Ind. Eng. Chem. Res.

1995,34, 4333-4342 4333

Kinetics of Catalyzed Organosolv Processing of Pine Wood

Juan C. Paraj6,* Jose L. Alonso, and Valenth Santos
Department of Chemical Engineering, University of Vigo (Campus Orense), Las Lagunas, 32004 Orense, Spain

The main phenomena involved in pine wood processing with HC1-catalyzed acetic acid media
(wood solubilization, delignification, degradation of both cellulose and hemicellulose, and
generation of hemicellulosic sugars and furfural) were studied. The effects of both reaction time
(in the range 0-180 min) and catalyst concentration (in the range 0.15-0.45%) on pulp yield,
residual lignin, polysaccharide degradation, and hemicellulosic sugar generation were correlated
by phenomenological kinetic models developed for the two operational temperatures considered
(115or 130 "C). The models (based on pseudohomogeneous, first-order kinetics) provided a good
interpretation of the experimental data.

Introduction (Davis et al., 19861, a previous study reported by the

Wood is a renewable, largely available resource with
great potential as raw material for the chemical indus-
try. Considerable attention has been directed toward
the development of efficient processes for wood upgrad-
ing into chemicals or fuels. Some processes proposed
for wood utilization are based on the "biomass refining"
philosophy (Myerly et al., 1981): by means of chemical
treatments, the raw material is "fractioned" into its
main polymeric constituents (cellulose, hemicellulose,
and lignin), which are recovered in separate streams
(untouched or as degradation products) and converted
into a set of marketable end products.
The above guidelines are followed by processes based
on the utilization of organic solvents (organosolvents)
as agents for wood fractionation. These technologies
allow an efficient and integrated utilization of the raw
material. Several authors explored the potentiality of
a variety of organosolvents (including alcohols, ketones,
acids, phenol, and phenol derivatives) as agents for wood
processing (Johansson et al., 1987). Among the several
possibilities reported in literature, acetic acid-based
processes show interesting features, such as (i) in a
single step, both extensive delignification and hemicel-
lulose removal can be achieved, leaving a solid residue
with high cellulose content; (ii) excellent selectivity
toward cellulose degradation reactions is reached under
appropriate operational conditions; (iii) acetic acid is a
process-derived product (this compound is generated
during treatments by hydrolysis of the acetyl groups
contained in wood); (iv) marketable products (sugars
and/or furfural) are derived from the hemicellulosic
fraction; (v) the lignin decomposition products can be
easily precipitated in the pulping liquors by water
addition, achieving an effective separation of the com-
pounds derived from hemicelluloses; and (vi) the solu-
bilization of lignin occurs without introducing sulfur-
containing groups (as happens in commercial pulping
technologies), leading to molecules with potential to be
used as chemical intermediates for obtaining a variety
of profitable end products (Nimz and Casten, 1986; Kin,
1990; Vazquez et al., 1992; Paraj6 et al., 1993a,b).
Both catalyzed and uncatalyzed acetic acid media
have been used for processing hardwoods and softwoods
(Davis et al., 1986; Young and Davis, 1986; Kin, 1990;
Vdzquez et al., 1992; Paraj6 et al., 1993a,b). Using
mineral acids as catalyst, a fast and selective separation
of fractions can be achieved in a single stage under mild
operational conditions. Although hardwoods are more
susceptible to delignification than softwoods owing to
the chemical differences between their respective lignins
Q888-5885/95/2634-4333$09.QQIQ 0 1995 American Chemical Society
authors (Paraj6 et al., 1993a) proved that a substantial
delignification of Pinus pinaster wood (from 30.2 to 7.7
wt % lignin) was achieved in HC1-catalyzed acetic acid
media. Under the operational conditions leaving to
maximum delignification, 46% pulp yield was obtained.
The purpose of this work was to establish the kinetic
pattern of the main phenomena involved in treatments
of pine wood with HC1-catalyzed acetic acid solutions,
including wood solubilization, delignification, and deg-
radation of both cellulose and hemicellulose. Temper-
ature, reaction time, and catalyst concentration were
considered as operational variables. From the experi-
mental data, phenomenological, kinetic models giving
a quantitative interpretation of the experimental results
were developed.
Materials and Methods
Raw Material. Pinus pinaster wood samples were
milled, screened to select the fraction of particles with
a size between 0.25 and 1mm, air-dried, homogenized
in a single lot to avoid differences in composition, and
stored.
Analysis of Wood. Aliquots from the homogenized
wood lot were subjected to moisture determination and
to quantitative acid hydrolysis with 72% sulfuric acid
following standard methods (Browning, 1967; Vazquez
et al., 1987). The solid residue after hydrolysis was
considered as Mason lignin. The monosaccharides
contained in hydrolysates were determined by spectro-
photometric or high-performance liquid chromatography
(HPLC) methods (see below).
Processing of Wood Samples. Wood chips, acetic
acid, concentrated HC1 solutions, and water were re-
acted using a liquorlwood ratio = 8 glg. The moisture
of wood was considered as water in the material
balances. Mixtures of wood samples, acetic acid, and
water were heated to the normal boiling temperature,
and then the catalyst was added. The reaction vessels
were capped and the temperature was raised to the
desired value (115 or 130 "C). The effects caused during
the heating or cooling periods were neglected for cal-
culation purposes. At the end of treatments, the solid
residues were recovered by filtration, washed with
acetone, air-dried, and subjected to quantitative sac-
charification. As an approximation useful for most of
the cases studied, the acid-insoluble residue was con-
sidered as lignin, although in experiments performed
under harsh experimental conditions non-phenolic com-
pounds can appear in this fraction, causing an overes-
4334 Ind. Eng. Chem. Res., Vol. 34, No. 12, 1995

