Hd["~l 7 ai~ Roll- uutd
Holz als Roh- und Werkstoff44 (1986) 415-418
Selection of operational conditions in alkaline lixiviation
of Pinus pinaster bark
G. Vfizquez, G. Antorrena and J. C. Paraj6
Chemical EngineeringDepartment, Faculty of Chemistry, University of Santiago de Compostela. Spain
The amounts of formaldehyde-condensable polyphenols extracted
from Pinus pinaster bark through alkaline lixiviations performed
under different operational conditions are determined. Under the
best conditions, both the losses of polysaccharides from the solid
phase and the additional extracted polyphenols, coupling two stages
of alkaline lixiviation, are evaluated. The effect of particle size on
kinetics and yields of the lixiviationsis determined.
Zur Bestimmung der Arbeitsbedingungen
fiir die Alkali-Extraktion yon Pinus pinaster Rinde
Die Mengen formaldehyd-kondensierbarer Polyphenole, die aus Pi-
nus pinaster Rinde durch Alkali-Extraktion unter verschiedenenAr-
beitsbedingungen gewonnen werden konnten, wurden bestimmt.
Unter den jeweils giinstigsten Bedingungenwurden die Verluste an
Polysacchariden der festen Phase und die zus/itzlJch gel6sten Poly-
phenole aus einer zweistufigenAlkali-Extraktion gemessen. Der Ein-
flug der Partikelgr6Be aufden Verlauf und die Ausbeute der Extrak-
tion wurden untersucht.
1 Introduction
After determining the amount and type of compounds which
form Pinus pinaster bark, the possibility of its utilization in
an industrial process based on an alkaline lixiviation was
suggested (VAzquez et al. 1985 a, b). The extracts are utilized
to produce wood adhesives (Anderson et al. 1974, 1977; Ayla
et al. 1981, 1982; Hall 1960; Hemingway 1978; Weissman et
al. 1980 a) and the raffinate (after hydrolysis) gives products
to be used as fermentation substrate. Therefore, the influ-
ence of some variables on yield and kinetics of alkaline lixi-
vitations was studied, using samples of bark from different
origin with different composition (V~zquez et al. 1985b).
However, the comparison between different conditions is
difficult because the yields of formaldehyde-condensable
polyphenols, i.e. the fraction which accumulates the active
compounds in adhesive production, (according to Yazaki
1977), are strongly dependent on the origin of the sample. In
order to obtain better comparative results, several extrac-
tions were performed under equal conditions. Average
values served for selecting four experimental conditions
which were carefully examined, taking into account some
factors not previously considered. Under these selected oper-
ational conditions, experiments were carried out using ho-
mogenized bark samples in order to measure the advantage
obtained by coupling two lixiviation stages in crossflow, be-
cause the yield of raffinates with high polyphenol content
_i lffldg..A Werkstofl'
(~ Springer-Verlag 1986
could be difficult. Special attention was devoted to the
amount of polysaccharides extracted during the lixiviation,
because they would markedly influence the profitability of
the proposed process. As additional data necessary for an
economic analysis of the bark profit, the influence of particle
size on the lixiviation kinetics was examined under condi-
tions which were considered to be most promising.
2 Material and methods
The sampling of Pinus pinaster bark was performed in the
debarking drums of a particleboard plant in Santiago de
Compostela, Spain. The raw material used included all tree
tissues exterior to the vascular cambium.
The samples were air-dried to a moisture content below
30% and milled to obtain particles of less than 1 ram. The
particle size distribution was analogous to values already re-
ported by VAzquez et al. (1985b).
The alkaline extractions were performed in a glass reac-
tor of 600 ml volume at 250 rpm. The solid/liquid ratio used
was l : 10 and the lixiviations were prolonged for 15 min. An
increase of contact time will not result in a substantial in-
crease of the amounts of extracted polyphenols (V/tzquez et
al. 1985 b), but could give rise to undesired carbohydrate los-
ses from the solid phase.
The determination of formaldehyde-condensable poly-
phenols (Stiasny polyphenols) from the first alkaline extrac-
tion was performed by using a combined spectrophotomet-
ric-gravimetric method already reported by Vfizquez et al.
(1985 b). In the extracts from the second stage, the measure
of Stiasny polyphenols was done using the procedure re-
ported by Wissing (1955).
The total of dissolved fractions by alkaline extraction was
calculated as the loss of weight during lixiviation.
The quantitative acid hydrolysis of the polysaccharides
contained in bark and in bark raffinates from alkaline ex-
traction was carried out according to Browning (1957).
The determination of reducing sugars from the above hy-
drolysis was performed according to the Somogyi-Nelson
method (Somogyi 1952). The glucose contained in the ex-
tracts from acid hydrolysis was measured with the YSI-27
Industrial Analyzer (Vfizquez et al. 1985).
The solid residue from acid hydrolysis does not exactly
agree with the Klason ligqlin determined according to Chang
(1955) because the lixiviation with NaOH was not carried
out under the same conditions. Therefore, this fraction is re-
ferred to as "Klason lignin and unsolved polyflavonoids".
416 Holz als Roh- und Werkstoff44 (1986)

