United States Patent (19) 11) 4,174,976

Tsao et al. 45) Nov. 20, 1979

(54) ACID HYDROLYSIS OF CELLULOSETO 2,945,777 7/1960 Riehm .................................... 27/37
YELD GLUCOSE 4,058,411 1 1/1977 Bellamy ................................. 127/37
(75) Inventors: George T. Tsao; Michael R. Ladisch; Primary Examiner-Sidney Marantz
Arindam Bose, all of West Lafayette, Attorney, Agent, or Firm-John R. Nesbitt
Ind.
57 ABSTRACT
(73) Assignee: Purdue Research Foundation, West A process to yield glucose from cellulose through acid
Lafayette, Ind.
21 Appl. No.: 884,478 hydrolysis. Cellulose is recovered from cellulosic mate
rials, preferably by pretreating the cellulosic materials
(22 Filed: Mar. 8, 1978 by dissolving the cellulosic materials in Cadoxen or a
51) Int. Cl. ................................................ C13K 1/02 chelating metal caustic swelling solvent and then pre
52 U.S. C. ...................................................... 127/37 cipitating the cellulose therefrom. Hydrolysis is accom
58 Field of Search .......................................... 127/37 plished using an acid, preferably dilute sulfuric acid, and
the glucose is yielded substantially without side prod
(56) References Cited ucts. Lignin may be removed either before or after
U.S. PATENT DOCUMENTS hydrolysis.
2,323,022 6/1943 Ferrari ................................... 127/37
2,752,270 6/1956 Specht ... - - - - - - - - - - - - - - - -- - - - - - a 127/37 8 Claims, No Drawings
 4,174,976
1. 2
It is another object of this invention to provide a
ACID HYDROLYSS OF CELLULOSE TO YIELD process for acid hydrolysis of cellulose to yield glucose.
GLUCOSE It is still another object of this invention to provide a
process for acid hydrolysis of cellulose to yield glucose
The Government has rights in this invention pursuant 5 wherein cellulosic materials are pretreated to disrupt.
to Contract No. E(11-1)-2755 awarded by the United the crystalline structure prior to acid hydrolysis.
States Energy Research and Development Administra With these and other objects in view, which will
tion. become apparent to one skilled in the art as the descrip
FIELD OF THE INVENTION
tion proceeds, this invention resides in the novel
O method substantially as hereinafter described, and more
This invention relates to acid hydrolysis of cellulose particularly defined by the appended Claims, it being
and, more particularly, relates to a process for yielding understood that such changes in the precise embodi
glucose through acid hydrolysis of cellulose. ment of the herein disclosed invention are meant to be
included as come within the scope of the Claims.
BACKGROUND OF THE INVENTION 5
DESCRIPTION OF THE INVENTION
The utilization of cellulosic waste materials, such as
cornstalks, sawdusts, straws, bagasse, and the like, has As is well known, cellulosic materials have a highly
been the subject of strong interest recently, particularly ordered crystalline structure. In addition, in cellulosic
with respect to utilization of such waste materials for materials, lignin in middle lamella poses as a physical
developing alternate sources of fuels, feedstuffs, chemi 20 seal surrounding the cellulose fibers in such materials.
cals and other useful products. In the process of this invention, acid hydrolysis is
Cellulosic materials include the principal component utilized to yield glucose from cellulose. Cellulosic mate
s-cellulose, hemicellulose and lignin. Methods for rials are preferably pretreated to disrupt the crystalline
extraction of hemicellulose have heretofore been sug structure and the cellulose precipitated therefrom prior
gested and/or utilized and such extracted hemicellulose 25 to acid hydrolysis.