timation of lignin as discussed below. Aliquots from the k e t r acid water HCI solutions

'9-.-
Wood
pulping liquors were taken before filtration, mixed with 1
water (l:lO), and centrifuged to separate the lignin
fraction as a precipitate. Aliquots from supernatants
%lid nridw Water
were filtered through 0.45 pm membranes and analyzed
by HPLC.
HPLC Analysis of Monosaccharides and Fur-
fural. Samples from quantitative acid hydrolyses or
from pulping liquors were analyzed for glucose, hemi-
cellulosic sugars (non-glucose monosaccharides), and
furfural using a Waters HPLC. Monosaccharides were
determined with a refractive index detector, and W
detection (A = 300 nm) was employed for furfural
analysis. The operational conditions were the follow-
ing: columns Shodex SHlOll (two); mobile phase, H2-
, 3 0 4 0.015 M; column temperature, 90 "C; flow rate, 0.6
mumin.
Fitting of Data. The experimental data were fitted
to the proposed kinetic models by nonlinear regression
using commercial software (Tablecurve from Jandel
Scientific, Corta Madera, CA).

Results and Discussion .-._.

---. _ _ --
---l:- --=&=.-
j
,
'

Raw Material Composition and Operational Figure 1. Scheme of the experimental plan carried out in this
Conditions Used in Experiments. The wood samples work.
used in experimentation contained 31.5% lignin and
59.6% polysaccharides, with a glucadpolysaccharide Table 1. Lignin Content of Solid Residues from
ratio = 0.630 g/g. Glucan was considered as cellulose, Treatments and Pulp Yields Obtained in Treatments
owing to the limited fraction of this polysaccharide lignin content of solid pulp yield (g recoveredl100 g
belonging to hemicelluloses. In the same way, the residues (g/lOO g, O.D. basis) of initial wood, O.D. basis)
composition of solid residues from treatments was time 0.15% 0.25% 0.35% 0.45% 0.15% 0.25% 0.35% 0.45%
(min) HCl HCl HCl HC1 HCl HCl HCl HC1
defined by their content in lignin (measured as acid- -
insoluble residue) and polysaccharides, as well as by (a) Experiments Performed at 115 "C
their glucadpolysaccharide ratio. Other fractions in 0 31.5 31.5 31.5 31.5 100 100 100 100
15 26.5 26.4 25.9 24.3 86.3 81.0 80.0 74.6
treated wood (acid-solublelignin, for example) were not 30 24.2 22.0 21.7 15.8 75.9 69.4 66.7 55.5
determined owing to their little importance for the 60 20.1 18.1 9.5 8.7 65.7 59.0 47.9 47.5
purposes of this work. 90 13.4 10.2 10.1 8.4 55.5 50.5 47.0 46.1
120 14.2 11.2 10.1 9.2 53.8 48.4 45.8 44.1
Previous studies reported on the Pinus pinaster wood 180 9.1 9.3 10.3 12.0 48.5 46.3 44.7 44.2
processing in catalyzed acetic acid media (Paraj6 et al.,
(b) Experiments Performed at 130 "C
1993a) showed that extensive delignification can be 0 31.5 31.5 31.5 31.5 100 100 100 100
achieved under selected operational conditions. In order 20 20.2 17.4 14.9 6.8 63.5 55.0 52.4 43.3
