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2416 Ind. Eng. Chem. Res.

1991,30, 2416-2425
temperature. This can be attributed to the loss of volatile
with increasing temperature.
4. Effect of Impregnation Ratio and Reagent on
Yield. From Figure 12, one can observe that yield in-
creases with impregnation ratio. However, this increase
in yield is marginal beyond an impregnation ratio of 25%.
This is true for both reagents studied and holds good for
both fluidized bed and static bed processes.
5. Effect of Gas Medium on Yield. The influence of
the gas medium (nitrogen, air, and carbon dioxide) on yield
is shown in Figure 13. I t can beclearly seen that the static
bed process gives a higher yield. Use of nitrogen and
carbon dioxide results in a better yield compared to air as
the medium. Phosphoric acid gives a slightly better yield
than ZnC12, when nitrogen and carbon dioxide are em-
ployed.
When air is used as the medium, H3P04 gives a low yield
compared to ZnC1,. This may be due to the combustion
reactions, which are more pronounced with H3P04 because
of its lower temperature stability (boiling point 213 OC).
From the experimental data it may be concluded that air
is unsuitable as the medium of activation since it gives low
activation and also low yield compared to nitrogen and
carbon dioxide.
Conclusions
On the basis of the experimental study carried out, it
can be concluded that the fluidized bed process gives better
activation (high adsorption capacity of carbon) in less time
and at a lower temperature compared to the static bed
process. High activation and greater yield are both possible
with nitrogen and carbon dioxide compared to air as the
medium of activation.
Under the experimental conditions investigated for the
chemical activation of coconut shells in the fluidized bed,
a process time of 2 h, a temperature of around 500 "C with
zinc chloride as the activating agent, and an impregnation
ratio of 25% in the presence of nitrogen or carbon dioxide
may be taken as optimal parameters.
Nomenclature
$ =temperature, O C
t =time, min
Abbreviations
I.R. =impregnation ratio
MED =medium of activation
R =reagent for activation
37-9; COz, 124-38-9; carbon, 7440-44-0.
Literature Cited
Edwards, G. D.; Robert, Y.; J oseph, T.; Loveday, P. E.; Williams, F.
D. Steam Activation of Charcoal: A systematic study of weight
and volume losses. Proceedings of the Fifth Carbon Conference;
Pergamon Press: New York, 1963; Vol. 2, pp 265-285.
Hassler, J . W. Activated Carbon; Chemical: New York, 1977; pp
171-177.
Kirubakaran, C. J . Studies on Activated Carbon Production from
Coconutshells Using a Fluidized Bed Reactor. M.S. Thesis, In-
dian Institute of Technology, Madras, 1990.
Kunii, D.; Levenspiel, 0. Fluidization Engineering; Wiley: New
York, 1969 pp 8-11.
Mantell, C. L. Carbon and Graphite Handbook; Interscience: New
York, 1977; pp 181-184.
Ruiz, Bevia, F.; Prats Rico, D.; Marcilla Gomis, A. F. Activated
Carbon from Almond Shells. Chemical Activation. 1. Activating
Reagent Selection and Variables Influence. Znd. Eng. Chem.
Prod. Res. Dev. 1984a, 23, 266-269.
Ruiz Bevia, F.; Prats Rico, D.; Marcilla Gomis, A. F. Activated
Carbon from Almond Shells. Chemical Activation. 2. ZnC12
Activation Temperature Influence. Znd. Eng. Chem. Prod. Res.
Dev. 1984b, 23, 269-271.
Snell, F. D., Ettre, L. S., Eds. Encyclopedia ofzndustrial Chemical
Analysis; Interscience: New York 1973; Vol. 17, pp 28-32.
Vogel, A. I. Text Book of Quantitative Inorganic Analysis, 4th ed.;
ELBS and Longman: London, 1978; pp 370-379.
Wagner, N. J .; J ula, R. J . Activated Carbon Adsorption. In Acti-
vated Carbon Adsorption for Waste Water Treatment; Perrich,
J . R., Ed.; CRC Press: London, 1981; Chapter 3.
Received for review December 6, 1990
Revised manuscript received May 29,1991
Accepted J une 20,1991
=average particle diameter, mm
Registry No. ZnC12, 7646-85-7; H3PO4, 7664-38-2; Nz, 7727-
Phenomenological Kinetics of Complex Systems: Mechanistic
Considerations in the Solubilization of Hemicelluloses following
Aqueous/Steam Treatments
K. Belkacemi,? N. Abatzoglou,t R. P. Overend,+?$ and E. Chornet*t+
Departement de genie chimique, UnioersitB de Sherbrooke, Sherbrooke, Quebec, J l K 2R1, Canada, and
Division of Biosciences, National Research Council of Canada, Ottawa, Ontario, K1A OR6, Canada
The solubilization of hemicelluloses from a lignocellulosic matrix is generally described by two parallel
fint-order reactions. In this paper we develop a phenomenological description that relates the kinetic
parameters associated with the hydrolysis of the glucosidic bond to linear free energy correlations
of the Leffler type. Such a description has resulted in the correct prediction of the acid hydrolysis
kinetics of a number of substrates including the published data on Populus tremuloides and Betula
papyrifera and our own work on corn stalks and Stipa tenacissima. The key advantage of our
approach is that it facilitates the obtention of kinetic data for a given substrate with fewer ex-
perimental points than frequently used in isothermal experiments.
