Journal of Cleaner Production 18 (2010) 395401

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Journal of Cleaner Production

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Formic and acetic acid as agents for a cleaner fractionation of Miscanthus

x giganteus
Juan Jose Villaverde, Pablo Ligero, Alberto de Vega*
Department of Physical Chemistry and Chemical Engineering, University of A Coruna, A Coruna 15071, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Miscanthus. x giganteus bark was subjected to acetic and formic acid fractionation. The kinetics of the
Received 19 May 2009 process were explained by a model of two parallel rst-order reactions, for pulp yield and delignication,
Received in revised form and by Saemans kinetics based models, for total polysaccharides and viscosity of pulps. The inuence of
21 October 2009
hydrochloric acid concentration on both organosolv processes was studied at two levels: 0.10 and 0.15%
Accepted 29 October 2009
by weight. The models provided a good t of the experimental data and helped to predict the best set of
Available online 6 November 2009
independent variables to obtain a good fractionation.
Both systems achieved similar delignication levels and pulp characteristics, although the evolution in
Keywords:
M. x giganteus formic acid was faster than in acetic acid, mainly due to the great extent of reactions in the warming up
Delignication period that accounted for about a third part of the initial dry weight of the raw material.
Organosolv fractionation 2009 Elsevier Ltd. All rights reserved.
Acetic acid
Formic acid
Kinetics

1. Introduction environmental problems derived from cooking with sulphur

The fast human development since half of the XVIII century is
based on the exploitation of fossil sources. However, in the 1960s
the rst clear evidence of environmental impacts of the industrial
development, and later in the early 1970s, with the rst oil crisis,
demonstrated the risk of the dependence on fossil sources. The
development and decline of civilizations or societies based on the
overexploitation and exhaustion of natural sources, accompanied
by serious environmental damage is not a new phenomenon [1]. To
overcome such risk, society must start to prepare the transition
from a development model based on non-renewable, to a renew-
able resources based model, in order to no longer depend on fossil
sources. Vegetal biomass looks the most logical solution for the
sustainable production of energy and chemicals. Among these
renewable biomass sources, different non-woody materials, such as
annual and perennial grasses, should become the object of impor-
tant research work for industrialised countries if they want to full
their demands.
Nowadays the kraft process still continues to be the predomi-
nant method to produce cellulose pulps from lignocellulosic
materials. But the Kraft process is accompanied by signicant
* Corresponding author. Fax: 34 981 167065.
E-mail address: devega@udc.es (A. de Vega).
compounds that generate malodour substances like hydrogen
sulphide, methyl mercaptan and dimethyl sulphide, and from, in
some cases the bleaching of pulps with chloride compounds [2]
which have not yet been completely solved [3]. Furthermore, the
growing world demand of pulp for paper has unquestionable
impacts on forests. Nevertheless an alternative approach to exploit
lignocellulosic materials is available. With regard to cooking, it is
obvious that the best way to avoid the problems associated with the
use of sulphur compounds is not to use them. This idea has led the
design and improvement of organosolv processes. In short, in an
organosolv process, the removal of lignin from the solid matrix, is
achieved replacing sulphur compounds by organic solvents. These
organic compounds (with or without the aid of small amounts of
mineral acid) produce the delignication of the raw material in
a more gentle and effective way than the kraft process does. This
milder way to operate means that the natural polymers present in
plant material are separated in a less degraded way, thus opening
up possibilities for its use with higher added value, while lignin
solubilised in kraft process is on-site burned to produce energy,
adding more environmental impacts [4]. In other words, organo-
solv processes can be designed as fractionation methods rather
than pulping methods [5]. That is, they could be operated to
virtually achieve a complete exploitation (fractionation) of raw
materials, yielding the main components of vegetal tissues (cellu-
lose, hemicelluloses and lignin) in a less degraded form [6]. This