can be utilized by many existing methods including The pretreatment of the cellular materials can be
hydrolysis, fermentation, pyrolysis, and the like. accomplished by selective solvent extraction as follows:
cellulosic materials are first extracted with a dilute acid
Lignin has also been isolated from cellulosic materials or alkali to remove hemicellulose; the residue is then
and since it is higher in hydrogen and carbon and lower 30 dissolved in Cadoxen made up of 25 to 30% ethylenedi
in oxygen content than cellulose and hemicellulose it amine and 70 to 75% water with about 4.5 tp 7% cad
has the highest fuel utility of the three. Isolated lignin mium added as oxide or hydroxide (for example, about
can be burned to generate steam and electricity and can 10 grams of cellulose may be dissolved in 100 grams of
also be used to produce a number of useful products Cadoxen); separating lignin, which does not dissolve,
including vanillin, dimethylsulfoxide, dimethyl sulfide, 35 from the cellulose-Cadoxen mixture by filtration or
and methyl mercaptan and catechol. centrifugation; and precipitating cellulose from the cel
Recovery of cellulose and/or utilization of the same, lulose-Cadoxen mixture (as by adding water or an acid).
as by hydrolysis to provide glucose, has presented a In addition, the cellulosic materials may be pretreated
problem heretofore primarily due to the crystalline by contacting the materials with a chelating metal caus
structure of the cellulose molecules and the presence tic swelling solvent. Such an agent may include an
therein of a lignin seal. aqueous solution of 17% sodium tartrate, 6.6% ferric
Attempts have been made to hydrolyze cellulose, and chlorideand 7.8% caustic which is stabilized by 6.2%
these attempts have included the use of acids or en sodium sulfite (all in weight percent). While particu
zymes, but such attempts have not been completely larly, such an agent may be formed by:
successful, at least not in providing an economically 45
attractive method that is capable of providing a satisfac
torily high yield of glucose for the cellulose in such FeCL36H2O about 10 g
Tartaric Acid about ,
cellulosic materials. NaOH about 22 g
Also, while solvents have been suggested and/or Na2SO3 about 13 g
utilized in conjunction with cellulosic materials, im 50 - Water to a total of 200 g.
provements in such solvents can still be utilized in re
covering cellulose. In this regard, dissolution of pure The pretreatment of the cellulosic materials in this
cellulose using a ferric sodium tartrate based solvent has case involves contacting the materials with solvent in a
been heretofore suggested. 1 to 4 weight ratio of residue to solvent.
55 The acid hydrolysis of cellulose can be envisioned as
SUMMARY OF THE INVENTION
a sequential reaction:
This invention provides an improved process for
hydrolysis of cellulose to yield glucose. In the process A KB K2C
of this invention, acid hydrolysis of cellulose is effected
to yield glucose with the cellulose being recovered where A is cellulose, B is glucose, and C is undesirable
from cellulosic materials through treatment of the cellu side products. Reports on the acid hydrolysis of woods,
losic materials to disrupt the structure thereof prior to based on research conducted during World War II by J.
acid hydrolysis. Lignin is removed either before or after F. Saeman of the U.S. Forrest Products Laboratory,
hydrolysis. states that the rate of A kB is about the same as Bk2C.
It is therefore an object of this invention to provide 65 In other words the formation of side products from
an improved process for hydrolysis of cellulose to yield glucose occurred at about the same rate as formation of
glucose, while minimizing formation of undesirable side glucose from cellulose. Consequently, the maximum
products. glucose level in the hydrolysate was only 23% of the
 4, 174,976
3 4
sugar potentially available from the cellulose. Over the EXAMPLE 2
years some improvements in yields have been obtained
by reducing reaction times, increasing temperature and Untreated and pretreated cellulose were subjected to
pressure, and modifying processing equipment. Yet hydrolysis using ca. 5% H2SO4 at 125 C. in a closed
with all these improvements, the best yields obtained to vessel. At the end of three hours, the untreated cellulose
date, using this "conventional' technology, are less showed only 18% conversion to glucose while the pre
than 50%.
treated cellulose showed 29% conversion to glucose.