be modeled by combining the three main operational
variables (i.e., residence time, temperature, and acid con-
centration) within a single reaction coordinate, named ROH,
which describes the severity of the thermochemical
treatment. The use of ROH leads to the derivation of three
parameters: the energy-related parameters w' and y have
been interpreted as indicators of the nonhomogeneity of
Introduction
In a previous work, Abatzoglou et al. (1991), wehave
shown that the kinetics of hemicellulose solubilization can
* Author to whom correspondence should be addressed.
t National Research Council of Canada.
Universit6 de Sherbrooke.
0888-5885/91/2630-2416$02.50/0 0 1991 American Chemical Society
Ind. Eng. Chem. Res., Vol. 30, No. 11, 1991 2417
the biomass substrates studied, while the parameter X is
linked to the catalytic role of the acid. In the present paper
wedevelop a link between the reaction coordinate ROH and
the thermodynamic parameters (i.e., activation energy and
entropy) that characterize the hydrolytically induced
glucosidic bond splitting.
The so-called prehydrolysis of lignocellulosic materials
leading to the hemicellulose solubilization will be the focus
of our analysis. In this type of treatment the biomass
undergoes significant structural and chemical changes,
under appropriate combinations of temperature, acid
concentration, and reaction time, as described by Roudier
and Eberhard (1967) and Casebier et al. (1969).
The polymeric carbohydrates treated with acids in
aqueous media participate at least in two distinct reactions:
hydrolysis of the glucosidic bonds; dehydrations, as re-
ported by Feather and Harris (1973). The mechanism of
the hydrolysis and the reaction rates of both poly-
saccharides and oligosaccharides have been extensively
studied (Capon, 1967; Casebier et al., 1969; Defaye, 1981;
Harris, 1975). The concept of the conformational mech-
anism is generally accepted. Although there is some un-
certainty on whether the proton H+attacks the oxygen in
the ring or the glucosidic bond preferentially, the con-
formational mechanism remains the most accepted ex-
planation of the homogeneous hydrolysis of glucosides in
the aqueous phase.
Wayman (1980,1983) reviewed the main reactions tak-
ing place during the hemicellulose hydrolysis and studied
their kinetics. Since then a limited number of works have
been published, proposing kinetic models for the hydrolysis
of hemicelluloses. Maloney et al. (1984), Conner et al.
(19851, and Harris et al. (1985) showed that the hemi-
celluloses are solubilized following first-order kinetics and
claimed the existence of two distinct profiles of solubili-
zation due to the coexistence of reactively different hem-
icellulosic components. On the other hand, Carrasco et
al. (1987) claimed that a single kinetic law is sufficient to
describe the same reaction system.
None of these kinetic models has, however, been linked
to the basic conformational mechanism. The reason is that
the mathematical calculations of the kinetic parameters
of the overall reaction via optimization methods lead to
results lacking precise physical meaning. The term
pseudokinetics is then used as in the case of the cellulose
hydrolysis to signify a phenomenological approach. The
obvious lack of a model linking classical thermodynamic
concepts, reaction mechanisms, and the kinetics of the
complex carbohydrate solubilization led us to the present
work, which is based on the severity factor concepts de-
veloped by our group (Abatzoglou et al., 1991).
Hydrolysis of Lignocellulosic Materials:
Rsactions and Mechanisms
The solubilization of hemicellulose is dependent on both
the acid concentration of the aqueous medium and the
nature of the hemicellulosic material. The salient con-
trolling parameters according to Harris (1975), Defaye
(19811, and Fengel and Wegener (1984) are the acid type,
the concentrations, the acid strength, the temperature and
pressure, the phase in which the reaction takes place, the
physicochemical structure and the accessibility of the
reactants, if the reaction is heterogeneous, the conforma-
tion effects, and the electronic effects due to the chains
structure and their substitutes.
The process of fragmentation (a partial de-
polymerization) to yield soluble glucosides takes place by
means of scission of the glucosidic bonds (C-0-C). Two
mechanisms are possible: (a) protonation of the C-0-C
a. Hydrolysis vis the cyclic arbonium-oxonium ion
H HP OH
CH,OH
H OH
H! &
b . Hydrolysis via the acyclic carbonium ion
Figure 1. Mechanisms involved in scission of glucosidic C-O-C
bonds.
glucosidic bond followed by formation of a cyclic carbanion
and the elimination of the aglycon part through scission
of the corresponding bond; (b) protonation of the anomeric
oxygen taking part in the glucosidic ring followed by an
opening of the latter and formation of an acyclic carbanion
complex. These two mechanisms are described in Figure
1. The most probable case is that both oxygen atoms are
protonated with the position of the scission depending
upon the distribution of the electronic density on the in-
termediate carbanion (Harris, 1975).