to develop technical and economic studies on this 40 19.0 8.3 7.5 6.1 60.8 46.5 44.1 41.3
process, additional information is necessary on the 60 13.5 13.5 14.3 17.2 51.2 46.3 44.3 45.7
kinetics of the several effects caused by treatments. 120 10.6 17.8 24.7 33.1 46.2 45.5 48.7 53.0
180 9.53 22.4 33.2 41.7 43.3 48.4 52.4 58.1
Experimental work was carried out in order to establish
the interrelationships between the operational condi- [acetic acidY[mineral salts in wood] is extremely high
tions and dependent variables selected to measure the in our case.
degree of delignification, wood solubilization, polysac- The dependence with time of the several phenomena
charide degradation, and generation of marketable considered were found to follow pseudohomogeneous,
products from hemicelluloses (sugars and furfural). first-order kinetics (in single or consecutive reactions).
With this objective, experiments were carried out during The experimental plan developed, including dependent
0-180 min at 115 or 130 "C in media formulated with and independent variables, experimental determi-
95% acetic acid and 0.15,0.25,0.35, or 0.45% HC1, which nations, and handling of samples, is summarized in
acted as catalyst. Figure 1.
As is well-known, the neutralizing ability of wood is Lignin Contents and Pulp Yields. Table 1shows
a factor influencing the acid hydrolysis of wood in the operational conditions considered for treatments, as
aqueous media: the mineral salts contained in wood well as the results obtained on the lignin content of
react with the H+ species provided by the catalyst, processed samples (LC, g of lignid100 g of solid residue
decreasing its concentration (and so its effect). This from treatment, oven-dried (O.D.) basis) and on the pulp
decrease in concentration becomes significant when a yield (PY, g of pulp/lOO g of untreated wood, oven-dried
dilute, mineral acid is used as a source of H+, because basis). The minimumlignin content (6.1%)was achieved
the amounts of neutralizing agent and hydronium ions in a treatment with 0.45% HC1 at 130 "C lasting 40 min,
are of the same order. However, the neutralizing ability at good pulp yield (41.3%). The delignification degree
of wood was neglected in our study because an acid- obtained in this experiment improved our previous
base equilibrium exists in the reaction media: both the results, which were determined for longer treatment
HCl (catalyst) and acetic acid (main constituent of the times (Paraj6 et al., 1993a). Both lignin content (LC)
reaction media) can act as H+ donors, and the mass ratio and pulp yield (PY) showed a similar dependence on the
 Ind. Eng. Chem. Res., Vol. 34, No. 12, 1995 4336
Table 2. Regression Parameters Obtained in the Table 3. Calculated Values for the Corrected Pulp Yield
Modeling of Delignification (g of Sample/lOO g of Initial Wood, O.D. Basis)
~

