IMPROVEMENTS IN THE METHOD OF AND APPARATUS FOR THE MANUFACTURE OF GLUCOSE
Year: 1875

page_text: LETTERS PATENT to Samuel Henry Johnson, of Lea Bank Works,
Warton Road, Stratford, in the County of Essex, for the In-
vention of "IMPROVEMENTS IN THE METHOD OF AND APPARATUS FOR THE
MANUFACTURE OF GLUCOSE.”
PROVISIONAL SPECIFICATION left by the said Samuel Henry
Johnson at the Office of the Commissioners of Patents, with
his Petition, on the 4th March 1875.
I, SAMUEL HENRY JOHNSON, of Lea Bank Works, Warton Road,
Stratford, in the County of Essex, do hereby declare the nature of
the said Invention for "IMPROVEMENTS IN THE METHOD OF AND APPAratus
FOR THE MANUFACTURE OF GLUCOSE," to be as follows:-
''
This Invention has for its object the manufacture of glucose from
permeable" grain, the purification thereof by the means herein-after
described, and improvements in the apparatus to be employed therein.
Where the term "permeable" grain is mentioned it must be under-
stood to 'include grain whole, crushed, bruised, or broken, or in such

page_text: .
other form that steam can permeate every part of a layer or bed of it
with facility. Whole grain is generally preferred in this process, but
in some cases it may be more convenient or cheaper to employ broken
grain. The grain, however, must not be in the form of flour.
For the purpose of this Invention rice or other grain containing
starch may be employed, and for the conversion of such rice, for
example, into glucose .I proceed as follows:-The grain is first
macerated in a wooden vat or other suitable receptacle with as much
diluted hydrochloric acid containing about 2 per cent. of real acid as is
necessary to cover the grain completely, with the liquid. Other acids
may be employed as herein-after described. When the grain has
absorbed as much as possible of the dilute acid I draw off the liquid
which remains unabsorbed by withdrawing a plug from a hole in the
bottom of the vat or by other suitable means, but so as that by the inter-
position of a filter or diaphragm the grain shall be prevented from
flowing away with the liquid.
The dilute acid which has been drawn off from the grain will be
found to have increased considerably in specific gravity, due to the pro-
tein and albumenoid compounds which have become dissolved in it from
the grain. It will have also acquired an aromatic odour, due to the
essential oils removed from the grain by this treatment.
In order the more completely to remove the nitrogenous principles
and the essential oils which still remain in the grain, I macerate it with
clean water in such a manner as that when the grain has becomo
covered with the water the liquid is allowed to flow off at the bottom of
the vat through an aperture provided with a filtering diaphragm. The
water is supplied at the top at the same rate as the liquid percolatos
through the grain. This percolation is continued until the liquid.
running away from the grain no longer gives an acid reaction to litmus
paper. When this neutral condition is attained the grain is allowed to
drain, and it is afterwards again macerated for a few hours in dilute
hydrochloric acid containing 1 or 2 per cent. of real acid. This
maccration is continued until the acid dialyses through the tissues of
the grain to such an extent that it will contain enough acid to effect
its conversion into glucose when treated by the method herein-after
mentioned.
The proportion of acid varies according to the nature of the grain, the
temperature at which the conversion is effected, and the amount of
=

