Journal of Chemical Technology and Biotechnology

J Chem Technol Biotechnol 81:196200 (2006) DOI: 10.1002/jctb.1383

Kraft pulping of Drimys winteri wood chips biotreated with Ganoderma australe
Heriberto Franco, Juanita Freer, Jaime Rodrguez, Jaime Baeza, Juan Pedro Elissetche and Regis Mendonca
Laboratorio de Recursos Renovables, Universidad de Concepcion, Casilla 160-C, Concepcion, Chile

Abstract: Drimys winteri, a native hardwood from Chile, presents some interesting characteristics that make it suitable for the pulp and paper industry. In this work, the potential of D winteri for the conventional kraft and biokraft pulp production was evaluated. For biokraft pulping, wood chips were biotreated with the white-rot fungus Ganoderma australe. During the biotreatment, a selective pattern of biodelignication was observed and the wood chips biotreated for 15, 30 and 45 days were submitted to kraft cooking. At low cooking severity (H-factor below 1500 h1 , 15% active alkali and 25% suldity), all biopulps presented lower kappa numbers than control pulps and approximately the same screened pulp yield. Biopulps were easily rened in a PFI mill, requiring less PFI revolutions to achieve the same brillation degree. The strength properties of the biopulps were similar to those of the control pulps. 2005 Society of Chemical Industry

Keywords: wood biodegradation; biopulping; kraft pulping; Drimys winteri; Ganoderma australe INTRODUCTION Drimys winteri is a native hardwood species widely distributed in Chile. In the dry regions of Chile, it grows as a bush with a height of 35 m; in the rainy, cold, southern region, it grows as a tree with heights up to 30 m and the estimated volumetric productivity is similar to that of Pinus radiata (2025 m3 ha1 yr1 ), the main species used for cellulose production in Chile.1 Its chemical composition and anatomical characteristics make D winteri a transition species between hardwoods and softwoods. The tree is able to produce owers and fruits as an angiosperm, but the ber length (1.54.3 mm), low density (0.380.50 g cm3 ) and lignin content (2831%) are characteristic of gymnosperms.2 Some exploratory studies had demonstrated that D winteri produces kraft pulps with strength properties similar to those prepared from P radiata.1,2 A biotechnological process, known as biopulping, could further increase kraft pulp quality.3,4 A logical choice for biopulping of D winteri is Ganoderma australe, which is a white-rot fungus responsible for a eld decomposition process that results in a biodelignied material know as palo podrido.5,6 Previous work carried out on the biodegradation of D winteri and N dombeyi by G australe for periods of 39 weeks had shown that, despite an increase in the brightness of the decayed wood chips, no extensive biodelignication was observed in the decay period studied.7 However, it has been extensively reported that the amount of lignin removal during fungal pretreatment is not related either to energy savings in biothermomechanical pulping8 or to the increase in delignication rates observed in chemical pulping processes.4,9,10 The most important aspect of the biodegradation process is the modication of native lignin in wood by the white-rot fungi and also extractives removal, which facilitates the subsequent pulping process. The aim of this work was to evaluate the biotreatment of D winteri wood chips with G australe for kraft pulp production from this native Chilean wood species. EXPERIMENTAL Wood preparation Three 25-year-old trees of D winteri JR et G Forster harvested in the VIII Region of Chile were cut into wood chips measuring approximately 2.5 1.8 0.4 cm. Before fungus inoculation, the wood chips were immersed in water for 16 h. Residual water was drained and 100 g (dry basis) of moist wood chips were sterilized in 800 cm3 bioreactors at 121 C for 45 min. After the soaking and sterilization steps, the wood chip moisture was 60% on a dry weight basis. Fungus, inoculum preparation and wood biodegradation G australe (Fr) Pat, strain A464, from the IJFM culture collection of CIB-CSIC (Madrid, Spain) was

Correspondence to: Regis Mendonca, Laboratorio de Recursos Renovables, Universidad de Concepcion, Casilla 160-C, Concepcion, Chile E-mail: rteixeira@udec.cl Contract/grant sponsor: FONDECYT; contract/grant numbers: 1040614; 1020161 (Received 31 January 2005; revised version received 9 July 2005; accepted 6 July 2005) Published online 23 September 2005