Lignin may be separated by filtration or centrifugation
We have found that microcrystalline cellulose dis either before or after hydrolysis.
solved in the solvent Cadoxen can be converted, almost 10 These examples clearly indicate that pretreatment of
instaneously, to glucose and other soluble products cellulose followed by acid hydrolysis (using relatively
when concentrated sulfuric acid is added. Using an acid: mild conditions) greatly enhances the conversion to
cadoxen/cellulose ratio of 10:1, a 69% yield of glucose glucose. Acid hydrolysis of cellulose is of economic
was obtained within 1 minute after the two solutions importance since presently the only way to obtain quan
were mixed together. Therefore, under the right condi 5 titative yields of glucose from cellulose without side
tions, cellulose dissolved in a solvent such as Cadoxen is product formation is to use cellulase enzymes. This
very susceptible to acid hydrolysis and gives good enzyme is costly and constitutes a major operating ex
yields of glucose. pense in the saccharification of cellulose. With the pro
cess of this invention, saccharification of cellulose can
Although the quantity of acid necessary to produce 20 be accomplished using inexpensive acid instead of
glucose as discussed is not practical on a large scale, the costly enzyme, and this reduces the price of making
results achieved show that high conversions of cellulose glucose from cellulose.
to glucose can be obtained by acid hydrolysis if the Although sulfuric acid was used in the above exam
cellulose is in the proper form. In this case the cellulose ples, other acids, such as, for example, hydrochloric and
was dissolved and therefore its physical structure may 25 phosphoric acids, could just as well be used. Or, instead
be considered as being completely disrupted. Herein lies of mineral acids, organic acids may also be used to carry
the key to quantitive saccharification of cellulose by out the hydrolysis.
acid hydrolysis in that the cellulose when subjected to Thus from the foregoing, it can be appreciated that
this invention provides an improved process for acid
such hydrolysis must be much less strongly crystallized 0 hydrolysis of cellulose.
than it naturally occurs. Starch, another polymer of What is claimed is:
glucose, which is much less strongly crystallized in its 1. A process for hydrolyzing the cellulose in a cellu
natural state than cellulose, gives very few degradation losic material to obtain glucose therefrom comprising:
products and almost quantitative yield of glucose when contacting the cellulosic material either with a sol
hydrolyzed with acid. This implies that in the reaction 35 vent comprising ethylenediamine, cadmium hy
scheme Akl BK2C for oligosaccharides, k1 is much droxide and water or with a solvent comprising a
greater than k2 when a less strongly crystallized sub chelating metal caustic swelling agent whereby the
strate is used. solvent dissolves the cellulose to form a solution,
In the case of acid hydrolysis of cellulose using con precipitating the cellulose from the solution; and
centrated acid, the glucose formed must be separated hydrolyzing the precipitated cellulose with acid to
from the acid. To avoid this potentially formidable obtain glucose.
separation step, a process using dilute acid is preferred. separated from anyofnon-soluble
2. The process claim 1 wherein the solution is
non-cellulosic portion
The acid hydrolysis using a dilute acid is carried out in of the cellulosic material before precipitating the cellu
a closed vessel at 100' to 200 C. in an approach similar 45 lose.
to that proposed by Saeman in 1945. However, the 3. The process of claim 1 wherein said acid is selected
cellulose is preferably first pretreated in the manner as from the group consisting of mineral and organic acids.
described hereinabove. 4. The process of claim 1 wherein said acid is selected
To test the validity of this approach, the following from the group of mineral acids consisting of sulfuric
examples were performed: 50 acid, hydrochloric acid, and phosphoric acid.
5. The process of claim 1 wherein said acid hydrolysis
EXAMPLE 1 is practiced at a temperature range of ambient to about
Untreated microcrystalline cellulose was hydrolyzed 2006. The C.
with 0.1% H2SO4 at 125 C. for 42 hours and gave 8% 55 is carriedprocess out in
of claim 1 wherein said acid hydrolysis
a closed vessel at a temperature of
yield of glucose. Liquid chromatographic analysis of between 100 C. and 200 C.
the hydrolysate showed formation of side product. In 7. The process of claim 1 wherein lignin is separated
comparison, the same material, pretreated by dissolu from said glucose by filtration or centrifugation.
tion in Cadoxen followed by reprecipitation, and wash 8. The process of claim 1 wherein lignin is separated
ing, gave 13% conversion to glucose with no apparent from said precipitated cellulose before hydrolysis to
formation of side products when hydrolyzed under yield glucose. a k is
similar conditions as used for the untreated cellulose.

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