IMPROVEMENTS IN OBTAINING GLUCOSE AND ALCOHOL FROM LIGNEOUS MATERIALS, AND IN APPARATUS THEREFOR
Year: 1880

page_text: LETTERS PATENT to Alexander Melville Clark, of 53, Chancery Lane, in the
County of Middlesex, Patent Agent, for an Invention of "IMPROVEMENTS IN
OBTAINING GLUCOSE AND ALCOHOL FROM LIGNEOUS MATERIALS, AND IN
APPARATUS THEREFOR." A communication from abroad by Emile Stanislas
Dangivillé, of Paris, France.
PROVISIONAL SPECIFICATION left by the said Alexander Melville Clark
at the Office of the Commissioners of Patents on the 21st January 1880.
ALEXANDER MELVILLE CLARK, of 53, Chancery Lane, in the County of Middlesex,
Patent Agent. "IMPROVEMENTS IN OBTAINING GLUCOSE AND ALCOHOL FROM
LIGNEOUS MATERIALS, AND IN APPARATUS THEREFOR.' [A communication from
abroad by Emile Stanislas Dangivillé, of Paris, France.]
"
The transformation of cellulose into gummy substances, and further into glucose,
is well known as a laboratory operation.
This reaction has been heretofore employed for obtaining alcohol from wood but
has given no practical result, even at a time when alcohol was sold at a high price, as
the considerable quantity of sulphuric acid at 66° B. required for the transformation
rendered the process very expensive.
This Invention relates to a new process for transforming wood or ligneous
materials into glucose, and further, into alcohol if required. The Invention consists
in the employment of hydrochloric acid for this transformation, the acid employed
in a first operation being used again in a second one, and so on.
I have observed that pure cellulose when impregnated with a certain quantity of
water (the weight of which must not exceed the weight of cellulose treated) and
submitted to the action of hydrochloric gas without heating, is slowly and thoroughly
transformed into a thick and syrupy liquid soluble in water, which is but slightly
colored when the required precautions are taken.
When ligneous materials, such as soft and even hard wood cut into pieces are
submitted to the same treatment they are only dissolved in the proportion of 70 to
75°, because they are not pure cellulose. The soluble sustances so obtained when
distilled in vacuo part with the bydrochloric acid, and the residuum is glucose.
In carrying out the Invention various arrangements of apparatus may be

page_text: employed, and I will now proceed to describe with reference to the annexed
The ligneous
Drawings some arrangements which have given good results.
materials must be cut up into pieces of about the size of the wood chips employed in
dyeing operations. The materials are then impregnated with rather weak hydro-
chloric acid, and I prefer to employ the acid resulting from the above mentioned
distillation. The materials are fed through a hole A, Figure 1, Sheet 1, into
stoneware cylinders and submitted to the action of hydrochloric gas supplied
through apertures a, a, a, a. The substances are continuously fed in the first
cylinder and fall from the saine into a second one, from which they pass into suitable
tanks. Agitators M inattackable by acids or coated with substances suitable for
the purpose, stir the ligneous materials in order to thoroughly expose them to the
action of the hydrochloric gas flowing regularly into the cylinders, besides which
they serve to force the materials from the first cylinder into the second, and from
the latter into the tanks. The products received in the tanks are methodically
washed, ie, the weakest solutions are employed for washing the most highly
charged materials.
The evaporation of the concentrated solutions so obtained is made in the
apparatus shown in Figure 1, Sheet 2. This apparatus is formed of lava made in
parts A, A, placed one upon another and luted at e, e, e, e, each of these parts
comprising a trough into which the liquid to be evaporated is supplied at L.
The troughs are heated by series of pipes a, a, in which circulates steam or hot
water; these pipes are made of glass, earthenware, or other suitable substance
inattackable by acids.
The liquid supplied at L in the upper trough flows into the second trough, and
so on till it passes out at N. S, S, are two chambers filled with coke or pieces of
earthenware upon which weak hydrochloric acid for condensing the vapors is
caused to flow through a perforated pipe K; the condensed liquids are extracted
from the apparatus at M, M, by a pump working without interruption. H, H, are
apertures connected with a vacuum pump or other suitable apparatus, and R, R, are
glazed sight holes for surveying the operation.
1
The apparatus shown in the Drawings has only four troughs but I can employ as
many troughs as are required for effecting a complete evaporation. The only
important precaution to be observed is to so regulate the passage of the liquid in
the apparatus that the product flowing out at N may consist of glucose containing
but a small percentage of acid. In order to render the evaporation more rapid and
efficient thin layers only of liquid should be treated; it is also necessary to increase
the heating surfaces and obtain the most perfect vacuum and condensation
possible; any apparatus realizing these conditions may be used instead of the
arrangement shown in the Drawings. The condensed acid comes out from the
apparatus at 15° B., about, and in order to obtain from it the hydrochloric gas
required for the first described operation, the apparatus shown in Sheet 3 may be
employed. This apparatus consists of a vat B partly filled with sulphuric acid at
60° B., which is heated by a lead steam worm from 308° to 340° F.
Streamlets of the hydrochloric acid at 15° B. are supplied by apertures d. d, and
fall into the heated sulphuric acid; the required gas is thus obtained and conducted
through pipes e to the cylinders in which are placed the ligneous materials to he
treated. The diluted sulphuric acid passes through the pipe b and flows at g into
a large covered tank A provided with an inner lead lining and heated by a steam
worm at about 300° F.; the sulphuric acid when concentrated in this tank at 60 B. is
forced again into the vat B by a suitable pump to produce by a new operation a
certain quantity of hydrochloric gas or vapor.
The concentration of the sulphuric acid is rendered more rapid by means of a
current of air heated in the stove G, and which is supplied from a blowing fan and
escapes at N after having swept the surface of the liquid. The hot and wet air
escaping at N is then allowed to pass into a series of jars for condensation, the jars
placed near N containing weak hydrochloric acid. The liquid glucose flowing from

