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 Bioresource Technology 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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