Year: 1888

page_text: Date of Application, 26th June, 1888
Complete Specification Left, 19th Mar., 1889
Complete Specification Accepted, 25th May, 1889
:
I, ALBERT HENRI JACQUES BERGÉ of 122 Rue de La Poste, Schaerbeck Brussels,
in the Kingdom of Belgium Dr. of Natural Sciences, do hereby declare the nature of
this invention to be as follows :-
It is generally supposed that the saccharification of starch is more rapidly
accomplished, and rendered more complete when the quantity of acid used for the
purpose is stronger, the temperature higher, and the duration of the operation longer.
There are however, great difficulties to be met with in order to satisfy these conditions.
Too great a quantity of acid is injurious as it impairs the quality of the products to be
prepared too high a temperature carbonizes the products, and too long a duration of
the process is also, for several reasons, a disadvantage.
The fact that pressure plays an important part in chemical reactions led me to
utilize it also in saccharifying starch. A series of experiments with various acids has
shown that the saccharification becomes more rapid and more complete in proportion
as the pressure is increased.
For instance, in two trials in which the quantity of acid, temperature and duration
of the process were the same, but of which one took place in a closed vessel under the
pressure of steam corresponding to the said temperature, whilst the other was effected
under a much greater pressure produced by the compression of air or other gases in
the vessel, the second trial resulted in a far more complete saccharification.
The consequence of this is that the saccharifying power of all acids is promoted
by compression or by forcing air or other gases into the vessels in which the operation
is effected, and that in consequence a smaller quantity of acid may be used, whilst the
usual conditions of temperature remain the same.
The application of this general principle in connection with the application of
sulphurous acid to the saccharification of starch has justified in a complete manner
these suppositions. In this particular case the principle is of great importance, for
it is here a question of treatment with the least concentrated solutions. It is in fact
generally known that it is very difficult to prepare rich solutions of sulphurous acid,
whereas acid solutions containing from 1 to 3 per cent. can easily be prepared.

page_text: By forcing into the vessel wherein the operation is effected, carbonic acid gas,
nitrogen, or any other non-oxidising gas so as to obtain a great pressure, the products
are transformel completely into sugar by means of a slightly concentrated solution of
sulphuric acid. As in this process the action of the oxygen is to be eliminated, the
Intter is excluded from the vessel wherein the reaction takes place. Although the
process may be effected in various manners, I shall describe only the following, as it
gives the best results in practice.
When the product to be saccharifier has been placed in a boiler along with the
solution of sulphurous acid, carbonic acid gas is introduced into this boiler, this
gas laving a greater density than air, expels the Intter from the boiler. As soon
as a lighted candle placed near the opening of the boiler is extinguished, the latter
is closed and carbonic acid gas compressed into it until the required pressure is
reached. Of course any other gas, sulphurous acid or a mixture of non-oxydising
gases which are heavier than air, can fulfil the same purpose.
When concentrated solutions of sulphurous acid are used so that the great prossure
required is produced by the reagent itself, it is of the greatest importance to remove
entirely the air, which would otherwise be injurions to the process owing to its
oxydising action. Particular stress must be laid on this point in practice, as
sulphurous acid is, at temperatures above 100 degrees easily transformed into sulphuric
neid, so that when the greatest care has not been exercised, it may be supposed that
the transformation into sugar was due to the sulphuric acid formed. In following
the process as first described, no sulphuric acid whatever will be formed. The
production of sulphuric acid presents the disadvantage that the latter must afterwards
be neutralized either with carbonate of lime or baryta, but this always spoils the
taste and alters the purity of the product obtained. Besides this, this mixture
corrodes the copper, and when vessels provided internally with a lining of lead are
used, a small quantity of sulphate of lead is always produced.
When the operation is over, the sulphurons acid is collected for the purpose of
utilising it in a subsequent operation. The saccharified product is freed from the
particles of sulphurous acid adhering to it, by means of a steam jet. When this acid
has been re-generated, it can be used indefinitely.
The sulphites act in the same manner as the sulphurous acid, they require when
nse for saccharifying purposes, the same precautions as the latter acid. The
application of sulphurous acid and sulphites under the aforesaid conditions is highly
preferable to that of other acids as the latter exercise a special action on the volatile
oils, which are contained in various substances, especially in potato-starch. The action
on pointo-starch is such that the grape sugar resulting therefrom gives through
fermentation an excellent alcohol.
In short, the process consists in the saccharification of amylaceous substances by
means of all sorts of organic or inorganic acids and neid salts, but more especially
by means of sulphurous neid in closed vessels wherein a high pressure is maintained,
that is, a pressure much above that which would be produced by heat alone, said
pressure being obtained by forcing gas into the vessel.
The pressure to be produced is in proportion to the quantity of acid used, the
temperature, the duration of the process, and the nature of the substance to be
transformed to sugar. Generally speaking an initial pressure of 6 or 7 atmospheres
gives good results. For certain cases I reserve to my self the right of saccharifying
amylaceous substances by means of pure sulphurous acid or a mixture of the latter
with carbonic acid gas or nitrogen without using the original pressure or additional
pressure of the gas, but in all cases however the process takes place under pressure in
closed vessel, wherefrom the air has previously been exhausted.
I have besides effected the transformation of amylaceous substances into sugar by
means of carbonic acid gas compressed at a high pressure; the best results are
obtained by treating dry, or at least nearly dry substances or better by treating
substances which have been previously heated to a temperature of 100 degrees for the
purpose of removing the superfluous water and keeping the substances hydrated to a
certain extent only. Under those circumstances no starch paste is formed during the

