Chemical composition and pulping of date palm rachis and Posidonia oceanica A

comparison with other wood and non-wood bre sources

R. Khiari
a,b
, M.F. Mhenni
a
, M.N. Belgacem
b,
*
, E. Mauret
b
a
Research Unity of Applied Chemistry and Environment, Department of Chemistry, Faculty of Sciences, Monastir 5019, Tunisia
b
Laboratoire de Gnie des Procds Papetiers UMR CNRS 5518, Grenoble INP-Pagora, B.P. 65, 38402 Saint Martin dHres Cedex, France
a r t i c l e i n f o
Article history:
Received 29 June 2009
Received in revised form 20 August 2009
Accepted 21 August 2009
Available online 18 September 2009
Keywords:
Date palm rachis
Posidonia oceanica
Chemical composition
Pulping
Fibre properties
a b s t r a c t
In the present paper, the valorisation of two residues: Posidonia oceanica and date palm rachis was inves-
tigated. First, their chemical composition was studied and showed that they present amounts of holocel-
lulose, lignin and cellulose similar to those encountered in softwood and hardwood. Extractives in
different solvents and ash contents are relatively high. Moreover, ash composition assessment showed
that silicon is the major component (17.7%) for P. oceanica. The high ash quantity and the low DP (about
370) may be considered as serious disadvantages of P. oceanica, in the pulping and papermaking context.
Oppositely, the properties of rachis date palm and those of the ensuing pulp, obtained from a classical
soda-anthraquinone cooking, demonstrated the suitability of this agricultural by-product for papermak-
ing. Preliminary tests conducted on unrened pulp suspensions and handsheets from date palm rachis in
terms of freeness, Water Retention Value and mechanical properties allowed conrming the good quality
of date palm rachis bres.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Paper consumption is continuously increasing in the world even
in countries where wood resources are very limited. Furthermore,
the valorisation of agricultural residues or marine biomass through
rational and innovative ways of utilization is of potential interest,
in such countries, since they can be considered as new cellulosic -
bre sources. Such strategies were already applied to valorize vari-
ous agricultural crops available for instance in Portugal (Antunes
et al., 2000; Cordeiro et al., 2004), India (Dutt et al., 2008), Malaysia
(Wan Rosli et al., 2003), Iran (Hedjazi et al., 2008), Sudan (Khristova
et al., 2005) or Tunisia (Aguir and Mhenni, 2006; Gezguez et al.,
2009). In this work, we investigated the valorisation of two
lignocellulosic materials, largely available in Tunisia, as a source
of cellulosic bres, namely: Posidonia oceanica balls and date palm
rachis.
P. oceanica is the dominant sea grass in the Mediterranean Sea.
Important quantities of P. oceanica fragments accumulated on
Tunisian coasts, which imposes the cleaning of the beaches every
summer. The valorisation of this available and renewable lignocel-
lulosic biomass can be considered as a suitable solution for this
problem. Nowadays, P. oceanica is studied as a low cost and renew-
able adsorbent for removing dyes or phenol (Ncibi et al., 2006,
2008; Gezguez et al., 2009) or as a source of cellulose (Aguir and
Mhenni, 2006). In that case, P. oceanica is treated in order to ex-
tract cellulose and convert it into carboxymethyl cellulose. To the
best of our knowledge, no complete data about the chemical com-
position of P. oceanica are available in the literature. Moreover, its
potential use as a source of lignocellulosic bres for the production
of pulp and paper has never been tested.
Date palm (Phoenix dactylifera) is one of the most cultivated
palms in the arid and semi-arid regions of the world. Tunisia has
more than 4 millions date palms which occupy 32,000 ha (statis-
tics from the Tunisian Ministry of Agriculture, 2003). After the date
fruit harvesting, important quantities of date palm rachis wastes
accumulated every year in Tunisian agricultural lands. Here also,
rational ways of valorising this abundant renewable resource
should be nd. For instance, it is well known that the use of natu-
ral bres in composites is a way of meeting the increasing demand
in biodegradable and renewable materials. In this context, date
palms agricultural residues (rachis or leaves) can be viewed as
sources of reinforcing bres for polymeric matrices in composite
materials. Such way of valorisation has been recently undertaken
(Al-Sulaiman, 2002; Abou-Shark and Hamid, 2004; Taha et al.,
2007; Bendahou et al., 2008; Sbiai et al., 2008). Oppositely, only
few studies evaluated the potential use of date palm by-products
for pulp and paper manufacturing and most of them are dedicated
to the pulping of date palm leaves (Ezzat, 1974; El Morsy, 1980; El
Morsy et al., 1981). To the best of our knowledge, only Khristova
et al. (2005) compared pulps produced from rachises and leaves.