3 Results and discussion
In order to obtain extracts with high proportions of formal-
dehyde-condensable polyphenols and raffinates containing
polysaccharides in the highest possible proportion, aqueous
and alkaline extractions of Pinus pinaster bark were carried
out under several conditions chosen on the basis of published
results and on own experience..
The experiments were carried out at 30'L 60~ or 95 C us-
ing NaOH or NazCO 3 in concentrations up to 2 g alkali/
I00 g water. In each set of operational conditions, eight ex-
periments were performed using barks of different origins;
the concentrations of Stiasny polyphenols in the extracts
were measured. To get a more reliable comparison between
the experimental results by eliminating the values imposed
~30
by random sampling, in Fig. 1 average values are given for
each of the studied conditions.
It can be seen from Fig. 1 that aqueous extractions only
dissolve 4% of Stiasny polyphenols, a proportion which is
markedly lower than results published elsewhere (Weiss-
man et al. 1980b; Dix et al. 1983). The addition of small
amounts of NaOH notably increases the polyphenol yield.
The results obtained with Na2CO 3 are markedly lower than
those with NaOH. From Fig. 2, four experimental condi-
tions may be selected to reach high amounts of extracted
polyphenols: alkali concentrations of 0.5 or I g NaOH/100 g
water at 6@" or 95 ~
The decrease in the amount of dissolved polyphenols ob-
served in Fig. 1, from 0.5 to 1 g water at 60 ~ or 95 ~ is sur-
prising. This could be due to bark samples with different
composition.
In order to confirm this hypothesis and to get further in-
formation comparing the most promising conditions, experi-
ments were carried out using homogenized bark samples.

g
>.
// For this purpose the four treatments that gave the highest
proportions of solved polyphenols were chosen. Six lots of
homogenized bark (A to F) were prepared. Each lot was di-
vided into 5 samples (1 to 5) and subjected to alkaline extrac-
~18 J! " li--/I~ tions and acid hydrolysis as shown in Fig. 2, where the deter-
minations are also indicated. The results obtained are shown
in Table 1.
The experimental data show that when changing from
6@' to 95 ~'C at the same alkali concentration, the amount of
dissolved polyphenols is increased. The previous assumption
~B that the anomalous behaviour shown in Fig. 1, was due to
>.
different origins of the samples is confirmed. The influence
of temperature dominates over the concentration effect. The
I I 1 I
smallest amount of extracted polyphenols is achieved at 60 ~'C
0.25 0.50 1.0 g/lOOg water 2.g
Alkali r-encentrotion and 0.5 g NaOH/100 g water (conditions a), followed by
60 ~ and 1 g NaOH/100 g water (conditions b), 95 ~ and
o Water 95 ~ ~, No 01-1g5 ~ - - 95~ isotherm
0.5 g NaOH/100 g water (conditions c) and 95 ~'C and 1 g
9 CO,Noz 95% 9 60~ ----60~ NaOH/100 g water (conditions d). Using condition a) as a be-
9 C03No2 60% vNGOH 30~ ---%% isolherm sis for comparison, the relative increases when proceeding to
Fig. I. Yieldsof formaldehyde-condensablepolyphenols(Stiasny po- stronger conditions are: 0-11% for b), 14~30% for c) and
lyphenols) obtained when bark samples are treated with alkali 2 1 ~ 1 % for d). The Stiasny polyphenols overall solved frac-
(NaOH or CO3NA2) during ! 5 min under various temperatures and tionratio measures the fraction of extracted products, corre-
concentrations. Each point represents an average obtained from sponding to polyphenols. The average values obtained for
eight bark samples with different origin
Bild 1. Ausbeute an formaldeyhd-kondensierbaren Polyphenolen the six bark lots vary between 0.827 (conditions b) and 0.917
(Stiasny Polyphenole)bei Alkali-Behandlung(NaOH oder CO3Na2) (conditions c). These values are higher than those found in
15 rain, bei unterschiedlichenTemperaturen und Konzentrationen. literature, which is probably due to the short duration of the
Die MeBpunkte sind Mittelwerte aus acht Rindenproben unter- extractions. Under the conditions studied, an increase in the
schiedlicher Herkunft. selectivity of polyphenol extraction can be noticed when the