page_text: water present at the time of conversion. Rice, for example, ordinarily
requires about 4th part of its weight when dry of real bydrochloric
acid to be present in the grain to effect the conversion under the cir-
cumstances and conditions of temperature and moisture that would
obtain with it when treated as herein described, but the amount of
acid necessary for conversion varies with different grains and with
different samples of the same species of grain. It is therefore necessary
when treating a particular lot of grain to ascertain by experiment the
least proportion of acid which under all circumstances it would be most
desirable to employ, and so as that during the process of conversion the
grain shall not be exposed to the high temperature necessary for such a
length of time as would materially affect the color of the resulting
product.
i
The grain when prepared as above described and well drained is
introduced into a strong wrought-iron vessel lined with lead, or with a
silicate enamel capable of resisting the action of the acid, or the vessel
may be made of gun metal, and in such case it need not be lined with
lead. The vessel should be of such a shapo that when steam is
introduced through a perforated diaphragm at the bottom it shall be
able to pass with facility through every part of the material contained
in the vessel. For this purpose I form the lower portion of the vessel
in the shape of an inverted truncated conc, the whole area of the small
truncated portion being covered internally by a perforated diaphragm
for the admission of steam. This vessel is further provided with a
suitable opening at the top for the introduction of the prepared grain,
which opening is capable of being hermetically closed. It is also pro-
vided with a steam pressure gauge, a draw-off cock, and a sampling
cock connected beneath the perforated diaphragm before mentioned.
When such vessel is formed of wrought or cast iron lined with lead it
becomes necessary to perforate the iron at intervals with small holes, so
as to prevent the accumulation of steam in caso any moisture or
dampness existed between the shell and the lead lining. Such accumu.
lation of steam would inevitably occur in the absence of the precaution
indicated and when the contents of the vessel were removed, thus
withdrawing the internal pressure the leaden lining would collapse.
When the prepared grain is introduced into the vessel it still retains
its form, and the mass is consequently quite porous, so that the steam
introduced beneath the perforated diaphragm at the bottom of the vessel

page_text: immediately permeates every portion of the material under operation,
and owing to the form of the vessel and the porous condition of the
grain the temperature of the mass is speedily raised without the aid of a
mechanical agitator to the point at which the conversion into glucose.
takes place, the requisite degree of temperature being reached before a
sufficient quantity of water has been formed by the condensation of the
steam to destroy the porous nature of the grain under operation. When
this point is attained the contents of the vessel become liquid, and are
put into a' state of violent agitation by the ingoing current of steam.
The pressure under which such steam is introduced should not be less
than 50 lbs. nor more than 100 lbs. to the square inch. The pressure is
varied between these limits according to the nature of the grain employed
or the required character of the resulting product. For example, if it
be desired that the product should retain a certain amount of dextrine,
then a lower pressure would be employed than that which would be 1
necessary for the complete conversion of the grain into glucose.
2
The mass may be sampled during the process by means of the samplo
cock, and after dilution and cooling the samples may be tested for the
presence of starcli and dextine by means of an aqueous solution of
iodinė. When the conversion is completed, which for rice requires from
10 to 15 minutes provided the steam has been injected with sufficient
rapidity, the contents of the vessel are forced out through the draw-off
cock into large shallow coolers. In these coolers the material is
neutralised with an alkali or alkaline earth or their carbonates in the
usual way. If the product is required for the purpose of brewing or 2
distilling, then the presence of the extraneous tissue, &c., is of little
consequence. In such case the syrup may be at once boiled down in a
vacuum pan to the degree of concentration necessary for its solidification.
It is found that glucose so obtained is free from the unpleasant bitter
taste of fusil oil, which is climinated by the hydrochloric acid treatment a
in the first stage of the process.
:
Hitherto in order to remove this taste it has been found necessary to
filter the glucose through animal charcoal, but such filtration for this
purpose is rendered unnecessary by this process. The syrup is also
produced in such a degree of concentration as has hitherto been found a
impracticable.