It is generally admitted that in homogeneous reactions
the mechanism through the cyclic carbanion is the most
probable (Capon, 1967). However, the step involving the
cyclic complex formation requires an important modifi-
cation of the conformation of the molecule whose activa-
tion energy depends on the steric and electronic hindrances
encountered (Fengel and Wegener, 1984); in fact the
mandatory "half-chair" conformation of the cyclic car-
banion is obtained through a slight rotation of the ring
constitutive (pendant) groups; thus the energy required
for this step depends on the steric and electronic inter-
effects of the latter and is likely to be difficult in the solid
state.
In the case of an heterogeneous reaction (i.e., the acid-
catalyzed depolymerization of the hemicellulosic poly-
saccharides) the reaction mechanisms described above are
still likely to bevalid but the measured rate of the (243-42
bonds cleavage isgenerally lower. Ross and J urasek (1978)
and Fengel and Wegener (1984) have proposed that limited
accessibility of the oxygen atoms of the C-0-C bonds is
the main reason; however, no means have been so far
proposed to satisfactorily quantify these effects. Given the
complexity of the overall reaction and the unknown nature
of some of the elementary steps taking place in the reac-
tion, the only positive way to monitor the phenomenon is
to follow the rate of the polymer disappearance from the
2418 Ind. Eng. Chem. Res., Vol. 30, No. 11, 1991
solid phase (its solubilization in the aqueous phase).
Kinetics of the Solubilization of the
Hemicelluloses
Veeraraghavan et al. (1982), Maloney et al. (19841,
Conner et al. (1985), and Harris et al. (1985) have shown
that the quantity of xylans remaining in the fibers fol-
lowing the prehydrolysis of lignocellulosic material as
function of the treatment time follows two distinct solu-
bilization profiles: an initial rapid solubilization process
and a subsequent slow step. Both profiles are well fitted
by first-order kinetics.
Simmonds et al. (1955), Kobayashi and Sakai (1956),
Springer et al. (1963), Brasch and Free (19651, Springer
(1966), Springer and Zoch (1968), Planes et al. (1981),
Harris et al. (1985), Veeraraghavan (1982), Trickett and
Neytzell de Wilde (1982a), Conner (1984), Maloney et al.
(1984), and Conner et al. (1985) have estimated through
their experimental results the pseudo-first-order reaction
rate constants k related to both rapid and slow solubili-
zation steps for a variety of biomasses including wood,
bagasse, and annual plants (Trickett and Neytzell de
Wilde, 1982b; Dutoit et al., 1983). The experimental data
generated by our work (to be described later) show that
the hydrolysis of corn stalks and Stipa tenacissima follows
the same pattern (two distinct solubilization profiles).
On the basis of structural considerations as well as the
experimental observations wecan formulate the following
set of assumptions which are the basis for the modeling
approach:
1. The mechanisms reported in the literature for the
homogeneous acid-catalyzed hydrolysis of the glucosidic
bonds are valid for the heterogeneous depolymerization
of the labile hemicellulosic polysaccharides present in
lignocellulosics; however, wemust consider that the ac-
cessibility of the oxygen atoms of the different C-O-C
bonds present in the macromolecules is not uniform, thus
leading to reaction rates that may vary with the extent of
the overall solubilization. I t is necessary to point out that
when introducing the hypothesis of varying accessibilities,
we do not consider the proton diffusion rates in the
polymeric matrix as being a limiting step; the small size
of the hydrogen proton, the high activation energies for
acid hydrolysis reported in the literature (higher than 126
kJ /mol), as well as the reduced particle size of the biom-
asses used (<0.5 mm) and the relatively high temperature
levels of these treatments are such that the proton diffu-
sion mechanism is much faster than the other chemical
steps taking place in the reaction environment. Therefore,
the reaction kinetics will be considered as governing the
solubilization process. This assumption is confirmed by
the work of Singh et al. (1984), who reported no effect on
hydrolysis for particles smaller than 0.5 mm.
2. There are many hemicellulosic families; however, they
behave as two major groups. The existence of these two
forms leads to two distinct depolymerization profiles.
3. The solubilization reaction for both hemicellulosic
groups follows an apparent first-order rate with respect
to the hemicelluloses remaining in the solid (fiber) phase.
Nonetheless, in all works published in the literature, as
well as in our experiments, the monitored variable is the
mass remaining and not the molar concentration as clas-
sical kinetics require.
4. The solubilization reactions are al so first order with
respect to the activity of the hydrogen proton in the
aqueous phase. Since the acidic solutions used are diluted
(less than 1 % in the aqueous phase), wecan assume that
the hydrogen proton activity is equivalent to its concen-
tration.
Let us use the following nomenclature: x , the fraction
of initial hemicelluloses remaining in the fiber after a given
reaction time; xfl, the initial fraction of the readily solu-
bilizable hemicelluloses (this is a fmed quantity, depending
only upon the nature of the substrate); x,, the fraction of
the readily solubilizable hemicelluloses remaining in the
fiber after a given reaction time; xBo, the initial fraction of
the hemicelluloses resistant to solubilization (also a fixed
quantity, depending only upon the nature of the substrate);
and x,, the fraction of the hemicelluloses resistant to
solubilization after a given reaction time; x , =1 - x,.