page_text: the vacuum evaporating apparatus contains but a very small percentage of hydro-
chloric acid; it is mixed with hot distillers' wash or water in order to obtain a
liquid containing about 12% glucose; this liquid is then allowed to boil during a
few hours in order to obtain a complete transformation of the gummy substances
into glucose, if such substances yet remain after the above described operations;
after that the acid is saturated with chalk or calcareous stone. The liquid so
obtained may be submitted to further fermentation, distillation, and concentration
in order to obtain alcohol, if required.
The above described apparatus for generating hydrochloric gas or vapor and
concentrating sulphuric acid may be heated by other means than by steam; I can,
for example, heat them directly by furnaces or use waste heat from other
apparatus.
I would observe that this improved process or method can be applied to every
kind of ligneous substances, such as saw dust, shavings of soft or hard woods, as
well as to wood residues of dyeing operations and tanners' bark, rice, maize, and
other straw and hop stalks.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said Alexander Melville Clark in the Great Seal Patent Office on the 21st
July 1880.
ALEXANDER MELVILLE CLARK, of 53, Chancery Lane, in the County of Middlesex,
Patent Agent.
"IMPROVEMENTS IN OBTAINING GLUCOSE AND ALCOHOL FROM
A communication from
LIGNEOUS MATERIALS, AND IN APPARATUS THEREFOR."
abroad by Emile Stanislas Dangivillé, of Paris, France.
The transformation of cellulose into gummy substances, and further into glucose,
is well known as a laboratory operation.
This reaction has been heretofore employed for obtaining alcohol from wood, but
has given no practical result, even at a time when alcohol was sold at a high price,
because the considerable quantity of sulphuric acid at 66° B. required for the trans-
formation is very expensive.
This Invention relates to a new process for transforming wood or ligneous
materials into glucose, and further into alcohol if required. This process consists
in using hydrochloric acid for this transformation, the acid employed in a first
operation being used again in a second one, and so on.
I have observed that pure cellulose when impregnated with a certain quantity of
water (the weight of which must not exceed the weight of cellulose treated) and
submitted to the action of hydrochloric acid gas without heating, is slowly and
thoroughly transformed into a thick and syrupy liquid, soluble in water, which is
but slightly colored, when the required precautions are taken.
When ligneous materials, such as soft and even hard wood cut into pieces, are
submitted to the same treatment, they are only dissolved in the proportion of 70
to 75% of their weight, because they are not pure cellulose.
The soluble substance so obtained when distilled in vacuo parts with the hydro-
chloric acid and the residue is glucose.
.
Many mechanical arrangements may be employed for carrying the Invention into
practical effect, and I will now proceed to describe with reference to the Drawings
an arrangement which has given good results.
The ligneous materials are first cut up into pieces of about the size of the wood
chips used in dyeing. The materials are then impregnated with water, or preferably
with rather weak bydrochloric acid, preferably the acid resulting from the above
mentioned distillation. The materials are fed into stoneware cylinders, seo
Figures 1 and 2, through the aperture A, and submitted to the action of hydro-
chloric acid gas introduced at apertures a, a, a, a.
The substances are continuously fed into the first cylinder, and fall from thence
into a second one, from which they pass out at B into suitable tanks.
Agitators M, inattackable by acids or coated with substances suitable for the
purpose, are employed to stir the ligneous materials in order to thoroughly expose
them to the action of the hydrochloric acid gas flowing regularly into the cylinders,
and to convey the materials from the first cylinder into the second, and from the
latter into the tanks.
The products received in the tanks are methodically washed, i.e., the weakest
solutions are employed for washing the most charged materials.
The evaporation in vacuo of the concentrated solutions so obtained is effected in
the apparatus shown in Figures 3, 4, and 5.
This apparatus is constructed of a series of rectangular chambers A, A, A, B,
composed of lava disposed one upon another, and luted at e, e, e, e, each chamber
being formed with a trough F, to the upper one of which the liquid to be evaporated
is supplied at L. The troughs are heated by a series of pipes a, a, a, in which circu-
lates steam or hot water, the pipes being made of glass, earthenware, or other
suitable substance inattackable by acids.