page_text: accompanying it, it will be necessary to dilute the syrup after neu-
tralization and filter it by any convenient method, whether under pressure
or otherwise.
If it be desired to produce glucose free from coloration it will be
necessary to filter it through animal charcoal, but it will be found that
after the treatment which I have described a much smaller proportion
of animal charcoal will be required than has hitherto been the
case.
For the purpose of removing the fusil oil and nitrogenous substances
other acids may be employed in lieu of hydrochloric acid, such as nitric,
sulphuric, and acetic acids, but hydrochloric acid answers the purpose
best. The hydrochloric acid may also be replaced by nitric and sul-
phuric acids for the purpose of conversion, but hydrochloric acid is the
most powerful, and effects the conversion with the smallest amount of
coloration. Where hydrochloric acid is used the quantity necessary is so
small that the common salt produced by neutralization with carbonate
of soda remaining in the glucose is of no material consequence.
Before macerating the grain with dilute hydrochloric acid for the
purpose of removing impurities I sometimes precede that treatment with
a maceration in a solution of caustic soda or other alkali for the purpose
of more perfectly removing the nitrogenous portion of the grain. The
alkali solution should contain to 1% of alkali.
After macerating a sufficient time I remove the alkaline solution,
which has dissolved in it a considerable portion of the gluten of the
grain, and I wash out the alkali in the same manner as described herein
in reference to the acid treatment; I then proceed with the acid treat-
ment as herein-before described.
When it is desired to produce glucose or dextrine at the cheapest
possible rate for brewing or distilling purposes I omit the purification
processes preceding the conversion, and adopt the following plan, which
I hereafter call my second process, I treat the grain in a revolving or other
suitable vessel, which procures the proper mixing of the grain with about
4 per cent. of its weight of dilute hydrochloric acid, of specific gravity
about 1060 until the acid is absorbed by the grain. After tho acid
has been allowed to remain in contact with the grain for the time ncces-
sary for the disintegration of the tissues, the mass may then be treated

page_text: in the converter in the manner herein-before described, when it will be
found that after expulsion from the converter neutralizing and cooling
the mass will become solid, or nearly so, provided the grain employed for
the purpose did not contain an undue amount of water. In such latter
case the excess of water above what is necessary for the conversion t
should be expelled by heat from the grain before it is employed for the
purpose by means of a kiln or other convenient apparatus.
In order to reduce the quantity of water to the smallest possible pro-
portion it is desirable that the neutralization of the acid should be effected
with dry reagents. For this purpose in the case of the employment of 1
hydrochloric acid I prefer to use dry carbonate of soda, but when I
employ sulphuric acid I prefer dry carbonate of lime. By this second
method I am enabled to produce glucose from normal rice in such a state
of concentration that after cooling with agitation to facilitate the evapo-
ration of the water the mass becomes solid, or nearly so, whereby the 1
expense of evaporation is saved and the prejudicial effect of heat on the
color of the resulting product is avoided. In this second process, as in
the first, the proportion of acid must be varied according to the nature
of the grain operated upon, the most convenient proportion having been
previously determined by experiment.
2
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Samuel Henry Johnson in the Great Seal
Patent Office on the 3rd September 1875.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, SAMUEL
HENRY JOHNSON, of Lea Bank Works, Warton Road, Stratford, in the
County of Essex, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Fourth day of March, in the year
of our Lord One thousand eight hundred and seventy-five, in the
thirty-eighth year of Her reign, did, for Herself, Her heirs and suc-
cessors, give and grant unto me, the said Samuel Henry Johnson,
Her special license that I, the said Samuel Henry Johnson, my
executors, administrators, and assigns, or such others as I, the said
Samuel Henry Johnson, my executors, administrators, and assigns,

page_text: should at any time agree with, and no others, from time to time and
at all times thereafter during the term therein expressed, should and
lawfully might make, use, exercise, and vend, within the United King-
dom of Great Britain and Ireland, the Channel Islands, and Isle of
Man, an Invention for "IMPROVEMENTS IN THE METHOD OF AND APPARATUS
FOR THE MANUFACTURE OF GLUCOSE," upon the condition (amongst
others) that I, the said Samuel Henry Johnson, my executors or
administrators, by an instrument in writing under my, or their, or one
of their hands and seals, should particularly describe and ascertain the
nature of the said Invention, and in what manner the same was to be
performed, and cause the same to be filed in the Great Seal Patent Office
within six calendar months next and immediately after the date of the
said Letters Patent.
NOW KNOW YE, that I, the said Samuel Henry Johnson, do
hereby declare the nature of the said Invention, and in what manner
the same is to be performed, to be particularly described and ascertained
in and by the following statement thereof, that is to say :—
"
This Invention has for its object the manufacture of glocose from
permeable" grain, the purification thereof by the means herein-after
described, and improvements in the apparatus to be employed therein.
Where the term "permeable" grain is mentioned it must be understood
to include grain whole, crushed, bruised or broken, or granular amyla-
ccous substances, being of such form and combined with only so small a
proportion of water or liquid that steam can permeate every part of a layer
or bed of it with facility, it being an essential feature in my Invention
that complete permeation of the steam should be effected, whole grain
is generally preferred in this process; but in some cases it may be more
convenient or cheaper to employ broken grain. The grain however
must not be in the form of flour as it would then form a paste
more or less gelatinous, and so prevent complete permeation of the
steam.
For the purpose of this Invention rice or other grain containing starch
may be employed, provided it be kept in a permeable condition, so as
to allow steam to penetrate and act upon it until the starchy portion of
all the grain becomes converted into dextrine. In all processes with
which I am acquanted that have been heretofore proposed to be used,
the grain operated upon has been treated with so much water as to