page_text: process. This substance placed in a closed vessel is then submitted to the pressure of
compound carbonic acid gas or mixture of other gases; said pressure varying in
proportion to the amount of saccharizing to be produced, whilst the substance is
brought to a temperature corresponding to this amount, but always exceeding
100 degrees. By forcing air in under the same circumstances, similar results would
be obtained.
The same results can also be obtained by treating solutions of amylaceous substances
or dextrine solutions which are heated under gas pressure in a closed vessel.
The reaction can also be effected by heating in a closed vessel dried starch or dextrine
as above, without forcing gas into the said vessel.
In a few words, the object of the invention is the discovery of chemical procosses
for the transformation into dextrine and glucose of all starchy substances, whether
they are in the natural state, or freed from foreign substances, such as potato-flour,
rice-starch, wheat-starch, or maize starch and so forth, which may previously be
transformed into dextrine or similar products. The process can generally be
employed for the preparation of saccharine ingredients (Succharin) and its application
extended to the numerous operations used in breweries, and the preparation of alcohol
for the purpose of transforming starchy substances into sugar.
WM. P. THOMPSON & Co.,
Of 6, Lord Street, Liverpool,
Agents for the Applicant.

page_text: Substances.
I, ALBERT HENRI JACQUES BERGE of Brussels in the Kingdom of Belgium, Dr.
of Natural Sciences 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 purpose of this invention is to effect the snecharification of starch or of other
raw materials containing starch in a quicker and more exhaustive manner than has
been possible through the processes heretofore employed.
This invention consists substantially in the use of sulphurous acid under high
pressure to exert its effect upon the material in an autoclave. The use of sulphurous
acid however has some inherent defects, among which is its tendency to transform
itself into sulphuric acid when it comes into contact with oxygen; the processes to
provent such action belong therefore also to my invention. The whole process can be
described in substance as follows:
The sulphurous acid is introduced into an autoclave in the proper quantity; then
through introduction of carbonic acid into the autoclave tho air contained in the same
is forced out thereupon the material to be transformed into sugar is introduced
slowly and mixed with the sulphurons acid. Then carbonic acid is pressed into the
autoclave until the highest pressure is reached, and finally all cocks of the same are
closed and the autoclave is heated during the whole time of the reaction.
Instead of carbonic acid also any other suitable gas may be used for the purpose of
keeping out the air and of obtaining the necessary pressure in the autoclave.
The apparatus shown in Figures 1 and 2 of the unexed drawings, is used for the
practical execution of the process. Figures 3 and 4, also 5 and 6, show only
con-tructive variations of the same.
The apparatus, Figures 1 and 2, is composed of a horizontal, cylindrical, solidly
fixed copper tank, closed at both ends by spherical covers which are supplied with
rubber rings in order to render them gas tight. The centre of the covers Qis
provided with bearings with stuffing boses E, in which rotates the mixer shaft W.
On the shaft Ware fixed four rakes, forming the mixer, composed of arms F, which
are provided with holes like grates and located at right angles relative to each other.
This mixer is moved by a cog-wheel, or pulley Z, solidly fixed on the mixer slatt and
connected with the motor. On the top of the tank, in the middle of the same, is
located an hermetically closing manhole la, which is used for the introduction of the
material to be subjected to the reaction. At both ends are located cocks 11, which
serve rospectively for the introduction or the escape of the gases.
Under one side of the tank is located a cock H, which serves for emptying the
autoclave, while under the other side is located a cock H2, which servos for obtaining
samples of the material while the process of saccharification is going on.
For the purpose of heating the material during the process above mentioned, the