page_text: The liquid supplied at L to the upper trough flows into the second trough, and so
on, till it escapes at N.
S, S, are two chambers filled with coke or pieces of earthenware, upon which
weak hydrochloric acid in a cold state is caused to flow continuously from a
perforated pipe K for condensing the vapours. The condensed liquids are extracted
from the apparatus at M, M, by a pump working uninterruptedly.
H, H, are apertures connected with a pump or other suitable apparatus for
creating a vacuum, and R, R, are glazed sight holes for surveying the operation.
The apparatus shown in the Drawings has only four troughs, but I can employ
such number of troughs as may be required for effecting a complete evaporation.
The only important precaution to be observed is to so regulate the passage of the
liquid through the apparatus that the product flowing out at N may be glucose,
containing but a small percentage of acid.
In order to make the evaporation more rapid and efficient it is necessary to treat
only thin layers of liquid and to multiply the heating surfaces and obtain the
most perfect vacuum and condensation possible. Any apparatus realizing these
conditions may be employed instead of that shown in the Drawings.
The condensed acid passes out from the apparatus at 15° B., about; and in order
to obtain from it the hydrochloric acid gas to be used again for the first described
operation, the apparatus shown in Figures 6, 7, 8, and 9 may be employed. This
apparatus consists in a vat B partly filled with sulphuric acid at 60° B., which is
heated by a leaden steam worm to from 266° to 275° Fahrt.
The hydrochloric acid at 15° B. is supplied in streamlets at apertures d, d, and
falls into the heated sulphuric acid, the hydrochloric acid gas becomes disengaged
and passes out through aperture e to the cylinders in which the ligneous materials
to be treated are placed.
The dilute sulphuric acid flows through the pipe b and enters at ginto a large
covered tank A provided with an inner lead jacket, and heated by a lead steam
worm to about 300° Fahr. The sulphuric acid is re-concentrated in this tank to
60° B., and returned by pipes h, a, to the vat B by a suitable pump for disengaging
more hydrochloric acid gas or vapour.
The concentration of the sulphuric acid is rendered more rapid by introducing a
current of air heated in the stove C, which is supplied from a blowing fan at m, and
escapes at n, after having swept the surface of the liquid. The hot and moist air
escaping at n passes thence into a series of jars for condensation, and in those
nearest the apparatus weak hydrochloric acid will be found.
The liquid glucose flowing from the vacuum evaporating apparatus contains but
a very small percentage of hydrochloric acid, it should be mixed with hot distillers'
wash or water in order to obtain a liquid containing about 12% glucose. This
liquid is then boiled for a few hours in order to effect the complete transformation
of the gummy substances into glucose, if such substances yet, remain after the
above described operations; after this the acid is saturated with chalk or
limestone.
The liquid so obtained may be submitted to the ordinary processes of fermenta-
tion, distillation, and rectification in order to obtain alcohol if required.
The above described apparatus for generating hydrochloric acid gas or vapours,
or concentrating sulphuric acid, may be heated by other means than by steam.
I can, for example, heat them directly by means of furnaces or by the waste heat
from other apparatus.
"
The process or method can be applied to every kind of ligneous substance,
including saw-dust, shavings of soft or hard woods, as well as to residues of woods
from dyeing operations and spent tan, rice, maize, and other straw and hop stalks,
&c., &c.
Having now described the nature of the Invention, I wish to have it well under-
stood that I do not confine myself to the above described apparatus, as any other
dispositions giving similar results may be employed without departing from the

page_text: essential features of the said Invention, but what I claim as the Invention to be
protected by the herein before in part recited Letters Patent is,-
1st. The transformation of cellulose into glucose by the action of hydrochloric
acid gas upon ligneous substances impregnated with a sufficient quantity of water
or weak hydrochloric acid, as and for the purposes set forth.
2nd. Evaporating the product of the above mentioned operation in vacuo so as
to permit of the hydrochloric acid being separated and employed again in further
operations, as set forth.
3rd. The combination of the above described processes for obtaining glucose or
alcohol from ligneous materials at a price lower than by the means heretofore
employed.
4th. The combination of the above described apparatus for carrying the Invention
into practice, as set forth.
In witness whereof, I, the said Alexander Melville Clark, have hereunto set
my hand and seal, this Twentieth day of July, in the year of our Lord
One thousand eight hundred and eighty.
A. M. CLARK. (L.S.)