page_text: allow of the starch to become so gelatinous and expand so much as to
form a paste more or less impermeable to steam. This inconvenience I
take care to avoid and I proceed as follows:-The grain is first macerated
in a wooden vat or other suitable receptacle, with as much diluted hydro-
chloric acid, containing about 2 per cent. of real acid, as is necessary
to cover the grain completely with the liquid. Other acids may be
employed as herein-after described. When the grain has absorbed as
much as possible of the dilute acid I draw off the liquid which remains
unabsorbed by withdrawing a plug from a hole, in the bottom of the
vat, or by other suitable means, but so as that by the interposition of a
filter or diaphragm the grain shall be prevented from flowing away
with the liquid.
་
The dilute acid which has been drawn off from the grain will be found
to have increased considerably in specific gravity due to the protein and
albumenoid compounds, which have become dissolved in it from the
grain. It will have also acquired an aromatic odour due to the essential
oils removed from the grain by this treatment.
In order the more completely to remove the nitrogenous principles
and the essential oils which still remain in the grain, I macerate it with
clean water in such a manner as that when the grain has become
covered with the water the liquid is allowed to flow off at the bottom
of the vat through an aperture provided with a filtering diaphragm.
The water is supplied at the top at the same rate as the liquid percolates
through the grain. This percolation is continued until the liquid
running away from the grain no longer gives an acid reaction to
litmus paper. When this neutral condition is attained the grain.
is allowed to drain, and it is afterwards again macerated for a few
hours in diluto hydrochloric acid containing 1 or 2 per cent. of real
acid. This maceration is continued until-the-acid-dialyses-through the
tissues of the grain to such an extent that it will contain enough acid
to effect its conversion into glucose when treated by the method herein-
after mentioned.
The proportion of acid varies according to the nature of the grain,
the temperature at which the conversion is effected, and the amount of
water present at the time of the conversion. Rice for example, ordi-
narily requires about 10th part of its weight, when dry, of real
hydrochloric acid to be present in the grain to effect the conversion

page_text: under the circumstances and conditions of temperature and moisture
that would obtain with it when treated as herein described, but the
amount of acid necessary for conversion varies with different grains, and
with different samples of the same species of grain. It is therefore
necessary when treating a particular lot of grain to ascertain by experi-
ment the least proportion of acid which, under all circumstances, it would
be most desirable to employ, and so as that during the process of con-
version the grain shall not be exposed to the high temperature necessary
for such a length of time as would materially affect the color of the
resulting product.
The grain when prepared as above described, and well drained is
introduced into a strong wrought-iron vessel lined with lead or with a
silicate enamel capable of resisting the action of the acid, or the vessel
may be made of gun metal, and in such case it need not be lined with
lead. Such a vessel is represented on Sheet 1 of the annexed Drawings.
The vessel should be of such a shape that when steam is introduced
through a perforated diaphragm at the bottom it shall be able to pass
with facility through every part of the material contained in the vessel.
For this purpose I form the lower portion of the vessel in the shape of
an inverted truncated cone, the whole area of the small truncated
portion being covered internally by a perforated diaphragm for the admis-
sion of steam. This vessel is further provided with a suitable opening
at the top for the introduction of the prepared grain, which opening
is capable of being hermetically closed. It is also provided with a steam
pressure gauge and a draw-off cock and sampling cock, connected
beneath the perforated diaphragm before mentioned. There is also at
the bottom a trap or small box to receive and retain any water which
may be brought over by the steam. When such vessel is formed of
wrought or cast iron lined with lead (such a vessel is represented on
Sheet 2 of the Drawings) it becomes necessary to perforate the iron at
intervals with small holes so as to prevent the accumulation of steam in
case any moisture or dampness existed between the shell and the lead
lining. Such accumulation of steam would inevitably occur in the
absence of the precaution indicated, and when the contents of the vessel
were removed, thus withdrawing the internal pressure the leaden lining
would collapse.
When the prepared grain is introduced into the vessel it still retains