<j~ ExfroCtS (determination of reducing sugars end glucose)

Acid
Semplel
hydrolysis
~Roffinotes {determinofion of Gold-insoluble residues]

Alkoline [ixivitQlion
Sample 2
(60~ 05 g
NOOH/lOOg wafer)
\ EXtFOCtS[determinotion of Sfiasny polyphenols)
Alkaline iix]vitofion
{600C: 1.0 g
No OH/I00 g water] deterrninotion of overGll fraction solved
Alkaline lixivitation
(95~ 0.5 g c, ~ . ~ . ~ (determination of reducing
NQOH/IO0 g water) /___. . //,,'L,,,,uc.~:~ sugarsend glucose)
/...,,. Roffinotes \ - hA%ti
Y Y
rol
sis- \ ..... - 9 [delerminofion of,.KIoson Ognin
beck lois Somple 5 Alkaline [ixivitetion ~, "-KOflllqOfeS ond unsolved polyfiovonoids")
(A,B,C,O,E,F) (95%; 1.0g
No OH/IOG g water) \~EG~ <..-~"EXtFOCtS(delerminotion of Stiosny polyphenols)
extrocUon ~ " ~ . R o f f i n o t e s
Fig. 2. Diagram of various treatments, performed with homogeneizedbark samples
Bild 2. Schema der verschiedenenBehandlungen der homogenisierten Rindenproben
G. Vfizquez et al.: Operational conditions for alkaline leaching Pinus pinaster bark 417

Table I. Results obtained for the bark samples processed according to Fig. 2

Bark Sample Alkaline lixiviations Acid hydrolysis

lot
T Conc" Stiasny polyphenols Total Reducing Glucose A.I.R. b or
~C fraction sugars K.L.+U.P. c
1 st extn. 2nd extn. dissolved

A 1 - - - 26.6 13.9 63.3

2 60 0.5 23.4 1.1 25.6 24.6 13.0 44.6
3 60 1.0 26.0 ] .3 29.4 25.2 13.3 43.3
4 95 0.5 30.5 2.8 32.1 24.5 12.7 41 .I
5 95 1.0 30.9 2.6 33.0 24.9 12.8 34.1
B 1 . . . . 25.7 13.2 64.3
2 60 0.5 22.3 0.4 25.4 25.4 13.1 42.5
3 6(1 1.0 22.6 0.7 29.1 24.0 12.2 41.3
4 95 0.5 28.1 3.7 30.7 24.3 12.3 39.5
5 95 1.0 31.4 0.2 35.4 25.0 12.6 33.4
C 1 - - - 27.6 13.9 62.7
2 60 0.5 23.3 0.8 27.0 27.0 13.9 43.5
3 60 1.0 23.3 0.8 28.2 27.2 13.9 40.6
4 95 0.5 26.6 3.9 29.2 26.2 13.7 38.5
5 95 1.0 29.0 2.3 34.7 27.5 13.1 32.1
D t - - - 26.1 12.6 65,4
2 60 0.5 24.5 1.6 28.0 24.2 11.7 42.3
3 60 1.0 27.0 1.5 32.9 23.8 I 1.6 37.6
4 95 0.5 31.8 5.5 34.3 24.1 11.9 37.1
5 95 1.0 33.4 5.1 41.0 24.1 12.3 3I .5
E 1 - - 27.5 14.5 65.2
2 60 0.5 25.6 1.1 26.8 25.2 13.8 41.2
3 60 1.0 26.0 0.4 31.7 26.0 13.1 36.4
4 95 0.5 29.7 1.2 33.0 24.9 I4.1 33.5
5 95 1.0 31.1 1.0 37.8 25.0 13.8 30.7
F 1 - - - 27.6 14.0 62.8
2 60 0.5 23.3 0.7 27.0 27.5 13.7 42.8
3 60 1.0 23.7 1.3 28.5 26.1 13.0 40.3
4 95 0.5 29.1 3.5 32.4 26.2 13.1 36.1
5 95 1.0 30.1 3.9 34.8 26.2 12.7 33.2

a Alkali concentration expressed as g NaOH/100g water

All other results are expressed as g/100 g of oven-dried bark
A.I.R.: Acid-insoluble residue (relative to samples not treated with alkali)
c K.L. +U.P.: Klason lignin and unsolved polyflavonoids (relative to samples treated with alkali)