0959-6526/$ see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jclepro.2009.10.024
396 J.J. Villaverde et al. / Journal of Cleaner Production 18 (2010) 395401
characteristic can open promising perspectives for the integrated
exploitation of the biomass, within the concept of the biorenery
[7], similar to that of an oil renery, whose main goal is to take
advantage of the compositional diversity of biomass to produce
high-value low-volume and low-value high-volume products and
energy using different concurrent methods, while minimizing
waste streams [7].
The genus Miscanthus comprises a number of tall perennial
rhizomatous grasses, belonging to Poaceae family, with C4 photo-
synthesis, native of tropics and subtropics, with an excellent
productivity, fast grown and low sensitive to illness [8]. Among
these grasses, Miscanthus x giganteus Greef & Deuter ex Hodkinson
& Renvoize [9], a sterile hybrid horticultural genotype, has attracted
the interest of the EU authorities as a biomass source. In 1993,
a project was set up under the European AIR program to know the
potential and limitations of M. x giganteus in Europe, and organo-
solv fractionation were carried out within the biorenery
perspective [10,11]. First designed for energy applications [12],
immediately it began to be investigated for its possible utilization
by chemical methods.
Acetic and formic acid, using hydrochloric acid as catalyst
(henceforth Acetosolv and Formosolv), have proved to be good
lignin solvents for Miscanthus, among others [13], yielding satis-
factory levels of delignication and physical properties [10,11]. This
work was carried out in order to establish the kinetic interrela-
tionships between the operational variables (time and catalyst
concentration) and yield, Klason lignin, intrinsic viscosity, and
carbohydrate content of pulps in treatments of M. x giganteus with
acetic and formic acid fractionation systems catalyzed with
hydrochloric acid. From the experimental data, a quantitative
interpretation of the experimental results, by kinetic models, was
developed.
This work is complementary to other organosolv fractionation
studies with M. x giganteus by short chain carboxylic acids [10,11],
and will assess the optimal fractionation conditions to use in future
studies of bleaching and exploitation of recovered hemicelluloses
and lignin.
2. Material and methods
2.1. Raw material
M. x giganteus was collected from an experimental plantation
established near Santiago de Compostela (Galicia, Spain) as a result
of the EU AIR Miscanthus Productivity Network project [8]. Stems
were harvested, and after air drying period, manually stripped of
leaves and core. Bark was milled to pass a 1 cm screen, let to attain
its equilibrium moisture and nally stored in hermetic plastic bags.
2.2. Kinetic studies
Fractionation kinetic studies were performed using mixtures of
ground M. x giganteus, water and acetic or formic acid, heated to
boiling point in 250 cm3 Pyrex asks. In this moment hydrochloric
acid was added, taking this as time zero. The selected concentra-
tions of hydrochloric acid were 0.10 and 0.15%, according to the best
results found in previous work [10,11]. The mixtures were reuxed
with stirring at atmospheric pressure along a desired time. Reac-
tions were stopped by removing the asks from the heating plates
and by fast ltration through medium-pore Gooch crucibles to
separate pulp and black liquors. Then pulps were treated four times