page_text: introduced beneath the perforated diaphragm .at the bottom of tho
vessel immédiately permeates every portion of the material under
operation, and owing to the form of the vessel and the porous condition
of the grain tlie temperature of the mass is speedily raised without the
aid of a mechanical agitator to the point at which the conversion into
glucose takes place, the requisito degree of temperature being reached
before a sufficient quantity of water has been formed by the condensation
of the steam to destroy the porous nature of the grain under operation.
When this point is attained the contents of the vessel become liquid
and are put into a state of violent agitation by the ingoing current of
steam. The pressure under which such steam is introduced. should not
be less than 50 lbs. nor more than 100 lbs. to the square inch, although
lower pressures can be employed, yet it is not at all advantageous to uso
them. The pressure is varied between these limits according to the
nature of the grain employed or the required character of the resulting
product. For example if it be desired that the product should retain a
certain amount of dextrine then a lower pressure would be employed
than that which would be necessary for the complete conversion of the
grain into glucose.
The mass may be sampled during the process by means of the sample
cock, and after dilution and cooling the samples may be tested for the
presence of starch and dextrine by means of an equeous solution of
iodine. When the conversion is completed, which for rice requires from
5 to 15 minutes (provided the steam has been injected with sufficient
rapidity) the contents of the vessel, are forced out through tlie draw-off
cock into large shallow coolers provided with suitablo agitators, or into
other suitable apparatus for reducing the temperature with rapidity.
In these coolers the material is neutralized with an alkali or alkaline
carth, or their carbonates in the usual way. If the product is required
for the purpose of brewing or distilling, then the presence of the
extraneous tissue, &c., is of little consequence. In such case the syrup
may be at once boiled down in a vacuum pan to the degree of con-
centration necessary for its solidification. It is found that glucose so
obtained is free from the unpleasant bitter taste of fusil oil, which is
eliminated by the hydrochloric acid treatment in the first stage of the
process.
Hitherto in order to remove this taste it has been found necessary to
filter the glucose through animal charcoal, but such filtration for this

page_text: purpose is rendered unnecessary by this process. The syrup is also
produced in such a degree of concentration as has hitherto been found
impracticable.
When it is required to separate the glucose from the insoluble matter
accompanying it it will be necessary to dilute the syrup after neu-
tralization and filter it by any convenient method, whether under
pressure or otherwise.
If it be desired to produce glucose free from colour it will be necessary
to filter it through animal charcoal; but it will be found that after the
treatment which I have described a much smaller proportion of animal
charcoal will be required than has hitherto been the case.
For the purpose of removing the fusil oil and nitrogenous substances
some other acids may be employed in lieu of hydrochloric acid, such as
nitric and sulphuric acids; but bydrochloric acid answers the purpose
best. The hydrochloric acid may be employed in the gascous state, and
may also be replaced by nitric and sulphuric acids for the purpose of
conversion, but a solution of hydrochloric acid is the most powerful and
convenient and effects the conversion with the smallest amount of
coloration. Where hydrochloric acid is used the quantity necessary is
so small that the common salt produced by neutralization with carbonate
of soda remaining in the glucose is of no material consequence.
Before macerating the grain with dilute hydrochloric acid for the
purpose of removing impurities I sometimes precede that treatment with
a maceration in a solution of caustic soda or other alkali for the purpose
of more perfectly removing the nitrogenous portion of the grain. Tho
alkali solution should contain ½ to 1 per cent. or more, of alkali, accord-
ing to the amount of nitrogenous substances in the grain.
After macerating a sufficient time (say 5 or 6 hours) I remove the
alkaline solution which has dissolved in it a considerable portion of the
gluten of the grain, and I wash out the alkali in the same manner as
described herein in reference to the acid treatment. I then proceed
with the acid treatment, as herein-before described.
When it is desired to produce glucose or dextrine at the cheapest
possible rate for brewing or distilling purposes, or where it is desired to
use amylaceous matters, such as sago, tapioca, &c., which have already
undergone purification processes for the purpose of freeing the starch