0960-8524/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.08.079
* Corresponding author. Tel.: +33 04 76 82 69 62; fax: +33 04 76 82 69 33.
E-mail address: naceur.belgacem@efpg.inpg.fr (M.N. Belgacem).
Bioresource Technology 101 (2010) 775780
Contents lists available at ScienceDirect
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j our nal homepage: www. el sevi er . com/ l ocat e/ bi or t ech
Thus, the main objectives of this paper are the characterization
of these two Tunisian cellulosic by-products (P. oceanica balls and
date palm rachis) and the evaluation of their properties, in the
papermaking context. The rst part of this work is devoted to the
determination of the chemical composition. Then, soda-anthraqui-
none cooking, which is considered as the most suitable process for
pulping annual plants (Antunes et al., 2000), is tested. The ensuing
pulps are characterised in terms of yield, kappa number, degree of
polymerisation (DP) and chemical composition (residual lignin,
holocellulose, cellulose and extractives). Finally, the physical and
mechanical properties of handsheets are presented and discussed.
The obtained results (chemical composition of pulps and physical
properties of papers) are compared to other wood and non-wood
sources thanks to a complete literature review.
2. Materials
2.1. Raw materials
P. oceanica balls and date palm rachis used in this study were
collected in Monastir in August 2007. These wastes were dried un-
der natural conditions during September 2007 (average relative
humidity = 65%; average temperature = 25 C). The date palm ra-
chises of about 1 m length and 67 cm diameter were then cut into
13 cm pieces before pulping. The P. oceanica balls were washed in
order to eliminate sand and contaminants and then dried again un-
der the same conditions.
2.2. Characterization of raw materials
Chemical composition of P. oceanica balls and date palm rachis
was determined. The evaluation of extractive substances was car-
ried out in different liquids according to common standards,
namely: cold and hot water (T207 cm-08), 1% sodium hydroxide
solution (T212 om-07) and ethanoltoluene (T204 cm-07). Ash
content (T211 om-07) was determined and analysis of the mineral
fraction was performed at the Service Central dAnalyse Vernai-
son (CNRS). The amounts of lignin, holocellulose, cellulose, as well
as the kappa number were also assessed by using the following
respective standard methods: T222 om-06, method of Wise et al.
(1946), T203 cm-99 and T236 om-06. As recommended by the var-
ious standards used, all the experiments were duplicated and the
difference between the two values was within an experimental er-
ror of 5%.
2.3. Pulping
The delignication of date palm rachis was carried out accord-
ing to the procedure described by Khristova et al. (2005) with a to-
tal alkali charge of 20% expressed in NaOH (based on w/w o.d.
rachis), an anthraquinone concentration of 0.1% (w/w with respect
to o.d. material) and a cooking time at constant temperature of
120 min. The liquor to solid ratio was changed and xed at 10
due to the experimental device used and different temperatures
ranging from 150 to 170 C were tested. All the experiments were
conducted in a 1 L reactor, in which the heating time to reach the
constant temperature was 1 h. The same procedure was applied to
P. oceanica balls.
2.4. Pulp and paper characterization
After cooking, the obtained pulps were washed several times
through a wire until obtaining a clear ltrate and characterised
in terms of yield, kappa number, residual lignin, holocellulose
and ethanoltoluene extractives. The cooking yield was calculated
as the ratio of the weight of o.d. material after washing to that of
initial raw material. The residual lignin was determined from both
the Klason lignin and the soluble lignin measured by UV absorption
of a ltrate specimen at 205 nm (Tappi method UM 250). The vis-
cosity of pulp (g in mPa s) dissolved in a cupriethylene-diamine
solution was determined according to Tappi standard (T230 om-
99). These values were then converted into degrees of polymerisa-
tion (DP) thanks to the following relation proposed by Sihtola et al.