with 85% acetic (in acetic acid system) and 80% formic acid (in
formic acid system) in w/v proportions of 0.4, 0.4, 0.2 and 0.2 in
relation to the initial dry weight of M. x giganteus. Finally, pulps
were washed with distilled water until the washings were neutral.
2.3. Analytical methods
Pulp yield (PY) was determined gravimetrically after drying to
constant weight. Lignin in raw material and pulps (residual Klason
lignin in pulp, RKL) was determined by weighing the residue
obtained following two-stage Klason digestion with 72% H2SO4 for
2 h at 15  C followed by 3% H2SO4 for 1 h at 120  C (TAPPI T222
om-88). Other standard TAPPI procedures were used to determine
the kappa number (KN) (TAPPI T236), intrinsic viscosity (VIS) of
pulps (TAPPI T230), ash (TAPPI T 211 om-02), and pentosans
(TAPPI T223 om-84). Total polysaccharide content of pulps (TP)
was quantied by spectrophotometric determination of reducing
sugars in the Klason hydrolysate by the SomogyiNelson method.
Holocellulose was determined by the chlorite method according to
Browning [14].
2.4. Fitting of data
Non-linear regressions between experimental data and
proposed models were performed using commercial software
(Statgraphics 5.0 from Manugistics).
3. Results and discussion
The chemical composition of depithed M. x giganteus stem, on
a dry weight basis, was determined analytically as 26.1% Klason
lignin (3 replications, standard deviation 0.42), 73.3% holocellulose
(2 replications, standard deviation 2.30), 18.8% pentosans (2 repli-
cations, standard deviation 0.47), and 0.4% ash (3 replications,
standard deviation 0.12).
Previous works [10,11] and preliminary experiments showed
that extensive delignication can be achieved under organic acid
concentrations of 90 weight% for Acetosolv and Formosolv systems,
using a liquor/wood ratio 12 w/w, and small proportions of
hydrochloric acid as catalyst. In order to further assess the best HCl
concentration to achieve the more suitable fractionation of the raw
material, a kinetic monitoring was performed in which two
different concentration of mineral acid were used (0.10% and 0.15%
by weight) in the range 0180 min.
3.1. Pulp yield and delignication
Kinetics proles of PY and RKL are very similar (Fig. 1): a high
decrease is observed in the rst minutes, followed by a slow phase
where values tend to an asymptotic limit. To simulate this behav-
iour, researchers usually have utilised a phenomenological kinetic
model based on the supposition of two simultaneous pseudo-rst
order reactions taking place [15,16]. This approach involves the
existence of two fractions of materials/lignin with different
susceptibilities towards solubilisation/delignication. One fraction
shows high ability to solubilise/delignify, reacting rapidly thus
becoming predominant at short times, while the second is difcult
to solubilise/delignify and proceeds slowly during more prolonged
times. Such stages are usually referred in bibliography as bulk and
residual phases, respectively.
As a strict kinetic model is not possible to build, due to the
substrate heterogeneity and complexity, the following were
assumed.
 The model will be built as for a homogeneous system.
 Due to the impossibility to know molecular weights of involved
species, the formulation of the model in molar units was let
apart and replaced for dry weight percentages.
 J.J. Villaverde et al. / Journal of Cleaner Production 18 (2010) 395401 397

