the like) is
subjected at the temperature of boiling point to the action of hypochlorite of
calcium and hydrate of lime in water. It is maintained at boiling point for an
hour or two according to the nature of the woody substance to be treated. At
the end of the operation a little sulphuric acid is added until the liquid is
slightly acid.
The material thus treated, or the raw material itself if it is not advisable to
subject it to this preliminary treatment, is treated at a temperature of 100° C.
with water acidulated by a mixture of about 2% total weight (calculated on the
raw materials subjected to the treatment) of sulphuric and phosphoric acids, com-
bined, about 1% of each being used but the proportions may be varied as
desired. When the material is deemed to be sufficiently attacked and disinte-
grated and when the presence of dextrine in the liquid is ascertained, the liquid
and pasty substances are conveyed into a digester where they are heated to
about 1500-160° C for some time, it being of course evident that the higher the
temperature, the shorter the operation.
The liquid is then neutralised by introducing into the apparatus itself the
necessary quantity of carbonate of calcium or barium and if it be only desired to
obtain dextro-glucose, there is added to the substance for the purpose of bleach-
ing it, water charged with sulphurous acid and a little zinc which transforms the
sulphurous anhydride into hydrosulphurous acid when the apparatus whilst
closed is again heated for some time.
If instead of glucose alone, it is intended to ultimately produce alcohol and the
brown colour of the liquid may be disregarded it is useless of course to make use
of the action of hydrosulphurous acid.
It is then sufficient to pass a voltaic current into the liquid in order to render
the major part of the introverted substances capable of fermentation and to mix
with the cellulose wort a little wort containing albuminoid substances (beetroot,
grain or the like) in order to obtain a maximum return.
The current may be produced by (1) immersing in the liquid a metallic element
or couple such as zinc and copper for instance which even in a neutral liquid but
the temperature of which exceeds 100° C. furnishes a sufficient voltaic current,
or (2) even by utilising for the same purpose an external voltaic current (bat-
teries, dynamo or the like); this second mode of operation having the advantage
of avoiding the use of a temperature superior to 120---140° C. whilst yielding the
same result.
In all the foregoing description it has only been a question of converting cellu-
lose substances (woody fibre shavings and the like). It is evident that electro-
lysis under pressure which forms the essential principle of the process herein before
described may be applied to all non fermentable products capable of being thereby
converted into fermentable sugar and consequently into ethylic alcohol, without
departing from the scope of the present invention.
The conditions of temperature, pressure etcetera, as herein before described, are
not absolute. They may, on the contrary, in practice be variable without limits,
according to the particular circumstances of every case.

page_text: The following laboratory experiment of easy reproduction, will give a more
complete idea of it, in that this experiment will actually show the sacchari-
fying or inversion-action of the electrolytic current.
800 grammes of neutral- or even alkaline-water, 80 grammes of ordinary sugar
or sucrose (which does not reduce Fehling's liquor and is not directly fermentable)
and finally a few grammes of a suitable salt such as sulphate of soda or sulphate
of magnesia intended to render the solution a conducting one, are conveyed into
an enamelled vessel having a flat bottom and vertical walls and capable of being
heated, and of holding one litre for instance.
Two platinum electrodes or more simply, two carbon electrodes of the kind
usual in batteries but as wide as possible, are immersed in the liquid and held
as near as possible parallel by means of a non conducting frame and connected
by means of metallic wires with the two poles of a strong battery.
The liquid being heated and maintained in a state of ebullition (the water
evaporated being replaced gradually by neutral or even alkaline water) and the
battery working properly and not polarising, it will be found by following the
operation with Fehling liquor that the saccharose is inverted progressively and
after some hours of ebullition it has been converted into reducing sugar which,
when exposed to fermentation after sufficient cooling, ferments immediately.
The same result with the same solution and the same arrangement, is obtained
if cold, but it takes a longer time. From this experiment which is scientifically
novel and conclusively demonstrative of the saccharifying or inversion-action of
the electrolytic current, the essential feature of the invention is deduced.
Having now particularly described and ascertained the nature of our said
invention and in what manner the same is to be performed, we declare that what
we claim is: :-
1. In the conversion of cellulose substances non-fermentable sugar, or carbo-
hydrates into fermentable sugar and consequently into ethylic alcohol, the use
of the electrolytic current either as principal agent or coadjutor under pressure
or in the open air, and either with or without the use of heat and before, during
or after fermentation substantially as hereinbefore described.
2. In a general manner, the use of an electrolytic current for obtaining a con-
version of sugar or a carbo-hydrate of a lower grade into a sugar or a carbo-
hydrate of a higher grade, that is to say one approximating more closely to a
fermentable condition, substantially as hereinbefore described.
Dated this 31st day of August 1899.
WM. P. THOMPSON & Co.,
Of G, Lord Street, Liverpool, Agents for the Applicants.