(1963):
DP 0:75954Log
10
g 325
1:105
1
All the experiments were duplicated and the difference between the
two values was within an experimental error of 5%.
After disintegration (standard method ISO 5263-1), the pulp
were passed through a slotted screen of 0.15 mm aperture size,
in order to remove uncooked materials. The screening yields were
determined as the ratio between the weights of o.d. material before
and after screening. Morphological properties of the bres were
studied by SEM observations (results not shown) and by using a
MORFI analyzer (Techpap): the main bre parameters were as-
sessed by image analysis of a diluted suspension owing in a trans-
parent at channel observed by a CCD video-camera. Water
Retention Values (WRV) were also determined by centrifugation
of wet pulp samples during 15 min at 3000g according to Silvys
method (Silvy et al., 1968). The samples were weighted, before
and after drying, and the WRV calculated. The pulp drainability
was evaluated by measuring the Shopper Riegler degree (SR
ISO 5267-1). The unbeaten screened pulps suspensions were di-
luted to 2 g L
1
. Then, conventional handsheets with a basis weight
of 60 g/m
2
were prepared on a Rapid Khten sheet former follow-
ing the standard method IS0 5269-2. Prior to testing, the hand-
sheets were conditioned (23 C, 50% relative humidity ISO 187)
and structural and mechanical properties were determined by
measuring basis weight, thickness, bulk and permeability, as well
as the tensile, burst and tear strength according to standards ISO
536, ISO 534, ISO 5636-3, ISO 1924-3, ISO 2758 and ISO 1974. As
recommended by the various standards used, all the measure-
ments were made 10 times, thus allowing the determination of
standard deviation. Paper thickness was measured 20 times.
3. Results and discussion
3.1. Characterization of the raw material
The chemical composition of P. oceanica and date palm rachis
are listed in Table 1, which shows that these raw materials are
characterised by relatively high amounts of extractives, especially
for ethanoltoluene extractives (10.7% and 6.3% for Posidonia and
date palm rachis, respectively). The main difference between Posi-
donia and date palm rachis is related to ash content, which is high-
er for Posidonia (12%) compared to that of date palm rachis (5%).
Cellulose content is similar for both raw materials studied (40%
for Posidonia and 45% for date palm rachis). For date palm rachis,
chemical compositions from other works are also reported in Table
1, which shows that, when available, data are relatively close to our
results apart fromthe content in lignin (Bendahou et al., 2007). Dif-
ferences may be related to climate conditions, soil chemical com-
position. . . Finally, it is worth noting that date palm rachis
contains higher amount of cellulose than leaves, as it can be ob-
served in Table 1; it implies that using rachis instead of leaves
would be more protable for papermaking applications.
Table 2 summarizes chemical compositions collected from liter-
ature for various cellulosic biomasses such as hardwood and soft-
wood, agricultural residues and other various non-wood sources.
The comparison with the present work leads to several comments
776 R. Khiari et al. / Bioresource Technology 101 (2010) 775780
concerning the amount of extractives. Thus, in cold and hot water,
the quantity of extractives for bothP. oceanica and date palm rachis
are higher than those found in hardwood and softwood but compa-
rable to the amounts usually encountered in non-wood sources.
The 1% NaOH extractives (16.5% for P. oceanica and 20.8% for date
palm rachis) are similar to those of wood sources, i.e. less than 20%,
but are lower than those of annual plants. Finally, the amount of
extractives in ethanoltoluene for the raw materials under investi-
gation is relatively high, although in the same order of magnitude
as those observed for other annual plants or agricultural crops.
Considering the structural components, Klason lignin for both
materials studied was also found to be quite high ( P. oceanica:
29%; date palm rachis: 27%), when compared to typical amounts
encountered in annual plants, non-wood and hardwood sources
which are close to 20%. Lignin content of these two materials is
then close to that of softwood. In the same way, the amounts of
holocellulose and cellulose for the two raw materials were similar
to those found in wood and non-wood plants. These important
fractions allow envisaging the valorisation of such crops as cellu-
lose derivatives and/or as lignocellulosic bres for bre-reinforced
composite materials or papermaking applications like in the cur-
rent study.