 Xf0 and Xs0 are the percentage, at time zero, of solids or lignin
a 95
that undergoes the fast and slow reaction, respectively.
90 Acetosolv, 0.10% HCl
 kf and ks are the rate constants of fast and slow reaction,
85 Acetosolv, 0
0.15% HCl respectively.
80 Formosolv, 0.10% HCl
 t is the reaction time.
Pulp yield (% d.b.)

75 Formosolv, 0.15% HCl

The integrated equations for this system are:
70
Xf Xf 0 ekf t
65

60 Xs Xs0 eks t
55
So, for a given time, PY can be measured as the sum of contri-
50 butions of the fast and slow reacting fractions:
45
0 20 40 60 80 100 120 140 160 180 200 PY PYf PYs PYf 0 ekf t PYs0 eks t
Time (min.) PYtot0  PYs0 ekf t PYS0 eks t
25
b In a similar way, for RKL:
Acetosolv, 0.10% HCl

Acetosolv, 0
0.15% HCl RKL RKLf RKLs RKLf 0 ekf t RKLS0 eks t
Residual Klason lignin (% d.p.b.)

20
Formosolv, 0.10% HCl RKLtot0  RKLs0 ekf t RKLS0 eks t
Formosolv, 0.15% HCl
15 Table 1 lists the obtained regression parameters for kf, ks, Xtot0
and Xs0 when the data of Table 2 were tted to previous equations,
as well the R2 statistical parameter measuring the correlation of
10 equations.
Fitting of data resulted in a good correlation between time and
both PY and RKL (Fig. 1). From observation of Fig. 1 and values of
5
PYtot0 (Table 1) it can be inferred that an extensive solubilisation
occurred during heating period, which accounted for about 15% and
33% for acetic and formic acid, respectively. In a similar way,
0
0 20 40 60 80 100 120 140 160 180 200 delignication in the heating period was more important for formic
Time (min.) acid (Fig. 1 and Table 1). As expected, parameters PYtot0 and RKLtot0
diminished as hydrochloric acid concentration rise, reecting the
Fig. 1. Experimental data and tted curves for the pulp yield and Klason lignin
inuence of mineral acid. Fig. 1 also reveals a higher solubilising
remaining in pulp.
ability of formic acid: yields around 47% were obtained for long
 As said above it is supposed that both reactions agree with lasting reactions, instead around 55% for acetic acid.
a rst-order progress with time. That is they follow pseudo- A similar trend is observed in the behaviour of RKL: a fast
rst order kinetics. reaction in the rst minutes, followed by a residual slow process.
Nevertheless signicant differences were observed between the
Chemical equations for the formulation for this process are: two processes. The end of the fast reaction depends on the organic
acid and on the studied variable (Fig. 1 and Table 1): for PY, the fast
Xf kf reaction appears to be stopped almost at the same time (aprox.
Solubilised 25 min) in the two systems, followed for a slow solubilisation that
ks materials seemed not to be dependent on HCl concentration (similar kf for
both systems). For RKL, the Formosolv system follows a similar
Xs
trend: a comparatively very fast reaction until about 25 min, and
a residual stage from this time on, whereas Acetosolv system shows
where a smoother fast delignication as it is more prolonged in time, until
approx. 5060 min. Furthermore, the ks showed a signicant
 Xf and Xs are the percentages, at time t, of solids or lignin that difference; their values for Acetosolv system are roughly 10 times
undergo the fast and slow reaction, respectively. higher, which means that, while Formosolv delignication was

Table 1
Values of the kinetic parameters for the solubilisation and delignication processes obtained by non-linear regression.

Regression parameters Acetic acid Formic acid

0.10% HCl 0.15% HCl 0.10% HCl 0.15% HCl

RKL PY RKL PY RKL PY RKL PY

Xtot0 (% d.m.) 23.30 82.37 23.78 88.32 15.83 71.25 11.78 62.02
Xf0 (% d.m.) 17.21 20.24 17.83 26.81 11.69 15.84 6.87 6.63
XS0 (% d.m.) 6.09 62.14 5.95 61.51 4.14 55.41 4.91 55.39
kf (min1) 0.0560 0.1056 0.0951 0.0891 0.1745 0.3560 0.1535 0.1543
ks (min1) 0.0051 0.00077 0.0071 0.00069 0.00016 0.00085 0.0026 0.0010
R2 0.9973 0.9672 0.9916 0.9826 0.9668 0.9673 0.9603 0.9088
398 J.J. Villaverde et al. / Journal of Cleaner Production 18 (2010) 395401

Table 2
PY, RKL, TP and VIS of pulps obtained in each treatment.