The kinetic expressions are
The analytical solution of (1) and (2) gives
X =X f i eXP[-k$~+t] +(1 - X,) eXp[-k,C~+t] (3)
Justification of the Kinetics Proposed for the
Acid-Catalyzed Hydrolysis of the Glucosidic Bond
The elementary steps to be considered are the following:
1. equilibrium between the polymer and the hydrogen
proton
k
polymer +H+& polymer-.H+
k-1
(fast)
2. formation of the cyclic carbanion
polymer.-H+- cyclic carbanion complex +
3. formation of the hydrolysis products
cyclic carbanion complex +H20 ==
k2
aglycon (or saccharide) (slow)
ka
k-a
products +Ht (fast)
The formation of the carbanion is, according to the liter-
ature, the slowest and consequently the rate-controlling
step of the process. The other two steps are essentially
in equilibrium state.
This leads to the following expression:
kl[polymer,] [H+] =k-l[polymer,.-H+] (4)
rr =k,[polymer,-H+] ( 5)
rr =(klk2/k-l)[~olymer,l [H+I (6)
Combining (4) and (5) gives
If welet
k, =kl kz/ k- l
then
r, =kr[POlymer,l [H+l (7)
The expressions for the s-type hemicelluloses are analogues
to the previous ones. Thus
r, =ks[polymer,l [H+l (8)
where
[polymer,] =x ,
[polymer,] =x ,
[H+] =CH+
Ind. Eng. Chem. Res., Vol. 30, No. 11,1991 2419
Equations 7 and 8 are respectively (1) and (2) used in the
preceding section to model the kinetics of solubilization.
Experimental Proof for the Existence of Two
Forms of Hemicelluloses
Dutoit et al. (1984) have developed an experimental
method to extract in 24 h the hemicelluloses contained in
bagasse using a 4% w/v aqueous solution of NaOH. Once
the final hemicellulose-rich liquid phase separated from
the lignin-cellulose-rich solid, they proceeded to a series
of precipitations from the filtrate using acetic acid and
absolute alcohol to obtain two types of precipitates which
were associated with the two different forms of hemi-
celluloses.
In the case of bagasse Dutoit et al. (1984) obtained the
following results on a basis of 100 g of oven-dry biomass:
17.75 g of type A hemicelluloses (or 55.29% of the initial
hemicelluloses) and 14.35 g of type B hemicelluloses (or
44.71 9% of the initial hemicelluloses). The hemicelluloses
of type A correspond to the readily solubilized hemi-
celluloses while those of type B correspond to the slowly
solubilized ones. To verify the claims of this method, we
have experimentally proceeded to its application to the
case of the corn stalks and the results obtained are as
follows: 20.9 g of shredded oven-dry corn stalk yields 4.53
g of type A hemicelluloses (or 74.18% of the initial hem-
icelluloses) and 1.58 g of type B hemicelluloses (or 25.82%
of the initial hemicelluloses).
Moreover, as Dutoit et al. (1984) have shown, these two
types of hemicelluloses also show different hydrolysis rates.
In fact, they have measured the amount of monomeric
sugars released upon hydrolyzing the two substrates
(hemicelluloses A and B) for 2 h at T =96 "C and CH+ =
5% w/v H2S04 and found that the ratio of the pseudo-
fmt-order rate constants (k, /kJ is equal to 1.84. Subscript
r refers to A-type hemicelluloses while subscript s relates
to B-type hemicelluloses.
Definition of a Severity Factor Based on
Thermodynamic Considerations
When applying the transition-state theory to elementary
step 2 describing the formation of the activated carbanion
complex, wecan define the rate expression as
(10)
where #is the activated complex in equilibrium with the
active center, polymer-H+, which werepresent by F.
F2 =vC' =( kBT / h) C#
Since
K#eg2 =- =exp[ $1 and v =kBT h (11)
C F
then
where
AG2,o =W , O - TAS2,o (13)
The combination of (12) and (13) leads to
r2 =kBT ex.[ %] exp[ F ] C F - W , 0 (14)
h
Meanwhile, the equilibrium assumption for the elementary
step 1 gives
K, =
CF
CpolymerCH+
ex.[
-%I
-1RT
and combination of (14) and (15) yields
AS1,O +AS2,O
h
where r is the overall reaction rate describing the polymer
solubilization.