2005 Society of Chemical Industry. J Chem Technol Biotechnol 02682575/2005/$30.00

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kindly provided by Dr Aldo Gonz lez. The strain was a maintained on 2% (w/v) malt extract, 0.5% (w/v) soybean peptone, 1.5% (w/v) agar culture plates at 4 C. Liquid medium (150 cm3 ) composed of 2% (w/v) malt extract and 0.5% (w/v) soybean peptone was inoculated with 10 discs (8 mm in diameter) of G australe-precultured solid medium. These liquid cultures were maintained unshaken for 15 days at 25 C. The grown mycelium mat was ltered and washed with 300 cm3 of sterilized water. Washed mycelium obtained from several cultures was blended with 100 cm3 of sterilized water in three cycles of 15 s. The mycelium suspension was used to inoculate the sterilized wood chips in the 800 cm3 bioreactors. Each 100 g of wood chips was inoculated with a volume of suspension corresponding to 500 mg of fungal mycelium per kilogram of dry wood. The inoculated wood chips were incubated at 25 C and maintained unshaken for periods of 15, 30 and 45 days. All experiments were performed in triplicate. After the biodegradation, the bioreactors were opened and the wood chips were washed with water to remove the supercial mycelium. The decayed wood chips were air-dried, their moisture was determined and the calculated initial and nal dry weights were used to determine weight losses due to fungal biotreatment. Component losses were calculated on the basis of the weight loss values and chemical compositions of the wood chips. Undecayed wood chips (without fungus) were prepared in a similar manner to be used as a control sample. Kraft pulping The undecayed control and the wood chips biotreated for 15, 30 and 45 days were submitted to kraft pulping. Each cooking was carried out in a 1 dm3 Parr reactor with 20 g of wood chips (dry basis) and 120 cm3 of cooking liquor, consisting of 15% of active alkali and 25% of suldity (both concentrations were expressed as Na2 O equivalents on dry wood basis). A reactor heating time of 90 min was used and all cookings were carried out at 170 C for different periods to achieve a wide range of H-factors (from 580 to 2900 h1 ). The H-factor, a control parameter in the pulping process, includes time and temperature as a single variable. It is also used to correct the heating time necessary to reach the maximum cooking temperature and occasional uctuations of this temperature during pulping. The H-factor was calculated based on plots of relative reaction rate as a function of cooking time. Relative reaction rates were calculated based on the Arrenhius equation using an activation energy of 134 kJ mol1 for kraft pulping. The area under these plots for each pulping experiment represents the H-factor.11 After pulping, the residual material was ltered, washed with owing water for maximum black liquor removal and disintegrated with 2 dm3 of water in a TAPPI standard debrillator for 3000 revolutions. The pulp was classied in a 0.15 mm slot screen (Somerville screener). The moisture on the screened
J Chem Technol Biotechnol 81:196200 (2006)

pulp was measured and the screened pulp yield was calculated. The reject content on pulp (shives retained in the 0.15 mm slot screen) were dried at 105 C until constant weight. Total pulp yield was the sum of the dry weights of screened pulp plus shives. Kappa number (TAPPI T 236) and hexenuronic acid content12 were determined in the screened pulp. Another set of kraft pulping was performed to produce enough pulp to determine strength properties. These cookings were carried out in a Parr reactor with a total volume of 3.8 dm3 with 250 g of wood chips (dry basis) and 1.5 dm3 of pulping liquor. All other cooking conditions were the same as used before. Pulps produced from this set of experiments presented kappa numbers of 32 for the control and 25 for 15 day biopulp. Strength and optical properties of kraft pulps Screened pulps prepared from untreated control and 15 day biotreated wood chips were rened in a PFI mill (TAPPI T 248) from 2000 to 10 000 revolutions. A SchopperRiegler test was performed to measure the drainage rate of rened pulps (ISO 5267-1). Handsheets prepared from these pulps (TAPPI T 205) were analyzed for their tensile (TAPPI T 494), tear (TAPPI T 414) and burst (TAPPI T 403) indexes. Pulp brightness was measured following TAPPI T 525. Chemical analysis of wood chips Untreated and biotreated wood chips were milled to pass through a 0.5 mm screen. Approximately 1.5 g of milled samples (in triplicate) were extracted with ethanoltoluene (1:2, (v/v) for 6 h followed by extraction with 95% ethanol for a further 6 h. The soluble extractives were determined based on the dry weight of extracted and non-extracted wood samples. The chemical composition of the extracted wood samples was determined by acid hydrolysis with 72% sulfuric acid as described elsewhere.13,14