Time (min) Acetic acid Formic acid

0.1% by weight 0.15% by weight 0.1% by weight 0.15% by weight

PY (%) RKL (%) TP (%) VIS (mL/g) PY (%) RKL (%) TP (%) VIS (mL/g) PY (%) RKL (%) TP (%) VIS (mL/g) PY (%) RKL (%) TP (%) VIS (mL/g)
0 83.2 23.5 70.6 120 88.4 23.9 73.6 213 71.3 16.1 77.9 350 62.0 11.8 78.9 573
5 72.1 18.6 76.6 237 78.6 16.6 77.6 308 57.3 7.9 86.2 1085 58.5 7.9 85.2 1053
10 67.9 15.4 80.5 301 72.2 12.3 81.0 399 56.6 7.0 87.8 1130 55.6 6.6 86.7 1221
15 67.6 13.6 81.1 420 66.8 10.1 83.3 468 56.8 5.4 88.6 1142 54.9 5.2 88.2 1225
20 63.4 10.9 85.7 386 64.5 7.5 88.8 612 53.4 4.9 89.5 1138 54.5 4.9 89.7 1168
25 63.3 9.9 90.1 429 64.1 6.4 90.7 685 53.0 4.7 90.6 1085 56.1 4.2 90.1 1107
30 62.3 8.2 91.0 526 63.3 6.1 90.8 716 53.4 4.5 91.6 1131 54.7 5.5 90.5 1069
40 60.1 6.9 92.2 666 61.9 5.8 91.0 913 52.9 3.8 92.2 1098 53.5 4.8 91.0 1094
50 59.9 5.6 93.6 752 60.2 4.1 92.3 942 54.0 4.2 92.5 1045 53.3 4.4 91.3 879
60 59.1 5.4 92.3 809 56.9 3.5 90.1 1017 53.3 3.8 92.8 1084 52.4 4.3 92.1 1005
70 60.5 4.3 93.0 1078 60.2 3.4 91.7 966 52.0 3.6 93.6 1054 49.8 3.5 90.4 973
80 54.9 4.1 93.7 1089 58.6 4.4 91.2 1093 51.9 3.5 92.9 1057 51.9 4.5 90.7 944
90 57.0 3.8 93.5 1066 55.8 2.4 91.0 1057 51.0 3.6 92.0 993 48.0 3.2 89.6 999
100 58.7 4.4 93.4 929 57.9 2.2 90.7 1151 51.1 3.7 94.0 948 50.4 3.4 90.9 974
120 56.7 2.9 92.1 1129 55.1 2.6 91.7 1105 48.6 3.7 92.5 886 48.6 3.5 90.4 908
150 55.5 3.0 93.8 1120 54.9 1.8 91.2 1016 50.0 5.0 91.9 851 47.1 3.4 90.6 853
180 54.7 2.4 93.2 1058 56.0 2.6 91.7 969 47.6 4.3 91.4 838 48.7 3.6 90.9 951

virtually stopped at around 40 min, Acetosolv solubilisation of

kS
lignin continues in an almost linear process until 180 min. This Polysaccharides in unpurified pulp !
Solubilisation
could make possible an extended delignication that could not be kH
accomplished in the Formosolv system. In fact, the differences of Polysaccharides in purified pulp ! HP
Degradation
RKL, predicted by the models, between both systems for the most kS kH
prolonged experiments are lower in the acetic process by 1.4 and Pup / TP / HP
1.6%. Nevertheless, no clear signs of lignin recondensation and/or The rate equation for the content of polysaccharides in pulp is:
reprecipitation were observed for the two systems.
No important differences in solubilisation were found when
dTP
comparing the use of one or other HCl concentrations. The same kS Pup  kH TP
dt
was observed for delignication with formic acid: both tted curves
are almost superimposed. Acetosolv delignication revealed more and the corresponding integrated expression:
sensitivity to HCl concentration since kf for 0.15% HCl is roughly kS  kS t 
TP TP0 ekH t Pup0 e  ekH t
twice that kf for 0.10% HCl. In other words, the tted line for 0.15% kH  kS
HCl is always below the corresponding to 0.10%, what means lower
where:
lignin content in pulp is obtained, for the same time treatments,
when working with 0.15%.
 (TP)0 and (Pup)0 are constant of the model that can be identi-
ed as the fraction of pulp polysaccharides, at time zero,
3.2. Total polysaccharides in pulp available and unavailable for degradation composition,
respectively.
The determination of reducing sugars after quantitative hydro-  k1 and k2 are the pseudo-rst order rate constants for the
lysis of pulps was performed for all samples. These data are related solubilisation and degradation reactions, respectively.
with the process of cellulose purication which is concurrent with
delignication. Results (Fig. 2) show a very fast enrichment in 100
cellulose in the rst minutes, is in accordance with the already
mentioned fast delignication phase, followed by an almost hori-
Total polysaccharides in pulp (%d.b.)