Concerning now the ash content, it is high for P. oceanica (12%)
and comparable to that of rice dishes, Banana pseudo-stems and
Amaranth which exhibit the greatest contents, as already reported
in the literature (see Table 2). This can be attributed to the
Table 1
Chemical composition of Posidonia oceanica balls and date palm rachises and leaves comparison with data collected from previously published studies.
Amounts in % (w/w with
respect to oven dried
raw material) (%)
Posidonia oceanica balls Date palm rachis Date palm leaves
This work This work Khristova
et al. (2005)
Bendahou
et al. (2007)
El Morsy (1980) Khristova
et al. (2005)
Bendahou
et al. (2007)
Ezzat (1974)
Cold water extractives 7.3 5.0 n.d. n.d. n.d. n.d. n.d. n.d.
Hot water extractives 12.2 8.1 8.7 n.d. n.d. 10.8 n.d. n.d.
1% NaOH extractives 16.5 20.8 25.6 n.d. n.d. 29.9 n.d. n.d.
Ethanoltoluene extractives 10.7 6.3 12.8
a
4 n.d. 11.7
a
3 5.9
b
Ash 12 5 5.6 2.5 3.4 9.6 6.5 3.9
Lignin 29.8
c
27.2
c
23.8
d
14 25.8 31.2
d
27 n.d.
Holocellulose 61.8 74.8 n.d. 72 n.d. n.d. 59.5 n.d.
Cellulose 40 45 43.1 44 n.d. 30.3 33.5 n.d.
a
In ethanolcyclohexane.
b
In alcoholbenzene.
c
Klason lignin.
d
Residual lignin (Klason and soluble lignin).
Table 2
Chemical composition of some lignocellulosic plants.
Reference C.W. H.W. A.B. 1% NaOH Ash Hol. Lign. Hemi. Cell.
Wood
Brutia pine Copur and Tozluoglu (2008) 2.2 2.8 1.94 16.1 0.4 75.5 26.1 28.5 47
Pine pinaster
b
Jimenez and Lopez (1990) and
Jimenez et al. (2008)
n.d. 2 12.6 7.910.3 0.30.5 6967 2628 13. 7 56
Eucalyptus globulus
b
Jimenez and Lopez (1990) and
Jimenez et al. (2008)
n.d. 2.8 1.15 12.42 0.6 80.5 19.9 27.7 53
Olive wood
a
Jimenez and Lopez (1990) and
Jimenez et al. (1992, 2008)
15.5 17 10.4 30.0 1.4 65.83 15.64 24.33 41.5
Holm Oak (Quercus ilex) Eugenio et al. (2006) n.d. n.d. n.d. n.d. n.d. 71.2 16.3 28.3 43
Non-wood
Prosopis alba Jimenez et al. (2008) n.d. 4.7 4.65 20.8 n.d. 63.6 19.3 22.0 42
Chamaecytisus Jimenez et al. (2008) n.d. 3 3.43 16.1 n.d. 75.3 14.8 31.7 44
Phragmites Jimenez et al. (2008) n.d. 5.4 6.36 34.7 n.d. 64.1 23.6 24.4 40
Retama monosperma Jimenez et al. (2008) n.d. 3.8 5.03 16.9 n.d. 71.7 21.5 29.0 43
Arundo donax Shatalov et al. (2001) n.d. 6.7 9.2 n.d. 4.8 61.2 20.9 32.1 29.2
Banana pseudo-stems Cordeiro et al. (2004) n.d. 5.4 2.7 n.d. 14 65.2 12.7 25.2 40
Paulownia fortuna Jimenez et al. (1993, 2008) n.d. 9.6 5.5 31.5 n.d. 70.7 22.4 33.3 37
Annual and perennial plants
Wheat straw Schott (2000) 5.811 14 4.69.2 4142.8 49 n.d. 1121 2128.5 3345.5
Rice dishes Alcaide et al. (1990) 10.6 13 4.65.7 49.1 1320 n.d. 1113.5 1326.2 4249.8
Barley fodder Alcaide et al. (1990) 16 16 4.7 47 4.97 n.d. 718 24.5 3448
Rye straw Alcaide et al. (1990) 8.4 9.4 3.25.2 37.4 44.3 n.d. 18.519 2330.5 55
Oat straw Alcaide et al. (1990) 13.2 15 4.4 41.8 77.5 n.d. 1119.6 1627 3753.6
Sorghum stalks Jimenez et al. (1993) n.d. 21.7 7.99 41.6 4.85 71.7 13.4 29.3 42
Amaranth Fiserova et al. (2006) 23.5 28 2.51 46.8 12 58.4 13.2 26.1 32
Orache Fiserova et al. (2006) 4.6 6.5 1.87 27.5 2 74.9 19.5 38.8 36
Jerusalem artichoke Fiserova et al. (2006) 26.6 31 2.86 48.5 3 51.6 14.7 23.1 29
Cynara cardunculus L.