temp HC1 concn time 0.15% 0.25% 0.35% 0.45%

("0 (%) kl (min-l) kp (min-l) R2 F (min) HCl HC1 HC1 HCI
115 0.15 0.0172 0.0010 0.9867 370 (a) Experiments Performed at 115 "C
115 0.25 0.0229 0.0010 0.9898 487 0 100 100 100 100
115 0.35 0.0284 8.54 10-4 0.9877 483 15 86.2 80.9 79.9 74.5
115 0.45 0.0396 8.32 10-4 0.9890 542 30 75.6 69.0 66.3 54.9
130 0.15 0.0303 0.0012 0.9544 84 60 64.6 57.6 46.2 45.5
130 0.25 0.0639 0.0028 0.9907 428 90 53.1 47.4 43.8 42.5
130 0.35 0.0834 0.0045 0.9941 669 120 49.9 43.5 41.0 38.7
130 0.45 0.1656 0.0067 0.9632 105 180 41.0 37.6 36.5 35.6
(b) Experiments Performed at 130 "C
experimental variables: a first stage, characterized by 0 100 100 100 100
a fast decrease in LC or PY, was followed by a second 20 63.2 53.6 49.7 36.7
one where both parameters declined slowly or even 40 59.7 41.9 35.5 25.8
increased. The increase in PY observed under stringent 60 48.7 38.4 30.4 24.8
operational conditions was caused by condensation 120 39.2 28.1 23.7 21.3
180 31.3 24.6 20.4 20.8
reactions. It was assumed that condensation was
caused by lignin repolymerization. Material balances Table 4. Regression Parameters Obtained in the
evidence that, in the experiment performed under the Modeling of the Corrected Yield
severest operational conditions assayed (130 "C, 0.45% HCl insoluble
HC1,180 min of reaction time), other fractions different temp concn fraction
from lignin also participate in condensation. Since this ("C) (%) (IF,%) k3(min-l) R2 F
fact was important in a single experiment (which was 115 0.15 38.3 0.015 0.9954 1093
performed under conditions very different from the most 115 0.25 37.9 0.021 0.9947 937
desirable ones), we have neglected the participation in 115 0.35 36.1 0.026 0.9947 1132
condensation of fractions different from lignin. 115 0.45 36.5 0.036 0.9894 559
The behavior observed in experiments was closely 130 0.15 35.0 0.029 0.9617 100
130 0.25 28.1 0.044 0.9843 251
related t o that observed in previous studies: the exist- 130 0.35 23.3 0.049 0.9941 673
ence of two delignification stages was reported in both 130 0.45 22.2 0.082 0.9983 2419
kraft and organosolv processing of wood (Cho and
Sarkanen, 1985; Tirtowidjojo et al., 1988; Paraj6 et al., CPY=PY-CLR (3)
1993b), whereas extensive repolymerization was found
in acid-catalyzed treatments of beechwood in acetic acid where CLR gives the contribution of the lignin repoly-
media (Kin, 1990). merization reactions t o the pulp yield. Considering a
The kinetics of delignification was modeled in terms material balance to the lignin fraction and the kinetic
of the percent of lignin remaining in pulp (PLR). This model proposed, it can be inferred that
variable is related with LC and PY by means of the
equation
1 - exp(-k,t) -
PY
PLR = PY LC/LCo (1)
where LCOis the lignin content of untreated wood.
Assuming that lignin is degraded to soluble fragments
by the pseudohomogeneous first-order reaction (with The set of equations 2-4 provides an interpretation
kinetic coefficient kl), and that these soluble fragments of the two stages (solubilizatiodrepolymerization)con-
repolymerize by a subsequent first-order reaction (with cerning the behavior of the lignin fraction and its effect
kinetic coefficient kz), on pulp yield. On the basis of both the experimental
lignin - soluble lignin - repolymerized lignin
values of PY listed in Table 1 and the parameters of
Table 2, the contribution of lignin repolymerization
reactions can be calculated for the various experimental
it can be shown that conditions assayed, and the corresponding CPY can be
then evaluated using eq 3. Table 3 shows the calculated
values of CPY for the experiments performed. Assum-
ing that the initial wood is composed by two fractions
(an insoluble fraction, IF, and a second one that
where t is the reaction time. Table 2 lists the values decreases with time according a pseudohomogeneous,
obtained for k l and kz from regression analysis of the first-order reaction with kinetic coefficient k3), it can be
experimental data, as well as the R2 and F statistical followed that
parameters measuring the correlation and significance
of equations. Figure 2 allows an evaluation of the
agreement between experimental and calculated values
CPY = IF + (100 - IF)e? (5)
of PLR for the various catalyst concentrations used. Table 4 lists the regression parameters obtained when
The values found for the pulp yield (PY) were signifi- the data of Table 3 were fitted to eq 5. With these data,
cantly affected by repolymerization reactions. In order CPY can be estimated for given operational conditions
to obtain kinetic models describing the dependence of (temperature, reaction time, and catalyst concentration).
PY on the reaction time, a new variable (the corrected It can be noted that the above equations are useful
pulp yield, CPY) was defined according to the following for predicting pulp yields. From the information avail-
expression: able, the values of kl, k2, k3, and IF are known for
4336 Ind. Eng. Chem. Res., Vol. 34,No. 12, 1995