95
zontal prole. This means that puried cellulose in pulp suffered
a moderate subsequent damage by acid hydrolysis. This was also
90
conrmed by mass balances, since if there was no degradation, the
values of (100  RKL) should provide, for each treatment time, the
value of TP (given the low proportion of extractives which more- 85
over should be mostly solubilised).
Therefore, in order to simulate the kinetic behaviour of total Acetosolv, 0.10% HCl
80
polysaccharides a simple phenomenological model, based on that Acetosolv, 0.15% HCl
of Saeman [17], was used, in which two consecutive set of
75 Formosolv, 0.10% HCl
phenomena were taken into account (assuming that both follow
pseudo-rst order kinetics): A rst group of reactions combining all Formosolv, 0.15% HCl

the reactions that nally result in the solubilisation of lignin, 70

0 20 40 60 80 100 120 140 160 180 200
hemicelluloses and other components, thus enriching the content
Time (min.)
of polysaccharides in pulp, and a second one accounting for all the
degradation paths, mainly hydrolytic, of polysaccharides. Thus, in Fig. 2. Experimental data and tted curves for the total content of polyscaccharides
a very simplied way, we can write in pulp.
 J.J. Villaverde et al. / Journal of Cleaner Production 18 (2010) 395401 399

Table 3
Values of the kinetic parameters for total polysaccharides content of pulps obtained by non-linear regression.

Regression parameters Acetic acid system Formic acid system

0.10% HCl 0.15% HCl 0.10% HCl 0.15% HCl

Total polysaccharides in pulp (TP) C0 (% d.m.) 70.3 72.5 79.0 79.2
P0 (% d.m.) 24.5 19.8 14.0 11.8
k1 (min1) 0.0549 0.0697 0.0893 0.1103
k2 (min1) 0.00012 0.000086 0.000058 0.000033
R2 0.9777 0.9605 0.9463 0.9679
tmax (min) 87 74 61 55
TPmax (% d.m.) 93.7 91.6 92.6 90.8

Intrinsic viscosity (VIS) VIS0 (mL/g) 103 192 350 571

B (mL/g) 1987 1607 828 585
k1 (min1) 0.0100 0.0160 0.446 0.441
k2 (min1) 0.00424 0.00445 0.00201 0.00185
R2 0.9620 0.9870 0.9825 0.8045
tmax (min) 144 104 11 11
VISmax (mL/g) 1114 1101 1150 1131

Due to the high empirical grade of the proposed model, the
parameters (TP)0 and (Pup)0 are difcult to explain on a strict
chemical basis, but the tting of data resulted in a good correlation
between time and measured total polysaccharides in pulp (Fig. 2
and Table 3), giving a simpler equation to simulate the behaviour of
cellulose during reaction. Fitting parameters are presented in Table
3. As can be seen from Table 3 decomposition reactions of poly-
saccharides are greatly restricted, in the time range studied,
according to the very low values of the k2 constants. Nevertheless,
the maximum enrichment in polysaccharides is attained in a rela-
tively short time that can be calculated from the kinetic model by
derivation and equalling to zero the result. Such process yields the
following expression for the time to achieve the maximum poly-
saccharides content:
 