a
Antunes et al. (2000) and Gominho
et al. (2001)
n.d. 10 6 n.d. 8 64 20 26 38
Miscanthus sinensis Barba et al. (2002) n.d. 9.1 3.1 n.d. 0.7 72.5 19.9 30.3 42
Kenaf (Hibiscus cannabinus) Manfred (1993) n.d. n.d. n.d. n.d. 1.75 n.d. 14.518.7 n.d. 3139
C.W.: cold water solubility; H.W.: hot water solubility; A.B.: solubility in various organic solvents; 1% NaOH: 1% sodium hydroxide solubility; Hol.: holocellulose; Lign.: Klason
lignin (%); Hemi.: hemicellulose; Cell.: cellulose.
a
Average of 2 or 3 varieties.
b
Average of 11 varieties.
R. Khiari et al. / Bioresource Technology 101 (2010) 775780 777
chemical composition of the marine environment in which the
plants are growing or/and to a pollution of the balls by sand, even
if intensive washing was performed before analyses. On the oppo-
site, ash content in date palm rachis (5%) is lower but remains at
the same order of magnitude as most of the non-wood plants. Con-
sidering the important quantity of ashes for these two raw materi-
als, their chemical composition was determined. The results are
summarized in Table 3 in which literature data are also reported,
for comparison. For date palm rachis, ashes are mainly constituted
by Ca, Cl, K, Cl and Na atoms. The absolute amount of silicon is very
low (0.14% w/w on o.d. raw material) and similar to those reported
by Khristova et al. (2005) for both date palm rachises and leaves
(0.06% and 0.56%, respectively). In this case, the high quantity of
ashes cannot be considered as problematic, in the context of pul-
ping and papermaking processes, since the silicon-based salts are
negligible. Oppositely, silicon is predominant in P. oceanica (abso-
lute content of 2.1% w/w on o.d. raw material). This important
amount will negatively impact the chemical recovery process
and, therefore, could constitute a serious drawback, if considering
the valorisation of this marine plant in papermaking stream. Nev-
ertheless, it must be kept in mind that a possible pollution by sand
could be responsible. To conclude, comparison with other plants
(Amaranth and Banana pseudo-stems) shows that chemical com-
position of ashes may considerably vary from one species to an-
other, as shown in Table 3.