t e m p e r a t u r e is raised. T h e selectivity diminishes with rising
alkali concentration.
The yields o b t a i n e d when coupling in cross-flow a second
extraction stage, performed u n d e r the same conditions as the
first, are within 4 - 1 0 % of the total o f dissolved polyphenols.
Nevertheless, the coupling o f stages would be interesting in
order to obtain b o t h , raffinates with low polyphenol c o n t e n t
(facilitating their acid or enzymatic hydrolysis) as well as
more c o n c e n t r a t e d extracts (Hall 1960).
This m e t h o d is limited by the high viscosity of the con-
centrated extracts (Ayla et al. 1981).
The polysaccharide losses in the solid p h a s e can be seen
from Table 1 which c o m p a r e s the a m o u n t s o f reducing
sugars obtained t h r o u g h bark hydrolysis before and after
alkaline extractions. The values determined are low a n d do
not show a clear dependence on the experimental conditions
(4.5-6.8 g o f c a r b o h y d r a t e s lost/100 g o f initial c a r b o h y -
drates in samples as averages u n d e r the different conditions
studied). These results are below the values ( 1 1 - 5 0 % ) pub-
lished by C h a n g (1955), which seems to be related to the
short d u r a t i o n of alkaline extraction. The values determined
for glucose losses are in good agreement with the results
f o u n d for the total c a r b o h y d r a t e losses.
As an average value the reducing sugars o b t a i n e d by the
acid hydrolysis o f b a r k c o u n t for 27 weight % o f the samples
studied here. W h e n the raffinates o f alkaline lixiviations are
considered, their p r o p o r t i o n s rise to 38~J,3 weight % of the
solid. This is promising for reaching a utilization o f Pinus
pinaster bark.
Table 1 also shows o t h e r interesting facts: the non-reduc-
ing fraction o b t a i n e d t h r o u g h acid hydrolysis ( a b o u t 34 g/
100 g o f reducing c o m p o u n d s ) decreases to 19-23 g o f n o n -
reducing c o m p o u n d s / 1 0 0 g o f reducing c o m p o u n d s , w h e n
the raffinates from alkaline extractions are treated. Thus,
over 1/3 o f undesired impurities are eliminated when the
alkaline t r e a t m e n t is carried out. In order to evaluate the re-
sults, it m a y be t a k e n into a c c o u n t t h a t they are o b t a i n e d
from acid hydrolysis performed u n d e r t i m e - c o n s u m i n g con-
ditions given in literature ( B r o w n i n g 1957). T h e use o f
shorter times, as p u b l i s h e d for o t h e r lignocellulosic residues
(Shah et al. 1984), could diminish the a m o u n t of impurities,
but would also involve a decrease in the yield of polysac-
charide t r a n s f o r m a t i o n into sugars.
T h e extractions carried out at 95 "C with 0.5 or I g
N a O H / 1 0 0 g water (conditions c a n d d) seem to be the m o s t
favourable ones, because they provide extracts with highest
p r o p o r t i o n s o f polysaccharides, w i t h o u t severe losses in car-
bohydrates.
U n d e r the latter two conditions, the effect of particle size,
not considered u p to now, on the kinetics a n d yields o f alka-
418 Holz als Roh- und Werkstoff44 (1986)