The overall kinetic rate constant k can then be expressed
as
1
=-.'P[ k B T
ASl,O R +A S2P ] "P[ - ( M1, 0 RT +W , O )
h
(17)
Since the activation energy is given by (see also Benson
(1976) and Bamford and Tipper (1979))
and from (17) wecan derive
In ( k ) =
weobtain
8 In ( k )
1 + mi,o +mz,o
-- - -
dT T R P
Within the temperature ranges used one can assume that
RT <<CHi,o =MI,O +m2 , 0
E =M 1. 0 +m2 , o
A S =AS1,o +AS2,o
AH =M 1 , O +m2 , o
I
According to (18)
(19)
(20)
(21)
Let us define AS and AH as
The combination of (17), (19), (201, and (21) gives
In general, for organic reactions involving similar transition
states there appears to be a correlation between A S and
AH sometimes called a compensation effect. In the case
of the acid-catalyzed hydrolysis of glucosidic bonds in
polymers having different molecular size and spatial ar-
rangement of the monomer units (e.g., branching and
degree of substitution), the Leffler (1955) relationship can
be assumed to hold
=a +BAS (23)
where a and 0 are characteristic constants. @ is also known
as the "isokinetic" temperature. I t represents a temper-
2420 Ind. Eng. Chem. Res., Vol. 30, No. 11,1991
Table I. Kinetic Parameters Derived from Published Data Using Our Model
substrate k@," s-l kd," s-l E,, J /mol E,, J /mol AS,! J /(mol.K) AS,! J /(mol.K) reference
birch 6.3313 3.6316 126.5303 156.3303 18.3 70.8 Maloney et al. (1986)
red oakC 4.3307 4.6307 84.3303 95.3303 -99.3 -98.7 Conner et al. (1985)
corn stover 1.3316 2.9323 142.0303 176.0303 62.5 202.5 Kimet al. (1987)
southern red oakd 1.8309 1.1Ell 84.3303 127.0303 -68.3 -34.4 Conner et al. (1985)
aspen 2.8312 1.7E16 117.OE03 154.7303 -7.4 64.8 Grohmann et al. (1986)
Computational Results
type of hemicellulose Thy K a, J /mol roome D! s-l
r: fast hydrolysis 340.3 120.6E03 0.994 1.8 E46
E: slow hydrolysis 262.9 131.1E03 0.964 3.7 3-14
OFrequency factor (8-l). *AS =In (k&/(kBT))R (J /(mol-ZQ) and T =330 K. CHydrolysis with 5% w/w acetic acid. dAutohydrolysis.
This combined parameter will be used to correlate our
Application to the Solubilization of the
correlation coefficient. f D =(kBTh/h) exp(-a/(RTh)),
ature at which all reactions of a given type have the same
rate constant. experimental data.
Equation 23 can be expressed as
(24) Hemicelluloses
AH- CY E - CY
P P
AS=- =-
We have seen in the previous mathematical development
that the extent of the reaction of the acid-catalyzed solu-
bilization of the hemicelluloses in aqueous phase can be
Combining (22) and (26), wederive the final expression
for the reaction rate constant as
"1
RT
expressed by the sum of the solubilization of the two types
of hemicelluloses. Thus
x =~ f i exp[-k,C~+t] +(1 - ~f i ) exp[-k,C~+t]
(29)
and, rearranging
If weintroduce in this expression the factor RB+wehave
Since 6 =Th, wecan define two new functions as
T - Tb,
- -
[ R : ~ , T
=OPB; (30)
DaT
Tb,
k,CH+t =- eXp
D =- 0 h exp[ e]
The experimental data found in the literature concerning
T E T- Tb the acid hydrolysis of the hemicelluloses have been used
to derive the different kinetic constants, shown in Table
I.
The application of (25) to both types of hemicelluloses
is shown in Figurea2 and 3, where the experimental as well
as the optimization results are depicted. The severity
factors RB,+and R, + are
Ti00
and
k =D6
The overall hydrolysis rate leading to solubilization is
-dC,,ymer
(26) RB,+=- T exp[ - E, F ] c H + t T - Thor (31)
- RB,+=- exp[ - (32)
Tiao, R Tiso,
Cpolymer - Cpolymer(0) exp[-DaCH+t] Tiso, RTiso,
dt
r =kCplm,,CH+ =
If the process is isothermal, T #T(t), then integration of
(26) leads to T E, T- Tb,
Hence, the fraction of residual hemicelluloses can be
Defining RB =at, wehave
T E T - T b modeled introducing RB,+and RB,+as
RB =6t =- ex.[ - 7 ] t (27)
Tiso RTiso X =Xf i exp[-D&~,'] +(1 - Xf i ) exp[-D&~,+] (33)
The parameter RB allows us to estimate the severity of a
given process since it is function of the time and tem-
perature exposure. By introducing the acid concentration,
wecan define RB+as
RB+=R&H+
Concerning the units of the catalyst concentration to be
used in the kinetic expressions, we have opted for ?%
(weight of acidfweight of dry biomass). These units rep-
resent the acid loading with respect to the dry biomass
used. This is consistent with the units used by most
workers. The choice of these units renders the acid con-
centration dimensionless and consequently the constant
D is expressed in s-l and RB+in s. In the case of "auto-
hydrolysis" the acid concentration equals the inherent
acidity of the substrate associated with the uronic and
acetyl groups of the hemicellulose although it is rather
difficult to define it with accuracy.
Ind. Eng. Chem. Res., Vol. 30, No. 11, 1991 2421
I 4
lwooo ,
I I I I I
t
I !
, Er D 1. 2WE+5 +340.34'ASr I
Cornlation weificienl s 0.995
/
h Q U t :
Measurable rcaction extent (x) -
.12o - 2 0 a o
ASr (Jlmo1.K)
Multiple non -linear regression analysis
Optimizations according to
Figure 2. Linearity observed between the activation energy and
entropy for rapidly solubilized hemicelluloses.