3.2. Pulping pulp and paper characterization
3.2.1. Chemical composition of pulps extracted from date palm rachis
and P. oceanica
Soda-anthraquinone cookings of P. oceanica and date palm ra-
chis were conducted. The experimental conditions as well as the
composition of the ensuing pulps were listed in Table 4. Whatever
the raw material, a decrease of cooking yield, extractives, lignin
content, kappa number and viscosity occurred, when the cooking
temperature increases from 150 to 170 C. Oppositely, an increase
of the relative content in holocellulose is observed. Regarding the
ash contents, they are surprisingly unaffected by the pulping oper-
ation. This behaviour has to be taken into account since the per-
centage of silicon in P. oceanica is dramatically high. Analysing
more deeply the results, it appears that delignication is more pro-
nounced for date palm rachis with a mean cooking yield of 44%
compared to 63% for Posidonia, a mean relative content in lignin
of 4% compared to 9% for Posidonia and a mean Kappa number of
47 compared to 63 for Posidonia. Nevertheless, it is difcult to com-
pare the contents in lignin and holocellulose as the sum of compo-
nents (ash, lignin, holocellulose) reaches about 93% for P. oceanica
pulp and only 80% for date palm rachis pulps. This indicates that
some constituents of the pulp are lost during the analysis. This
trend is also observed for the majority of the non-wood plants,
as presented in Table 2. Thus, the total amounts of all the compo-
nents is generally comprised between 80% and 95%. This behaviour
is probably due to the fact that standard methods designed for
wood plants are used without modication for the determination
of chemical composition of non-wood or annual plants. Finally,
the DP of the unbleached pulps from date palm rachis is around
1200, which is similar to values obtained for unbleached Kraft
wood bres (generally about 13001500). The lower value of DP
for P. oceanica pulp (around 500) probably indicates the lower
strength properties of this material. Table 4 also includes the main
results taken from previously published works for pulp of date
palm. It clearly appears that, when pulping conditions are close,
pulp characteristics are similar: there is a good agreement between
our experimental values and those arising from the literature, par-
ticularly those of Khristova et al. (2005). Cooking conditions used
by El Morsy et al. (1981) seem to be not optimised: even if appar-
ent mild conditions of cooking are applied, the ensuing DP is sur-
prisingly low. Finally, the better quality of rachis over leaves is
once again demonstrated by comparing yields and viscosity of
the pulps obtained from these two raw materials. Thus, apart from
the ash content and the DP of P. oceanica pulp, the characteristics of
the studied bres, in terms of cooking yield and Kappa number are
close to those obtained from unbleached kraft pulping of softwood
and hardwood. Their pulping yield is even better than that ob-
served for annual plants and agricultural crops, generally around
35% (Alcaide et al., 1990; Jimenez and Lopez, 1990; Jimenez
et al., 1993, 2008; Schott, 2000; Fiserova et al., 2006).
3.2.2. Physical properties of pulp and paper from date palm rachis and
P. oceanica
Pulps of P. oceanica and date palm rachis were then character-
ised in terms of physical properties and used for making conven-
tional handsheets. Unrened pulps will be considered in this part
whereas the effect of rening on pulps and papers will be reported
in a next publication. From SEM photographs observations, it ap-
pears that the length of P. oceanica bres is signicantly lower than
that obtained from date palm rachis. This observation is conrmed
by morphological measurements collected in Table 5.
Whereas the bre width is roughly the same for the two raw
materials studied, the bre length of date palm rachis pulp is
approximately 60% higher than that of the corresponding bres ex-
tracted from Posidonia. Thus, the aspect ratio (length to diameter
ratio) is equal to 40 for date palm rachis bres and reaches only
25 for Posidonia bres, which is rather low. For comparison, the
length of softwood and hardwood bres is 23 mm and 12 mm,
respectively and the corresponding aspect ratios are around 100
Table 3
Ash composition for Posidonia oceanica and date palm rachis (in % w/w with respect to oven dried raw material). Comparison with data taken from previously published studies.
% Posidonia oceanica balls Date palm rachis Date palm leaves Amaranth Banana pseudo-stems
This work This work Khristova et al. (2005) Khristova et al. (2005) Fiserova et al. (2006) Cordeiro et al. (2004)
Si 17.7 2.8 1.1 5.8 0.25 2.7
Ca 9.12 21.5 n.d. n.d. 4.17 7.5
Mg 3.89 3.53 n.d. n.d. 0.035 4.3
Fe 3.78 240 ppm n.d. n.d. n.d. n.d.
Cu <100 ppm 360 ppm n.d. n.d. 0.01 n.d.
K 2.04 10.2 n.d. n.d. 36.67 33.4
P 0.12 0.7 n.d. n.d. n.d. 2.2
S 1.92 1.69 n.d. n.d. n.d. n.d.
C <0.3 1.5 n.d. n.d. n.d. n.d.