ln a  CP0 ab
k
0 1
tmax
b functional dependence of the type VIS exp (Constant $ RKL) that
where:
k2
a ; b k2 k1
k1
And according to this, maximum predicted values (Table 3)
around 92% d.m. could be achieved in relatively short times
between 55 and 87 min. Formosolv system evolutes a bit quickly
than Acetosolv, probably due to its higher solubilising power in the
heating period that contributes to a more important enhancement
in polysaccharides content of pulp. Although of lesser importance,
hydrolytic effects are observed in Fig. 2, where the near horizontal
phases of the process using 0.15% HCl is below the corresponding to
0.10% for both systems. Also, a small effect is observed in the use of
two organic acids, because from the maximum and beyond, acetic
acid yielded pulps a bit more puried.
3.3. Viscosity of pulps
Intrinsic viscosity was also determined for all pulps. A fully
empirical model was used to obtain regression equations from
experimental data. In Fig. 3, ln (VIS) is represented versus RKL. A
clear linear dependence is observed for acetic acid pulps, while
Formosolv system seems to follow a similar linear dependence until
about 6% RKL, and from here delignication proceeds at the
expense of the cellulose viscosity. This suggests an exponential
must be complemented, especially for formic acid (Fig. 4), for
hydrolytic decomposition. Moreover, as VIS is closely related to
both purity of samples (non-cellulosic compounds present in
partially delignied pulps are cross-linked polymers or low
molecular mass products that affect not the reproducibility but the
reliability of the determination) and polysaccharide chain length
(affected by hydrolytic and/or decomposition reactions) a simple
model that could reect this facts was chosen. Again that model
was that of Saeman, but in a fully empirical form in order to explain
the shape of curves obtained, in which a rst stage of purication/

8 .0 1400
Acetosolv, 0.10% HCl
1200
7 5
7.5 Acetosolv, 0.15% HCl

Formosolv, 0.10% HCl 1000

mL/g)

Viscosity (mL/g)

7.0
Viscosity (m

Formosolv, 0.15% HCl

800
6.5
600 Acetosolv, 0.15% HCl
ln (V

6.0 Acetosolv, 0.15% HCl

400
Formosolv, 0.10% HCl
5.5
200
Formosolv, 0.15% HCl

5.0 0
0 5 10 15 20 25 30 0 20 40 60 80 100 120 140 160 180 200
Residual Klason lignin (% d.p.) Time (min.)

Fig. 3. Dependence of the viscosity with the Klason lignin remaining in pulp. Fig. 4. Experimental data and tted curves for the viscosity of pulps.
400 J.J. Villaverde et al. / Journal of Cleaner Production 18 (2010) 395401

Table 4
Values of DV predicted from regression equations when VIS and TP are maximum.

0.10% HCl 0.15% HCl

Acetic acid system
t VISmax (min) PY (%) RKL (%) TP (%) VIS (mL/g) t VISmax (min) PY (%) RKL (%) TP (%) VIS (mL/g)
144 55.6 2.9 93.2 1114 104 57.3 2.9 91.5 1101

t TPmax (min) PY (%) RKL (%) TP (%) VIS (mL/g) t TPmax (min.) PY (%) RKL (%) TP (%) VIS (mL/g)
87 58.1 4.0 93.7 1014 74 58.5 3.5 91.6 1059

Formic acid system

t VISmax (min) PY (%) RKL (%) TP (%) VIS (mL/g) t VISmax (min) PY (%) RKL (%) TP (%) VIS (mL/g)
11 55.2 5.9 87.7 1150 11 56.0 6.0 87.5 1131

t TPmax (min) PY (%) RKL (%) TP (%) VIS (mL/g) t TPmax (min) PY (%) RKL (%) TP (%) VIS (mL/g)
61 52.6 4.1 92.6 1045 55 52.4 4.3 90.8 1047