Coupling a second lixiviation stage in cross flow, gives no

100 ~ c-
appreciable advantage. Although, this method could be in-
teresting to obtain more concentrated extracts.
80
The carbohydrates lost in the solid phase during alkaline
lixiviation are not important under any of the conditions
f0
studied ( 4 . 5 ~ . 8 % of the initial polysaccbarides present in
40 samples). The sugars obtained through acid hydrolysis of the
raffinates from alkaline lixiviation have less impurities than
c=l
20 those obtained when hydrolysing bark which was not pre-
treated with alkali. These results are favourable for devel-
&
oping an industrial process where polyphenols and polysac-
#
charides from Pinus pinaster bark could be used.
~oo "O
The effect of particle size on the kinetics and on the yields
x Y of alkaline lixiviations was evaluated at 95 ~C with 0.5 or i g
80
NaOH/100 g water. The increase in extraction rate is high
60 POl title sizes for particles smaller than 0.25 mm. With these particles, ex-
o 0-0.25 mm traction percentages of 90% are reached in periods as short
L'O ,~ 0.25-0.50 mm as 8 min.
9 D.50-0.75 mm
20 v O.75-1.0 mm 5 Literature
b
I I ;
2o [o 6o t~o 1oo rain ;20 L,~O Anderson, S. B.; Wu, K. T.: Wong, A. 1974: Utilization of Ponderosa
Time pine bark and its extracts in particleboards. Forest Prod. J.
Fig.& Dependence between extraction percentage and time for dif- 24:48-53
ferent particle sizes, a) NaOH, 0.5 g/100 g water, 95 ~C; b) NaOH, Anderson, A.B. 1977: Bark extracts as bonding agent for particle-
1.0 g/100 g water, 95 ~C board. In: Goldstein, I. S. (Ed.) ACS Syrup. Ser. No. 43, pp. 235
Biid 3. Zusammenhang zwischen Extrakt-Anteilen und Behand- 42 Am. Chem, Soc.
lungszeit fiir untersehiedliche Partikelgr6Ben. a) NaOH, 0,5 g/100 g Ayla, C.: Weissman, G. 1981 : Utilization of polyphenols from Pinus
Wasser, 95 ~C; b) NaOH, 1,0 g/100 g Wasser, 95 ':C brutia bark for the production of wood adhesives, ttolz Roh
Werkstoff 39:91 95
Ayla, C.: Weissman, G. 1982: Gluing tests with tannin formaldehyde
resins from bark extracts of Pinus brutia ten. Holz Roh- Werk-
line extractions was studied using the methods previously
stoff40:] 3 18
described by V/tzquez et al. (1985 b). The initial interval of Browing, B.L.: Sell, L.O. 1957: The analysis of some fractions of
particle size ((~1 mm) was divided into subintervals given in slash pinc bark. TAPP1 40:362-65
Fig. 3, which shows the dependence between extraction per- Chang, Y.P.; Mitchell, R.L. 1955: Chemical composition of com-
centages and time. The increase in the extraction rate is mon North American pulpwood barks. TAPPI 38:315-20
higher.when working with particles smaller than 0.25 ram. Dix, B.; Marutzky, R. I983: On the extraction of polyphenols fi'orn
Using this bark fraction, the highest proportions of Stiasny softwood barks. Holz Roh- Werkstoff 41:45-50
polyphenols are obtained (41.5--49.4% against 27.9-39.5%, Hall, R. B.; Leonard, J.H.; Nicholls, G.A. 1960: Bonding particle-
values determined, using particles greater than 0.25 mm). boards with bark extracts. Forest Prod. J. 10:263-72
Hemingway, R.W. 1978: Adhesives from southern pine bark. A re-
This increae was already reported for extractions of Pinus
view of past and current approaches to resin formulation prob-
radiata bark (Hall et al. 1960). lems. In: McMillin, C.W. (Ed.): Complete tree utilizalion of
The final choice of the optimum conditions among those southern pine. Proc. Syrup., pp.443 57. Medison: Forest Prod.
studied here must be based on economic factors, and has to Res. Soc.
include aspects such as the technological characteristics of Shah, R. B." Clausen, E. C.; Gaddy, J. L 1984: Production of chemi-
the adhesives produced with bark extract and the facility of cal feedstocks from biomass. Chem. Eng. Prog. lr:76-80
obtaining and fermenting sugars from the polysaccharides Somogyi, M. 1952: Notes on sugar determination. J. Biol. Chem.
present in the raffinates. 195:19-23
VAzquez, G.; Antorrcna, G.; Paraj6, J.C. 1985a. Studies on the
utilization of Pinus pinaster bark. I. Chemical constituents.
Wood Sci. Technol. (accepted for publication)
4 Conclusions Vfizquez, G.; Antorrena, G.; Paraj6, J. C. 1985 b: Studies on the uti-
lization of Pinus pinaster bark. II. Kinetics and yields of alkaline
F r o m the alkaline extraction of Pinus pinaster bark four lixiviations. Wood Sci. Technol. (accepted for publication)
experimental conditions that allow the achievement of the Weissman, G.; Ayla, C. 1980a: Utilization of natural polyphenols
highest amounts of formaldehyde-condensable polyphenols for the production of wood adhesives. Holz Roh Werkstoff
(roughly 26-31 weight percent of the initial oven-dried 38:245-49
samples) were selected for a more detailed study. U n d e r those Weissman, G.; Ayla, C. 1980 b: Investigation ofextractives of Pinus
brutia bark. Holz Roh- Werkstoff 38:307-12
experimental conditions (alkali, N a O H ; concentration 0.5
Wissing, A. 1955. The utilization of bark. II. investigation of the
or 1 g/100 g water, 60 ~ or 95 ~>C, 15 min) the yields of poly- Stiasny reaction for the precipitation ofpolyphenols in pine bark
phenols from two stages coupled in cross flow as well as the extractives Svensk. Papperstidn. 20:745-50.
losses of carbohydrates from the solid phase were studied Yazaki, Y.; Hillis, W.E. 1977: Polyphenolic extractives of Pinus
using homogenized bark samples. radiata bark. Holzforschung 31:20-25