1oo

90

80

70

00

2 60

40

30

20

10

100

90

80
70

g 6o
n 50
40

30
20

10

o !
0 50 100 150 200

DURATION OF TREATMENTS, mln

Figure 2. Experimental and calculated dependence of percent of lignin remaining in pulp after treatments (PLR) on operational variables
considered.
defined operational conditions, and the corrected pulp
yield CPY can be easily calculated using eq 5. Then,
eq 4 can be substituted in eq 3 to give an expression
where PY is the only unknown variable, which can be
calculated solving a second-order equation. In order to
confirm the reliability of these calculations, Figure 3
allows a comparison between experimental and calcu-
lated values of PY.
Polysaccharide Degradation. The chemical pro-
cessing of pine wood provoked several effects, including
extractives removal, delignification, lignin repolymer-
ization, and polysaccharide degradation. Table 5 lists
the results obtained on both the polysaccharide content
of solid residues obtained in treatments (PC, expressed
as the percent of polysaccharides in treated wood, O.D.
basis) and the glucadpolysaccharide ratio (GPR). A
preliminary analysis of data proved that the kinetics of
polysaccharide degradation showed features similar to
those of the well-known case of the acid-catalyzed
hydrolysis of lignocellulosics in aqueous media: the
hemicelluloses were more susceptible to degradation
than cellulose, leading to increased glucadpolysaccha-
ride ratios when the severity of the operational condi-
tions was increased. The contribution of lignin repoly-
merization reactions caused a decrease in the poly-
saccharide content of samples treated either at 115 "C
during 180 min or at 130 "C during 120-180 min. For
modeling the cellulose and hemicellulose losses from
solid phase, two additional variables were defined: the
percent of cellulose recovery (PCR), defined as the
proportion of cellulose remaining in solid phase after
treatments in relation to the cellulose contained in
untreated wood, and the percent of hemicellulose re-
covery (PHR), with an analogous meaning for the
hemicellulose fraction. Both variables can be calculated
from the experimental data using the expressions:
PY PC GPR
(6)
PCR= PC,GPR,
PY PC(1 - GPR)
PHR = (7)
PCo(1 - GPR,)
where PY, PC, and GPR are as above whereas PCo and
 Ind. Eng. Chem. Res., Vol. 34,No. 12, 1995 4337

0.15% HCl, 115 aC 0.26% HCI. 116 nC 0.36% HCI, 116PC 0.46% HCl, 115 OC
--I=+- --e- .......p......
0.15% HCl, 130 n C 0.28% HCI 130 EC 0.36% HCI, 150 E C 0.46% HCl, 130 P C
& --& .......

100

90
ae
5 80

%
* 70
4
2 eo

60

40

0 60 100 160 200

DURATIONOF TREATMENTS, min

Figure 3. Experimental and calculated dependence of pulp yield (PY) on operational variables.