page_text: autoclave is located inside of a steam mantle I. The manometers M are for the purpose
Instead of a
of measuring the pressure in the autoclave and in the steam mantle.
steam mantle, a steam pipe S, winding itself around the autoclave can be used for the
purpose of heating. The entrance and escape of the steam are marked i. G represents
a safety valve to avoid the high pressure in the autoclave. Ga safety valve to relive
the pressure in the steam jacket. A therinometer is connected at d with the autoclave
to show at any time the temperature in the same.
The apparatus so described can be used for the saccharification of all substances
containing starch. The following is the description of the process for different
materials.
A) Saccharification of potato, or, as the case may, bo starch-meal.
For the treatment of these substances, a solution of about 5 per cent. sulphurous
acid is used. This fills the apparatus about half, whereupon the air is driven out by
the introduction of carbonic acid. The carbonic acid enters through one of the
cocks H and the air escapes through the other one. Hereupon the potato, or starch
meal, is introduced in the proportion of about 5) kilograms weight to an autoclave
contents of one hectoliter. This material is poured in slowly through the manhole L,
and during the introduction, the mixer W, F. is set in rotation for the purpose of
securing an intimate mixture of the meal with the liquid, the carbonic acid keeping
away the air from the sulphurous acid during this time. The pouring in of the
material is continued until about 50 kilograms of material to 50 kilograms of liquid
are contained in the autoclave, the contents of which has to be a little larger than
1 hectoliter. There remains then between the surface of the liquid and the top of the
autoclave a free space of about 5 centimeters height; this free space may, if preferred,
be made much larger, that is to say, the capacity of the autoclave has no influence
upon the reaction to which the material is submitted. It can therefore be of any
convenient size.
After the filling is terminated, the manhole is hermetically closed and the air is
driven out by newly introducing carbonic acid. Hereupon the cock H is closed and
the carbonic acid is continued to be pumped in, until it reaches a pressure of say
6 atmospheres.
After closing the feeding cock the process of beating is commenced. Steam is
introduced into the mantle L, and the temperature is raised to about 135 degrees and
kept so high until the glutinous substances which are formed have been totally
changed into soluble starch. These changes are watched on samples taken through
the cock H.
When the process has reached this point, the temperature is lowered to about
120 degrees, and the heating under this temperature is continued until the desired
degree of saccharification is reached. Thereupon the gas escape H is opened, and the
gases used can either be allowed to escape freely into the open air, or they can be
stored in appropriate reservoirs, which can be located in columns, in tanks etcetera,
for the purpose of being used again at the next operation.
After the gases have entirely escaped, the outlet cock H¹ is opened, and through it
the saccharificated substance, which is more or less fluid, flows into a receptacle, where
it reumains undisturbed, and after a period of about three hours the saccharification is
completed.
If the product obtained out of the potato, or out of starch meal is destined, as
usual, to the production of glucose-syrup, the material is first filtered through a bone
filter, if it has to be entirely colorless, and then evaporated in vacuo.
When economy is no object it is of advantage to use solutions of less strength, that
is to say of greater consistency, as for instance of 2 per cent. to 3 per cent., and a less
proportion of starch, about 30 kilograms. But where it is necessary to limit the
number of operations, proportions of even over 50 kilograms to the hectoliter can be
worked; only the saccharification is more difficult in beginning.
B) Saccharification of cereals.
The most advantageons results can be reached through the reaction on cereals, that
is to say, on unbroken corn.