Cl 0.72 18.6 n.d. n.d. n.d. n.d.
Na 2.49 6.79 n.d. n.d. n.d. n.d.
Absolute silicon contents in raw materials
Si 2.13 0.14 0.06 0.56 0.03 0.38
778 R. Khiari et al. / Bioresource Technology 101 (2010) 775780
and 60. Then, date palm rachis bres present length to diameter ra-
tio comparable to that of certain hardwood pulps. Date palm rachis
pulp is also characterised by a great content of nes (30% in length)
compared to Posidonia pulp for which it is much lower (around 7%).
Finally, Water Retention Value (WRV) of date palm rachis pulp is
more important than that of Posidonia counterpart (see Table 5).
We can note that WRV for date palm rachis (138%) is signicantly
higher than that of unrened pulps arising from softwood and
hardwood (90100%). This property allows predicting a high level
of exibility of the bres and consequently good mechanical prop-
erties of the ensuing paper. Drainability of both pulps is similar to
that of unrened softwood brous suspensions and better than
that of other non-wood sources and plants like Cynara cardunlus
L. (Antunes et al., 2000; Gominho et al., 2001) or hemp and bamboo
(Khristova et al., 2005). P. oceanica pulp exhibits very high draina-
bility (10 SR), which is probably related to its low content in ne
elements. Concerning the date palm rachis pulp, combination of a
good drainability with a high WRV is surprising and difcult to
understand especially since morphological properties of the pulp
show a high content of ne elements. Unfortunately, no data are
available in the literature for a better understanding of such behav-
iour. Ezzat (1974) obtained a pulp with a Schopper Riegler degree
of 18.5, but the pulping conditions do not allow comparing the re-
sults. Only Khristova et al. (2005) produced a pulp in similar exper-
imental conditions of cooking which exhibits a Schopper Riegler
degree of 15; no further characterization was done apart from an
estimation of the morphological properties of the bres through
microscopic analysis. Nevertheless, it conrms the high drainabil-
ity of this pulp.
Pulps were then used for making handsheets. First, it is worth
noting that it was not possible to produce paper from P. oceanica
pulps as the strength of the wet web was dramatically low and
impeeded to undergo the ensuing operations of pressing and dry-
ing. This can be due to the low DP previously mentioned but also
to the morphological characteristics of the bres reported in Table
5 and especially the very low aspect ratio of the bres. Thus, no fur-
ther investigation was conducted with this raw material alone. The
valorisation of this marine biomass in papermaking eld may be
considered by blending it with other pulps, for example or by test-
ing the leaves instead of the balls. However, paper sheets from date
palm rachis based papers were made and their physical properties
are reported in Table 6. The obtained data shows that this raw
material could be considered as a promising raw material for
papermaking applications. Considering the structural paper
Table 4
Pulping conditions and chemical composition of unbleached pulps from Posidonia oceanica and date palm rachis or leaves.
Date palm rachis Posidonia oceanica Date palm rachis Date palm leaves
This work Khristova
et al. (2005)
El Morsy
(1980)
El Morsy et al.
(1981)
Khristova
et al. (2005)
El Morsy et al.
(1981)
Ezzat
(1974)
Total alkali charge expressed
in NaOH, %
a
20 20 23 12 15 13 20 12 18
c
Anthraquinone
concentration
0.1 0.1 0 0 0.1 0 0
Time at constant
temperature, min
120 120 120 20 120 20 300
Temperature, C 150 160 170 150 160 170 165170 100 150 165 150 150
Cooking yield, %
a
46.8 44.8 41.8 66.0 63.6 59.9 44.2 42.3 78.5 58.5 39.7 29.5 22.6 38.5
Screening yield, %
a
94 96 43.1 42 n.d. n.d. 39.7 28.2 n.d. n.d.
Ethanoltoluene extractives,
%
b
n.d. 1.81 0.91 n.d. 0.57 0.26 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Ash, %
b
4 12 n.d. n.d. 2.2 1.8 n.d. n.d. 3.6 6.15
Holocellulose, %
b
n.d. 69.3 75.2 n.d. 71.4 72.4 n.d. n.d. n.d. n.d. n.d n.d. n.d. n.d.