G P h are the corresponding data concerning untreated Table 5. Polysaccharide and Glucdolysaccharide
wood. Assuming that both PCR and PHR varied fol- Ratios of Solid Residues from Treatments
lowing a pseudohomogeneous, first-order kinetics, it can olysaccharide content
o f solid residues (g/lOO g) glucadpolysaccharideratio
be followed that
time 0.15% 0.25% 0.35% 0.45% 0.15% 0.25% 0.35% 0.45%
(mid HCl HC1 HCl HCl HC1 HCl HC1 HCl
PCR = 100e-k4t (8) -
(a) Experiments Performed at 115 "C
0 59.6 59.6 59.6 59.6 0.630 0.630 0.630 0.630
PHR = 100e-k5t (9) 15 61.4 61.0 63.2 62.9 0.711 0.721 0.711 0.759
30 65.1 65.3 68.8 71.9 0.719 0.738 0.774 0.822
where k4 and k g are kinetic coefficients. A first evalu- 60 71.0 74.1 84.2 83.4 0.780 0.810 0.899 0.916
ation of results showed that the catalyst concentration 90 76.6 81.6 83.7 83.0 0.867 0.875 0.923 0.916
120 80.8 82.9 84.5 83.7 0.900 0.950 0.960 0.960
caused little effect on the percent of cellulose recovery. 180 80.1 80.5 81.6 84.4 0.875 0.900 0.915 0.920
Because of this, the behavior of PCR was described by
two values of k4 (corresponding to operation at 115 or (b) Experiments Performed at 130 "C
0 59.6 59.6 59.6 59.6 0.630 0.630 0.630 0.630
130 "C). On the contrary, PHR strongly depended on 20 73.6 77.9 80.8 89.7 0.807 0.859 0.844 0.894
the catalyst concentration, and values of k j were cal- 40 75.7 82.1 87.7 89.0 0.802 0.871 0.879 0.906
culated for the various HC1 concentrations and temper- 60 79.9 78.4 78.5 74.9 0.908 0.977 0.977 1.000
atures assayed. Table 6 lists the results calculated for 120 84.6 77.5 73.5 63.1 0.934 0.954 0.960 0.990
180 80.6 66.8 61.8 52.9 0.981 0.940 0.972 0.997
k4 and k5, and Figure 4 shows the experimental and
calculated data of PCR and PHR. It can be remarked
that little cellulose loss occurred (0-10% a t 115 "C and charide fraction of wood, including monosaccharides
0-20% at 130 "C), whereas treatments performed under (glucose, arabinose, xylose, mannose, galactose) and
harsh conditions resulted in almost quantitative hemi- sugar decomposition products (furfural being the most
cellulose removal. important of them). In HPLC analysis, xylose, man-
Generation of Hemicellulosic Sugars. A variety nose, and galactose were eluted in a single peak,
of reaction products were generated from the polysac- hindering a separate study of pentoses and hexoses.
4338 Ind. Eng. Chem. Res., Vol. 34,No. 12, 1995

0.16% HCI, 1 1 5 P C 0.26% HCI, 1 1 6 PC 0.36% HCI, 115 P C 0.45% HCI, 116 O C
e --+- n - .Q -
0.15%
-r-
H U , 130O C 0.25% HCI 1 3 0 P C
--&- 0.36% HCI, 1 3 0 P C
A - -*-
0.46% HCl, 1 3 0 PC