184ooo
-
\ iz
1 -
=
a
W
@ooo
.200 . l o o 0 1 0 0 2 0 0 3 0 0
ASS (Jlm1.K)
1 . Connu el d. (1985)
2 -coma rt d. (lwa)
3. "rind J. (1985)
4- rt d. (1986)
5- Klm el d. (1887)
Figure 3. Linearity observed between the activation energy and
entropy for slowly solubilized hemicelluloses.
To model the hydrolysis of the hemicelluloses, the sim-
ulation routine shown in Figure 4 has been followed. We
have then proceeded to the modeling of the results from
eight different biomasses: (1) corn stalks (our experimental
Measurable indepeodent variables
Model
Results :
Non -measurable parameters ('1 : This parameter can also be measured
(2) : F.B.G.S :
as explained in the text.
FLETCHER-BROYDEN-GOLDF'ELDT
SHANNO
Figure 4. Kinetic modeling routine.
-
10' 1 o s 10' 10'
( 8)
0,004 ' ' ~" " " . ' ~'''''s ' ' """' ' ' """' ' ' "-
IO'
RE* (s)
Figure 5. Modeling of hemicellulose solubilization. Populus t .
(Springer et al., 1963).
data); (2) red oak (Harris et al., 1985); (3) Betula papy-
rifera (Maloney et al., 1985); (4) Populus tremuloides
2422 Ind. Eng. Chem. Res., Vol. 30, No. 11, 1991
Table 11. Simulation Results
biomass iter E,, J/mol E,, J/mol Xm A x 0 reference
St i m t . 1 85.5303 85.5303
Pinus r. 1 101.6303 109.9303
wheat stalks 2 123.5303 127.8303
corn stalks 5 91.7303 109.8303
Populus t . 6 149.3303 134.5E03
Betula p . 14 117.6E03 129.3303
aspen wood 2 126.3303 127.8303
red oak 1 118.5303 128.7303
a Ax =&(x - x y / N y .
0.849 0.059
0.210 0.156
0.675 0.111
0.698 0.037
0.786 0.056
0.652 0.035
0.712 0.059
0.800 0.015
this work
Brasch and Free (1964)
Grohmann et al. (1986)
this work
Springer et al. (1963)
Maloney et al. (1984)
Grohmann et al. (1986)
Harris et al. (1985)
Figure 6. Modeling of hemicellulose solubilization. Betula p .
(Maloney et al., 1985).
Michx. (Springer et al., 1963); (5) Pinus radiata of New
Zealand (Brasch and Free, 1964); (6) aspen wood (Groh-
mann et al., 1986); (7) wheat stalks (Grohmann et al.,
1986); (8) Stipa tenacissima (our experimental data). The
results of the modeling are reported in Table 11. Figures
5a, 6a, 7a and 8a show the fitting of the model to the
experimental data on four selected biomasses using the
severity factor Rg; in this fitting wecan see the grouping
of the experimental data for each particular acid concen-
tration. If, however, instead of using RB as the severity
parameter we replace it by the new combined severity
factor RB+, which includes the acid effect, weobtain the
fittings depicted in Figures 5b-8b. One weakness of the
model when the experimental data are fitted by means of
the new combined severity parameter RB+ is that the au-
tohydrolysis data are not very well modeled since the
precise acid concentration of the aqueous media is not
well-defined and, moreover, it changes with time. In Figure
8b wecan recognize this lack of fitting; in this particular
case wehave found that an acidity of 0.05% w/w H2S04
leads to the optimum fitting.
We should also point out that the proposed model has
been tried for all eight biomasses studied. Two optimi-
0,60
0,40
Klnelk model -
0,zo
0,w
10' 1 0 ' 1 0 '
I
0, 201
0,W
, , 1 0 A , Cy %: \ , CA=?XH2SOI
, , , I
0
I O ' 1 0 5 10' 1 0 ' 10'
FIB+@)
Figure 7. Modeling of hemicellulose solubilization. Corn stalks
(this work).
zation methods have been used to estimate the nonmea-
surable xro and E, These two methods are (a) the steepest
descent method, by Marquardt (1963) and (b) the method
described by Dennis and Schnabel(1983) using the Hes-
sien update matrix following the Fletcher-Broyden-
Goldfeldt-Shanno (FBGS) approach.