enrichment on cellulose and a second one representing cellulose
degradation were taken into account. So, a similar expression to the
Saemans model can be assumed:
k1  k2 t
VIS VIS0 ek2 t B e  ek1 t
k1  k2
Here, VIS0 is the intrinsic viscosity at time zero, B and empirical
constant, and k1 and k2 the corresponding kinetic constants for the
pulp cellulose enrichment and cellulose degradation, respectively.
Table 3 shows the calculated tting parameters and Fig. 4 the
experimental points and tted lines for formic and acetic acid
systems. Differences in using one or another acid become very clear.
Formosolv pulp viscosity grows very fast in the rst minutes,
reaching its maximum values (1150 and 1131 mL/g for 0.10% and
0.15% HCl, respectively) at 11 min for both HCl concentrations
tested. Furthermore, the predicted proles for these HCl concen-
trations are virtually the same (Fig. 4), meaning that the mineral
acid does not have inuence on pulp viscosity, even in the decom-
position phase that could be expected to be dependent on that
concentration. The relative high acidity of formic acid could explain
this result: the effect of mineral acid is hidden by the greater
concentration of formic acid, which contributes to proton formation
in much higher extent than HCl. In the case of acetic acid, the
situation differs; the more HCl is added the fast maximum viscosity
is achieved (144 min for 0.10% HCl, and 104 min for 0.15% HCl),
whereas the predicted viscosity values do not differ signicantly
(1114 mL/g for 0.10% HCl, and 1101 mL/g for 0.15% HCl) (Table 4).
Eventually, a look on the evolution graphs for both systems
(Fig. 5) enables to conclude that although the evolution is very
different depending on the organic acid, as was mentioned, the best
100
n pulp (% d.p.)
d
obtained pulps are very similar in VIS and TP. Therefore, the more
suitable conditions must be chosen depending on the rest of
dependent variables. Although the models predict very similar
values for VIS and TP, around the maxima calculated (Table 4), small

differences were found for PY and RKL, being its values more
favourable to Acetosolv system: 3.3% higher in PY, and 1.8% lower in
RKL, in average.
4. Conclusions
Acetic and formic acid systems were modelled with the
proposed kinetic models, and the used equations provided a satis-
factory prediction of the experimental data. M. x giganteus pro-
cessing with HCl as catalyst of aqueous mixtures of acetic and
formic acid provides an efcient way to separate the main fractions
of this grass. Thus, the presented kinetic models in this work
provide valuable information necessary to evaluate the feasibility
of the studied process.
Although Formosolv system, during the warming up period,
dissolves a higher amount of lignin from M. x giganteus, achieving
earlier a higher content of TP, Acetosolv system, after adding the
catalyst, is more efcient than Formosolv system. The small effect
observed in Formosolv system from the catalyst addition is
presumably due to a higher saturation of solution with soluble
lignin and carbohydrates during heating, and to the higher acidity
of formic acid in relation to acetic, that hides the effect of hydro-
chloric acid. Taking this into account, 0.10% HCl seems the more
adequate concentration to use in the formic acid system.
In view of the VIS and TP behaviour along the process, in the
acetic system, hemicelluloses together with lignin are dissolved
during reaction (hence VIS ascent), and only after the more
prolonged treatments cellulose is degraded. Formic acid system
evolution in the warming up period is very important since
signicant proportions of lignin are dissolved, whereas in acetic

90 acid system this effect is much lower. This is probably due to the
higher acidity constant of formic acid, which is 10 times higher than
that of acetic acid. Therefore, in Formosolv system, the necessary
80
charides in

time to get a pulp with kappa near 20 to start with a bleaching

process is achieved before than with Acetosolv system. Also, for
70 Acetosolv 0.10% HCl a given HCl concentration, TP curves in the formic acid system
al polysacc

Acetosolv 0.15% HCl always are below to the corresponding to acetic acid system, which
means that Formosolv system is less efcient for elimination of
60 Formosolv 0.10% HCl
lignin than Acetosolv.
Tota

Formosolv 0.15% HCl

50 Acknowledgments
0 250 500 750 1000 1250 1500
Viscosity (mL/g)
The authors are grateful to Xunta de Galicia for their granting
Fig. 5. Selectivity graphs for acetic and formic acid fractionation systems. of the research project (PGIDIT04RFO2659912PR: Obtencion de
 J.J. Villaverde et al. / Journal of Cleaner Production 18 (2010) 395401
biopolmeros de orixe vexetal a partir da biomasa do Miscanthus
sinensis, en condicions de cultivo enerxetico, por procedementos
solvolticos), to Dr. D. Manuel Bao Iglesias, from University of
Santiago de Compostela, for the kind supply of M. x giganteus, and
to University of A Coruna to grant a predoctoral fellowship to Mr. J. J.
Villaverde.
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