Lignin, %
b
n.d. 5.2 3.4 n.d. 9.1 8.5 n.d. n.d. 22.2 6.3 n.d. n.d. 10.8 2.2
Kappa-number 59 54 47 75 65 63 25.5 20.7 n.d. n.d. 50 20.9 n.d. n.d.
Pulp viscosity (mPa s) or
(mL g
1
)
n.d. 15.7
d
15.3
d
n.d. 5.4
d
n.d. 937
e
845
e
n.d. n.d. 618
e
780
e
n.d. n.d.
DP (pulp) n.d. 1203 1188 n.d. 513 n.d. 1403 1252 n.d. 880 886 1146 510 n.d.
a
w/w With respect to oven dried raw material.
b
w/w With respect to oven dried pulps.
c
Suldity 25%.
d
Pulp viscosity in mPa s.
e
Pulp viscosity in mL g
1
.
Table 6
Paper properties made from date palm rachis (average values and standard deviation)
comparison with data by Khristova et al. (2005).
This work Khristova et al. (2005)
Shopper Riegler degree (SR) 14 15.5
Basis weight (g/m
2
) 63.9 1.9 n.d.
Thickness (lm) 141 6 n.d.
Bulk (cm
3
/g) 2.21 n.d.
Permeabilty (cm
3
/s Pa m
2
) 450 0.042 n.d.
Breaking length (km) 3.13 0.23 4.40
Elongation (%) 1.09 0.09 n.d.
Specic energy (mJ/g) 221 37 n.d.
Young modulus (GPa) 2.51 0.14 n.d.
Burst index (kPa m
2
/g) 1.32 0.05 1.9
Tear index (mN m
2
/g) 4.4 0.37 10
Dry zero-span breaking length (km) 13.4 0.91 n.d.
Wet zero-span breaking length (km) 10.8 0.66 n.d.
Internal bond strength (J/m
2
) 94 8.8 n.d.
Short-Span Compression Test (kN/m) 1.32 0.13 n.d.
Table 5
Main properties of the pulps of Posidonia oceanica and date palm rachis (average of
three experimental data).
Date palm
rachis
Posidonia
oceanica
Shopper Riegler
degree (SR)
14 10
Fibre
morphology
Fibre length
a
(mm) 0.89 0.55
Fibre width (lm) 22.3 21.3
Fine elements (% in length) 30.8 7.5
WRV % (w/w on o.d. pulp) 138 110
a
Weighted mean.
R. Khiari et al. / Bioresource Technology 101 (2010) 775780 779
properties, it appears that the bulk is high but this property may
partially result froman overestimation of the thickness of the sheet
due to the presence of impurities not fully eliminated by the
screening operation. The permeability is also high despite the pres-
ence of ne elements in the pulp. All the mechanical properties
tested exhibit very good values for an unrened pulp: breaking
length (km), elongation (%), specic energy (mJ/g), Young modulus
(GPa), burst index (kPa m
2
/g), tear index (mN m
2
/g). The intrinsic
strength of the bres (zero-span breaking length wet) is about
10 km which is quite signicant and witnesses about the appropri-
ate conditions of cooking. No comparison with data arising from
the literature may be done as the previously published works did
not describe the properties of unrened pulps apart from a partial
characterization conducted by Khristova et al. (2005), which con-
rmed the good quality of date palm rachis based papers (see Table
6).
4. Conclusions
The chemical composition of two alternative sources of bres
was established. The obtained results showed that the two raw
materials studied contain high amount of cellulose which justies
their valorisation in cellulose derivatives or as a source of bres for
cellulose bres-reinforced composites or in papermaking applica-
tions. Thus, several chemical pulps were prepared and character-
ised, in terms of yields and morphology. Pulps from date palm
rachis gave paper sheets with good properties, without the need
of rening operations. This feature can be considered as a serious
advantage when looking for new alternative sources of bres for
papermaking.
Acknowledgements
The authors would express sincere thanks to IFC, Institut de
Coopration Francais de lambassade de France en Tunisie and
MIRA, Mobilit Internationale du rgion Rhne-Alpes for its
nancial support.
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