j 100 B
0
4
3

'&:
4
W 80
'
8 CELLULOSE

-
70
I
w 60

60

#9 d 40

30

20 ..
----
3
4
10 .... 2-----
W 0
0
j 100

80

# s8
W =
70

eo + 'Ot*\ CELLULOSE

HEMICELLULOSES
20
\ '\ .
A
W
# * 0
w
0 SO 100 150 200

DURATION OF TREATMENTS, min

Figure 4. Experimental and calculated dependence of percent of cellulose recovery (PCR) and percent of hemicellulose recovery (PHR)
on operational variables.
Table 6. Regression Parameters Obtained in the 1945; Ranganathan et al., 1985; Brennan et al., 1986;
Modeling of Polysaccharide Recovery Maloney et al., 1986; Kim and Lee, 1987;Abatzoglou et
al., 1990; Mok et al., 1992; Malester et al., 1993). The
interpretation of results was done according to the
(a) Cellulose Recovery following mechanism:
115
130
0.15-0.45
0.15-0.45
5.4 x 10-4
1.10 x 10-3
0.4620
0.3590 hemicelluloses -
hemicellulosic sugars -
(b) Hemicellulose Recovery
115 0.15 0.013 0.9598 decomposition products
115 0.25 0.018 0.9315
115 0.35 0.025 0.9720 where both reactions were considered of first order, with
115 0.45 0.036 0.9411 kinetic coefficients k6 and k7, respectively. Since pen-
130 0.15 0.029 0.9183 toses decompose to furfural and hexoses give hydroxyin-
130 0.25 0.053 0.9563 ethylfurfural, it can be noted that the above mechanism
130 0.35 0.051 0.9763
130 0.45 0.073 0.9785 does not give a rigorous kinetic interpretation of the
process, but it represents o u r best approximation to the
Owing to this, the results obtained in this step are problem based on the data available. Assuming the
expressed as "hemicellulosic sugars", which include all above hypotheses, the equation giving the dependence
the non-glucose monosaccharides present in pulping of the hemicellulosic sugar concentration (HSC) with
liquors. The experimental results (see Table 7) showed time is
a kinetic pattern similar t o that of acid-catalyzed
hydrolysis of polysaccharides in aqueous media: the
existence of sugar degradation reactions resulted in
decreased concentrations when the experiments were
performed under strong operational conditions (Saeman, where HSC, is the "potential concentration" of hemi-
 Ind. Eng. Chem. Res., Vol. 34,No. 12, 1995 4339

i - 0.1SW HCl, 115 P C 0.25% HCI. 115 PC

--e-
0.36% HCI, 115 *C
..........
..A.
0.45% HCI, 115 nC

I - 0.15% HCI. 130 ec 0.25% HCI 130

--&- nc 0.35% HCI, i w ec
.......&...... 0.45% nct, 130 o c

12

12

,--T---
.-.
.'...
... -+---

---__
---_
O Y
12,

10 --

..
--------
0 60 100 1so 200

DURATION OF TREATMENTS, rntn

Figure 5. Experimental and calculated dependence of hemicellulosic sugar concentration (HSC) on operational variables.

cellulosic sugars, corresponding t o a quantitative con-
version of hemicelluloses into sugars. Table 8 lists the
values obtained for the regression parameters k,j and
k7 when the results of Table 7 were fitted to eq 10.
Figure 5 shows the experimental and calculated values
of HSC. The maximal concentrations obtained a t 115
"C (10-11.5 g/L) corresponded to the amount generated
by quantitative conversion of 43-50% of initial hemi-
celluloses. In experiments performed a t 130 "C, the
strong dependence of k7 on temperature provoked a
marked decrease in the maximal HSC in relation to the
corresponding experiments carried out a t 115 "C.
Furfural Concentration. Figure 6 shows the fur-
fural concentrations obtained in the experiments per-
4340 Ind. Eng. Chem. Res., Vol. 34, No. 12, 1995