page_text: The above described process is simplified as first the sulphurous acid, and then
immediately cereals are introduced into the autoclave, and then only the forcing out
of the air through the introdution of the carbonic acid and the following compression
of the gas are rusorted to.
The mixer is not necessary under these circumstances, though it can be used in
accordance with one's own judgment. But the process succeeds with cereals in an
autoclave without mixer, as the sulphurous avil can exert its action separately upon
each individual corn, provided the autoclave is suitably disposed for the compression
of the gas as well as for the steam heating. The intensity of the sulphurous solution
varies according to the kind of cureals, from about 3 per cent. to 5 per cent. The
quantity of cereals used to one hectoliter can be the greatest possible, provided all
corn is drowned in the liquid.
The heating is accomplished differently, according to whether the product is
intended for breweries or distillation.
In the first case the object is to obtain products having a pleasant taste, and the
autoclave is therefore heated only to 110 or 12 degrees. In the second ease the
object is the saccharitiention of the whole mass, and for this purpose the temperature
of 1.0 to 145 degrees is the most convenient, especially for the transformation of the
material into soluble starch.
In the case of cereals, if the autoclave is not necessarily to be filled up to its utmost
capacity, solutions of a less degree, that is to say of 2 per cent. to 3 per cent.
sulphurous acid as above described can be usel with advantage.
Ground cereals, namely, flour, give less good results, as, when such material is used,
a glutinous substance is formed, which offers a great resistance to the reaction. This
is not the case with the unbroken corns which present a large surface to the action of
the acid, nor with potato, or starch meal, which form no glue.
The process is terminated as above, with the only difference that the olimination of
tho sulphurous acid is obtained through the introduction of steam, whereupon the
whole material is pressed in a filter. The product is then exposed as usual to
fermentation.
The remains can he used as food for animals or also as fertilizers.
() Saccharification of potatoes.
For this purpose the potatoes are first pressed, and then treated like starch meal.
The end of the process goes on in a similar manner to that described in A. or B.
If the purposo of the operation is to produce glucose, the potatoes must first be
freed from their skins.
Figures 3 and 4, also Figures 5 and 6, show analogous apparatuses which can be
used, as well as the one described at first for the treatment of cereals.
The autoclave shown in Figures 3 and 4 is composed of a rotating cylinder A
resting on two supports T. The introduction of the cereals takes place through the
manhole I.; the sulphurous acid is introduced through the pipes or ; also, hereaftor,
the carbonic acid; the air escapes then through r or through tho manhole L. The storm
heating pipe S has its steam in and outlets as shown by the arrows. The ends of this
pipo go through the hollow shaft of the rotating cylinder. On this shaft is fixed
a cog-wheel Z commanded by the motor, which sets the cylinder in rotation. The
inside of the cylinder A is provided with agitators N to keep the matter in constant
movement in a direction vertical to the plane of rotation.
The manometer is attached to a pipe fixed at the end of the other hollow shaft of the
cylinder, and through which it is connected with the inside of the same. This pipe as
well as the steam pipe, is provided at the places where they enter the cylinder, "with
the necessary stuff boxes to render the cylinder completely gas tight.
The autoclave shown in Figures 5 and 6 is composed of a cylinder of strong metal A
provided at the top and bottom with conical cast iron covers K; the latter are
hermetically closed through flat covers D. The whole rests on a T-shaped ring,
which is carried by several supports T.
The introduction of the cereals takes place through the upper cover D, which, when
the autoclave is filled to about 3-4 is hermetically closed. The introduction of

page_text: sulphurous acid can take place in different ways. It can either enter from a
reservoir R through a piper provided with the necessary cocks H and valve V into
the top cover K; or it can be introduced under pressure through a pipe provided
with a cock B into the bottoin cover K; then the introduction of carbonic acid
through the top or the bottom cover begins, and the air is driven out.
For the latter purpose the pipes are connected with reservoirs containing
carbonic acid under pressure, or with a suitable compression pump. The pipe leads
to the top, the pipe to the bottom of the autoclave; they are provided with the
valves and the lower one with the cock B. A triple cock H' permits the
introduction of the carbonic acid, at choice, into the upper or lower pipe. In the same
measure in which the space of the autoclave not taken up by material is being filled
with carbonic acid, the air contained in the same escapes through a suitably located
valve, which is closed as soon as all the air in the autoclave is replaced by carbonic
acid. Through further compression of carbonic acid or any other suitable non-
oxidating gas or gas compound, the pressure in the autoclave is then raised to the
convenient height.
The exclusion of the air can also be obtained by filling the autoclave at first entirely
with sulphurous acid, then pouring in the material, closing the cover, and thereupon
introducing the carbonic acid. The carbonic acid entering the cylinders then forces a
part of the sulphurous acid out, and this latter escapes through a corresponding valve
and is taken up in a proper receptacle to be used again. The whole is heated to a
convenient degree, by steam passing in the surpentine pipe S fixed on the bottom
cover K.
Instead of sulphurous acid a solution of hyposulphite of lime can also be used.
The quantity of lime dissolved must be proportional to the desired degree of intensity
of the solution. A solution of sulphurous acid is, howover, always preferable.
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is :-
The saccharification of starch or starch bearing raw materials in an autoclave with
a solution of sulphurous acid or hyposulphite of lime, after the autoclave has been
filled with carbonic acid for the purpose of excluding the air and preventing the
oxidation of the sulphurous acid and the subsequent heating of the same to about
110 to 145 degrees, while the pressure in the autoclave is raised to that of several
atmospheres by passing in carbonic acid or other non-oxidating gas, substantially as
described.
DIL! 101 1
' 1000