RESULTS AND DISCUSSION The chemical composition of sterilized wood chips of D winteri (undecayed control) was 39.9 0.3% glucan, 20.9 0.6% polyoses, 31.1 0.4% total lignin, 2.5 0.1% extractives and 0.53 0.02% ashes. Total carbohydrates and the lignin amount are in agreement with results reported previously for this species.7 Weight and component losses due to the fungal pretreatment of D winteri by G australe for periods of 1545 days are shown in Fig. 1. Weight losses were between 2.9 and 4.9%, lignin losses ranged from 4 to 9% and glucan losses were from 2 to 4%, indicating a selective, but not extensive, biodelignication pattern. Wood extractives removal was also high, reaching decay values of 5060% during these biodegradation periods.
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Sound and biotreated wood chips were cooked in kraft liquor containing 15% active alkali and 25% suldity (expressed as Na2 O on a wood basis) for a wide range of H factors (5802900 h1 ). Figure 2 shows no signicant difference in screened pulp yield and shives content in the kraft pulps produced from either control or wood chips biotreated for 15, 30 and 45 days. Screened pulp yields were 4345% at an H-factor of 580 h1 and 4042% at an Hfactor of 2900 h1 . A clear benet of the biotreatment in the production of the kraft pulps can be seen in Fig. 3, which shows that biopulps produced at an Hfactor below 1500 h1 presented lower kappa numbers than the control pulps for the same H-factor. Kappa numbers of biopulps were reduced by 811 points at 580 h1 and by 67 points at 1050 h1 . On the other hand, pulps with a kappa number of 30 could be obtained by cooking the 15 day sample at an H-factor of 760 h1 , whereas the undecayed control would need 1100 h1 to achieve the same kappa value (H-factor reduction of 31%). With increased pulping severity (H-factor >1500 h1 ), the differences in the kappa numbers between the control and biopulps decreased, as already reported for chemical pulps obtained from wood samples biotreated with a variety of white-rot fungi.4,10,14 The amount of hexenuronic acids generated during kraft pulping of D winteri was in the range of 5064 mol (g pulp)1 for control pulps
Weight and component losses (%) 10 8 6 4 2 0 0 15 30 45 Time of biodegradation (days)
Figure 1. Weight and component losses of D winteri wood chips decayed by G australe under biopulping conditions. ( ) Weight; ( ) glucan; ( ) polyoses; ( ) lignin.

and 5061 mol (g pulp1 ) for biopulps. These concentrations were in agreement with the values usually found in kraft pulps of hardwoods.15 17 For kappa numbers in the range 2035, biopulps presented slightly lower amounts of hexenuronic acids than did the control pulps (Fig. 4). Considering that hexenuronic acids are produced from 4-O-methyl-Dglucuronic acid groups of hemicelluloses,15 the loss of this component during biodegradation (Fig. 1) could be responsible for the diminution of these acids in the biopulps. Hexenuronic acid diminution in kraft pulps is an additional benet of the wood biotreatment since
45 40 Kappa number 35 30 25 20 15 10 0 500 1000 1500 H-factor (h
-1)

2000

2500

3000

Figure 3. Kappa number of screened kraft pulps of D winteri. ( ) Undecayed control; ( ) 15-day biotreated; ( ) 30-day biotreated; ( ) 45-day biotreated.

Hexenuronic acid (mol g pulp-1)

65

60

55

50

45 15 20 25 30 35 Kappa number 40 45

Figure 4. Amount of hexenuronic acids in screened kraft pulps of D winteri. ( ) Undecayed control; ( ) 15-day biotreated; ( ) 30-day biotreated; ( ) 45-day biotreated.

50 Screened pulp yield (%)

8 6 4 2

45

40

Shives (%)

35 0 500 1000 1500 2000 2500 3000 H-factor (h-1)

0 0 500 1000 1500 2000 2500 3000 H-factor (h-1)

Figure 2. Screened pulp yield and shives content on kraft pulps of D winteri. ( ) Undecayed control; ( ) 15-day biotreated; ( ) 30-day biotreated; ( ) 45-day biotreated.