2
i
0)
m

4
0
1.6

0 1.2

8
=) 0.8
LL
a
2 0.4

3 ,

4
32*5m

$ 2
0
1.5

zs 1
pe
a
u.
0.5

0
0 60 100 160 200

DURATION OF TREATMENTS, min

Figure 6. Dependence of furfural concentration on operational variables.
Table 7. Hemicellulosic Sugar Concentrations (gk) Table 8. Regression Parameters Obtained in the
Obtained in Experiments Modeling of Hemicellulosic Sugar Concentration
time 0.15% 0.25% 0.35% 0.45%
(mid HC1 HC1 HCl HC1
(a)Experiments Performed a t 115 "C 115 0.15 0.0094 0.0064 0.965 100
0 0 0 0 0 115 0.25 0.011 0.0081 0.9527 101
15 3.8 5.3 6.0 8.1 115 0.35 0.016 0.0098 0.9632 1312
30 4.4 5.8 7.0 9.1 115 0.45 0.023 0.0119 0.8874 39
60 9.0 8.3 10.2 11.1 130 0.15 0.012 0.017 0.8480 22
90 10.0 9.6 10.0 9.0 130 0.25 0.018 0.031 0.8178 18
120 8.9 10.3 9.9 8.7 130 0.35 0.016 0.041 0.9177 45
180 10.2 8.6 7.2 6.4 130 0.45 0.017 0.058 0.7826 14
(b)Experiments Performed at 130 "C
0 0 0 0 0 notably lower than the ones calculated from material
20 5.6 7.0 5.1 4.7 balances based on the fraction of hemicelluloses de-
40 6.2 5.5 4.8 3.7 graded. This fact proved that parasitic pathways (lead-
60 6.1 5.2 4.1 2.4
120 5.6 3.6 2.2 2.0 ing t o M r a l and/or hemicellulosic sugars consump-
180 4.9 2.1 1.7 1.5 tion) existed in the reaction media, similarly to reported
results (Brennan et al., 1986; Abatzoglou et al., 1990;
formed. The shape of curves is similar in all the cases Mok et al., 1992). Attempts in modelization of furfural
considered, with a kinetic pattern similar to that concentration by sequential reactions (furfural genera-
previously discussed for the hemicellulosic sugars. The tion from hemicellulosic sugars followed by furfural
existence of furfural degradation reactions was evident conversion into condensation products) were unsuccess-
in experiments carried out a t 130 "C. In the same way, ful, suggesting a complex mechanism involving ad-
it can be remarked that even at 115 "C, the overall ditional side reactions as proposed in the literature
amounts of hemicellulosic sugars and furfural were (Brennan et al., 1986; Abatzoglou et al., 1990; Mok et
 /-'
Ind. Eng. Chem. Res., Vol. 34,No. 12, 1995 4341

PREVIOUS INFORMATION

Temperature ( l l l o r 130QC) Rerdlon time (0-180 mln)

LCo PC GPR HSC
0 0 P Catalyst concentration (0.164.45 K HCI)

SELECTED EXPERIMENTAL CONDITIONS

/
/
I L
Fig. 8

(1 /------ -.
Furfural conc.
\
)
---------'
4

Figure 7. Calculation scheme for application of results obtained in this work.

al., 1992). However, it can be noted that the maximal
furfural concentrations obtained in experiments (1.6-
2.8 g/L)accounted for a limited part (10-18%) of the
hemicelluloses degraded, a conversion too reduced for
causing a significant impact in economic estimations.
Application of Results. As stated above, the main
objective of this work was to obtain information useful
for performing preliminary design and simulation stud-
ies on the studied process. Figure 7 summarizes a
calculation framework based on the data presented in
this work. This procedure allows the prediction of the
minimum set of variables necessary for performing
material and energy balances t o the studied process.
Conclusion
Pine wood processing with HC1-catalyzed acetic acid
solutions provides an efficient way to separate the main
fractions of the raw material: in a single step, deligni-
fication and hemicellulose degradation are provoked,
with good selectivity toward cellulose decomposition. In
order to obtain kinetic models useful for simulation and
design purposes, the main phenomena involved in this
process were studied. The effects of selected operational
variables (reaction time in the range 0-180 min,
catalyst concentration in the range 0.15-0.45%, and
temperature of 115 or 130 "C) on pulp yield, residual
lignin in pulp, polysaccharide degradation, and hemi-
cellulosic sugar generation were correlated by simplified
models based on single or consecutive reactions with
pseudohomogeneous,first-order kinetics. The equations
proposed provided a satisfactory reproduction of the
experimental data. Furfural was generated from hemi-
cellulosic sugars and decomposed in the reaction media,
with a complex mechanism. The small furfural concen-
trations achieved (0-2.8g/L) suggested that this byprod-
uct should have a limited importance in the economic
perspectives of the process. Thus, the kinetic models
presented in this work provide the technical information
necessary to evaluate the feasibility of the studied
process.
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Received for review July 28, 1994
Revised manuscript received July 11, 1995
Accepted July 25, 1995@
IE940465W
@Abstract published in Advance ACS Abstracts, October 15,
1995.