Discussion
If weaccept that during the heterogeneous reaction of
the acid-catalyzed hydrolysis of the hemicelluloses leading
to their solubilization the formation of the cyclic carbanion
is the rate-controlling step, wehave shown that a rigorous
derivation of the rate expression can be made to monitor
the extent of hemicellulose solubilization. Furthermore,
the use of the activated complex or transition-state theory,
together with Leffler's relationship, has led us to the
definition of a severity factor R B having a thermodynamic
foundation. Several authors working in this field, among
them Mehlberg and Tsao (1979) and Dutoit et al. (1984),
have claimed that the modeling of the hemicellulose sol-
ubilization can be expressed by two pseudo-first-order
reactions with respect to the hemicelluloses remaining on
the lignocellulosic fiber network. On the basis of this
Ind. Eng. Chem. Res., Vol. 30, No. 11, 1991 2423
Table 111. Estimation of the Pseudo-First-Order Rate Constants
biomass E,, J/mol E,, J/mol ASr, J/(mol.K) AS,, J/(mol.K) kd, s-l k&, s-l k,(150 " C), s-l k,(150 " C), s-l
Stim t . 85.5303 85.5303 -103.2 -173.3 2.8307 6.0304 0. 7343 1. 5347
8.2309 4.2308 2.33-03 1. 1345 Pinus r. 101.6303 109.9303 -55.9
wheat stalks 123.5303 127.8303 8.4
corn stalks 91.7303 109.8303 -85.1
Populus t . 149.3303 134.5303 84.2
Kinetic model -
0 CAd. OXHZS04
Experimenlr A CAd. 5 K H2S04
0 CA.1 .O X H2S04
- 8- ,
E E
(.a
0,40 -
.
- -
U D
Kinetic model -
;s
K 0,20 - 0 CAd0. 5KH2S04 o
, Erperimanls I A CA=l .O%HZSCd
4
J x -
Kinetic model -
Erperimanls I A CA=l .O%HZSCd
K 0 CAd0. 5KH2S04 o
i 0 CA=0.05 Y H2S04 (Aulohydrolyria caw)
0,w ' ' """~ ' ~ ' " " ~ I ' ""'"I . ' "_ "' I - . ' . '
10' I O ' 1 0 ' 105 1 0 ' 10'
RB*(s)
Figure 8. Modeling of the hemicellulose solubilization. %pa t .
(this work).
information and of the mathematical formalism developed
in a previous section, wehave proposed a new pseudoki-
netic model introducing the use of the severity factor RB+
=RBCH+. This new model fits well the variations of the
amount of nonsolubilized hemicelluloses remaining in the
fiber. I t also estimates reasonably well the readily solu-
bilized fraction of hemicelluloses. Moreover, the model
has shown that there are important differences between
the solubilization profiles obtained from the softwoods
(Pinus r. ), the hardwoods, and graminae plants; in fact
higher severities are needed in the case of the softwoods
to achieve the same solubilization levels.
The results obtained in our optimizations have also
shown that the amount of the readily recoverable hemi-
celluloses in the aqueous phase varies between 60 and 90%
w/w in the case of hardwoods and graminae plants. Torres
et al. (1986), working on the thermomechanical fraction-
ation of Populus t . , reported a 70% w/w readily solubilized
fraction of hemicelluloses. Maloney et al. (1984) and
Maloney and Chapman (1986) predicted a value of 68%
w/ w, using the classical pseudo-first-order kinetic model,
for the readily solubilized fraction of hemicelluloses derived
from Betula p . Our modeling results are in accord with
the results reported by these authors.
A comparison between the experimental values of xd
obtained by using the Dutoit et al. (1984) method and the
1.8E13 1.6312 1.OE-02 2.53-04
2.5308 4.OEO8 1.13-03 1. 1345
1.7317 3.3313 6.13-02 7. 9344
RB (SI
Figure 9. Fitting showing effect of optimizing xd starting from a
preestablished value.
predictions of our model in the case of corn st al ks is shown
below.
xdpred) xdexp) error, %
69.8 74.2 ==6
The optimization has been conducted in two ways: (a)
fixing xIo obtained experimentally and estimating the op-
timum activation energies; (b) estimating simultaneously
xd and activation energies.
As wecan see from the following tabulated results, we
have not observed any significant variations on the op-
timized values of the activation energies, which proves the
statistical robustness of the models.
XrO E,, J/mol E,, J/mol
exp =0.74 90.5303 108.9303
opt =0.70 91.7303 109.8303
In fact, a difference of 6% between the experimentally
obtained xd and the optimized one leads to a deviation of
1% in the activation energies. In Figure 9 wepresent the
differences observed for the two cases in terms of modeling.
The computation of the kIo and kBo values has been
conducted using the activation energies estimated by op-
timization, Leffler's relationship, and the equation
In Table I11 we present the estimation of the pseudo-
first-order rate constants. For the softwoods, represented
by Pinus r., the parameter xd is much lower than for
hardwoods; in fact the optimization gave us a value of 21 %.
However, weshould point out that the lack of extensive
data sets in softwood fractionation prevents us from ad-
vancing statistically consistent values. Nevertheless, the
results obtained seem coherent with what has been re-
ported in the literature, especially in terms of activation
energies; in fact wehave back calculated the activation
energies that lie in the region between 80 and 150 kJ /mol,
which are similar to those reported in related works.
The observation that the amounts of rapidly solubilized
hemicelluloses are lower in softwoods than either in
2424 Ind. Eng. Chem. Res., Vol. 30, No. 11, 1991
CHZOH OH CH,OH
I
OH COOH OH
Figure 10. Glucosidic chain showing a substituent, COOH, instead
of a regular hydroxyl, -OH, group.
hardwoods or in graminae plants should beassociated with
the existence of differences in the ultrastructure of the
hemicellulosic families encountered in the different sub-
strates (Belkacemi, 1990). In fact, the behavior of the
glucosidic bonds during their hydrolysis is influenced by
two effects which could be interdependent or not: the
conformation of the monomeric units of the osidic poly-
meric skeleton; the inductive effect of the substitutive
groups associated chemically with the polymeric chain. In
fact these different substituents (in Figure 10 wepresent
an example with carboxyl groups) create distinct distri-
butions of electronic densities around the oxygen atom,
thus determining its reactivity.