page_text: from albumenous matter, I omit the purification processes preceding
the conversion and adopt the following plan, which I hereafter call my
second process :-I treat the grain in a revolving or other suitable vessel
which procures the proper mixing of the grain with about 4 per cent. of
its weight of dilute hydrochloric acid of specific gravity about 1·000,
until the acid is absorbed by the grain. After the acid has been allowed
to remain in contact with the grain for the time necessary for the
disintegration of the tissues, the mass may then be treated in the con-
verter in the manner herein-before described, when it will be found that
after expulsion from the converter neutralizing and cooling the mass
will become solid, or nearly so, provided the grain employed for the
purpose did not contain an undue amount of water.
the excess of water above what is necessary for the conversion should bo
expelled by heat from the grain before it is employed for the purpose
by means of a kiln or other convenient apparatus.
In such latter case
In order to reduce the quantity of water to the smallest possible pro-
portion it is desirable that the neutralization of the acid should be
effected with dry reagents. For this purpose in the case of the employ-
ment of hydrochloric acid I prefer to use dry carbonate of soda, but
when I employ sulphuric acid I prefer dry carbonate of lime. By this
second method I am enabled to produce glucose or mixtures of glucose
and dextrine from normal rice in such a state of concentration that after
cooling with agitation to facilitate the evaporation of the water the mass
becomes solid, or nearly so, whereby the expense of evaporation is saved
and the prejudicial effect of heat on the color of the resulting product is
avoided.
When it is desired (for distilling purposes for instance) that the pro-
duct shall consist almost entirely of glucose, I then effect the conversion
as herein-before described, but before removing the material from the
converter I introduce into it a quantity of water or very dilute acid,
which by experiment is found to be sufficient for the grain employed,
and which has been previously heated under pressure to the temperature
of the contents of the converting vessel, and maintain it at this tempe-
rature until the desired result is obtained, which is determined by trial
during the progress of the operation. In this second process, as in the
first, the proportion or description of acid must be varied according to
the nature of the grain operated upon, the most convenient proportion
having been previously determined by experiment.

page_text: Having thus described the nature of my Invention and the manner of
performing the same, I would have it understood that I claim as my
improvements in the manufacture of and apparatus for the manufacture
of glucose,-
First. The treatment of grain in a permeable condition with dilute
acids, or in conjunction with alkalies, thereby removing fusil oil and
nitrogenous substances, substantially as described.
Second. The treatment of grain in a permeable condition by com-
bining with it such an amount of acid as is necessary to effect its
transformation into glucose, substantially as described.
Third. The treatment of acidified grain in a permeable condition by
causing steam to permeate the interspaces between the grains, sub-
stantially as described.
Fourth. The construction and use of converting apparatus, substan-
tially in the manner and for the purpose as herein described.
Fifth. The process of manufacturing glucose substantially as described.
In witness whereof, I, the said Samuel Henry Johnson, have
hereunto set my hand and seal, this Thirty-first day of August, in
the year of our Lord One thousand eight hundred and seventy-
five.
TTY
TATTÁSON