The global effect of the carboxylic groups as shown in
Figure 10 is a stabilization of the rings and a lower prob-
ability of hydrolytic reaction for the C-0-C bonds. This
explains the lower reactivity of highly branched xylan
having 4-0-methylglucuronic groups. Since the softwoods
are composed of uronic acid rich hemicelluloses (Fengel
and Wegener, 1984), it supports our interpretation of the
experimental data collected and the modeling results.
Barnet (1984) studied the fast autohydrolysis of Populus
and suggested that the hydrolysis of the hemicelluloses
does not proceed randomly along the xylan polymeric
chains but proceeds deterministically preferring the de-
acetylated positions. He concluded that the acetylated
groups stabilize the glucosidic bond because their hydro-
phobic behavior renders the proton attack more difficult.
However, weshould indicate that the acetyl groups as well
as the uronic groups play a double role during the hy-
drolysis; that is, they slow down the hydrolysis rates be-
cause of the Stabilization they bring to the glucosidic bonds
and they speed up the autohydrolysis rates because the
disengaged acetic acid can act as a catalyst. The same
stabilization phenomenon is also reported in the work of
Conner et al. (1984), and was previously proposed by
Moelwyn-Hughes (1928) and Ingvar et al. (1963).
Conclusions
We have proposed a kinetic model to simulate and
monitor the solubilization of polymeric carbohydrates (i.e.,
hemicelluloses), based upon classical mechanistic consid-
erations. This model leads to a severity factor which ex-
presses the common effect of the independent variables
grouped in a single reaction coordinate. Specific conclu-
sions are the following:
1. There exist two kinetic types of hemicelluloses.
2. The kinetics of the solubilization of the hemicelluloses
have been developed on the assumption that the con-
trolling step is the formation of a cyclic carbanion as
predicted by the conformational analysis; the successful
application of the derived model to the experimental re-
sults available in the literature has shown the usefulness
of our choice.
3. The hydrolytic treatment can be represented by the
severity factor RB, whose thermodynamic significance is
associated with the existence of an isokinetic temperature
and a compensation effect between the enthalpy and en-
tropy of the key elementary steps of the hydrolysis reac-
tion. This suggests that the same mechanism of bond
rupture prevails in all the solubilization reactions despite
the possible structural diversity of the hemicelluloses be-
longing to the different types of biomass.
4. The kinetic model developed in this work allows us
to have a good estimation of the rapidly solubilized fraction
of the hemicelluloses, 3cd, initially present in the original
biomass. The xd parameter is an intrinsic characteristic
of each particular biomass and is associated to ita char-
acteristic structure and chemical composition.
Acknowledgment
We are indebted to the Centre Quebecois de la Valori-
sation de la Biomasse and the Gouvernement du Quebec
(FCAR) for funding related to this research program. We
also gratefully acknowledge the financial participation of
the Algerian Government for the grant that allowed K.B.
to complete his Ph.D. program. M. M. J.-P. Lemonnier,
G. Phaneuf, as well as M. T. S. Nguyen and the analytical
team of the Laboratoire AssociB-Materiaux Ligno-
cellulosiques of the University of Sherbrooke are also
gratefully acknowledged for the technical and analytical
support they provided.
Nomenclature
A =constant (Arrhenius law preexponential factor)
B =constant (in equation expressing the compensation effed)
C =concentration
D =D =kB*Tb/h* exp[-a/(R*/Ti,)]
E =activation energy (in Arrhenius law)
G =Gibbs free energy
h =Planck constant
H =enthalpy (factor H)
k =rate constant
kB =Boltzmann constant
K =constant
K, =equilibrium constant
N =number of experimental points
r =reaction rate
RB+=severity factor based on mechanistic considerations
RB =severity factor corrected by the acid concentration
S =entropy
t =time
T =temperature
T =mean temperature
Ti, =isokinetic temperature
x =fraction of hemicelluloses present in the fiber
xro =fraction of hemicelluloses rapidly solubilized initially
xso =fraction of hemicelluloses slowly solubilized initially
Ax =mean difference between the experimental and the
Greek Symbols
a =constant (in Leffler's relationship)
6 ( T ) =(T/T,) exp[(E/RTb)((T- Tb)/2')] =characteristic
u =kBT/h =frequency factor
Indexes and Abbreviations
[ ] =concentration
eq =equilibrium
exp =experimental
F =polymer.-H+
is0 =isokinetic
max =maximum
mod =model
r =fast reaction
t =tabulated
0 =reference state (25 OC, 101.3 kPa)
1,2 =elementary step 1,2
present in the fiber
present in the fiber
theoretical values of x
parameter
Ind. Eng. Chem. Res., Vol. 30, No. 11, 1991 2425
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