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Biokraft pulping of Drimys winteri

60 50 40 30 20 10 0 0 2500 5000 7500 PFI revolutions 10000 12500 Tensile index (Nm g-1) Beating degree (SR) 100 80 60 40 20 0 0 10 20 30 40 50 60 Beating degree (SR) Burst index (kPa.m2 g-1) 8 6 4 2 0 0 10 20 30 40 50 60 0 10 20 30 40 50 60 Beating degree (SR) Beating degree (SR)

12 Tear index (mN.m2 g-1) 10 8 6 4 2 0

Figure 5. Beatability and strength properties of kraft pulps from undecayed and biotreated D winteri. ( ) Undecayed control; ( ) 15-day biotreated.

hexenuronic acids are known to consume a signicant amount of chemicals in the pulp bleaching process.18 Strength and optical properties were determined in pulps from control (kappa 32) and 15 day biotreated wood (kappa 25). Brightnesses of 27.2 and 25.5% ISO were obtained for unrened pulps from control and 15 day biopulp, respectively. Pulps were rened in a PFI beater to obtain rening curves (Fig. 5). Biopulps were easier to rene than control pulps since less PFI revolutions were required to reach a dened beating degree. This result represents a direct energy saving due to the reduction in beating time required to obtain pulps with a given drainability. For instance, to obtain pulps with 25 and 35 SR, the biopulps needed 28 and 21% less PFI revolutions than control pulps, respectively. Similar increases in the brillation and energy savings for biopulps in comparison with control pulps have also been reported previously.3,14 Although biopulp handsheets are easier to rene, their strength properties did not present signicant differences compared with control pulps (Fig. 5).

provided pulps with lower kappa numbers and better beatability with no losses in strength properties.

ACKNOWLEDGEMENTS H Franco acknowledges a scholarship from the ALFA Program and Graduate Program in Forestry of the Facultad de Ciencias Forestales de la Universidad de Concepcion. Financial support from FONDECYT (1040614 and 1020161) is also gratefully acknowledged.

REFERENCES
1 Rodrguez S, Antecedentes tecnologicos de Canelo, Drimys winteri. Bosque 19:9199 (1998). 2 Melo R and Paz J, Nuevas esp cies en la produccion de celulosa. e Celulosa Papel 3:1315 (1987). 3 Kang KY, Jo BM, Oh JS and Manseld SD, The effects of biopulping on chemical and energy consumption during kraft pulping of hybrid poplar. Wood Fiber Sci 35:594600 (2003). 4 Mendon a R, Guerra A and Ferraz A, Delignication of Pinus c taeda wood chips for preparing high-yield kraft pulps from Ceriporiopsis subvermispora-biotreated samples. J Chem Technol Biotechnol 77:411418 (2002). 5 Agosin E, Blanchette RA, Silva H, Lapierre C, Cease KR, Ibach E, Rabad AR and Muga P, Characterization of Palo Podrido, a natural process of delignication in wood. Appl Environ Microbiol 56:6574 (1990). 6 Barrasa JM, Gonz lez AE and Martnez AT, Ultrastructural a aspects of delignication of Chilean woods by Ganoderma australe and Phlebia chrysocrea. Holzforschung 46:18 (1992). 7 Elissetche JP, Ferraz A, Parra C, Freer J, Baeza J and Rodriguez J, Biodegradation of Chilean native wood species, Drimys winteri and Nothofagus dombeyi, by Ganoderma australe. World J Microbiol Biotechnol 17:577581 (2001). 8 Akhtar M, Blanchette RA, Myers G and Kirk TK, An Overview of biomechanical pulping research, in Environmentally Friendly 199

CONCLUSIONS The results show that D winteri is a potential wood species for kraft pulp production. Biokraft pulps of D winteri pretreated with G australe and produced using mild cooking conditions (low H-factor, high kappa number) had lower kappa numbers and similar screened pulp yields in comparison with pulps obtained from untreated wood chips. Biopulps were easily rened in a PFI mill, requiring less revolutions to achieve a dened brillation degree. The strength and optical properties of the biopulps were similar to those of the control pulps, indicating that the biotreatment
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Technologies for the Pulp and Paper Industry, ed. by Young R and Akhtar M. Wiley, New York, pp. 309340 (1998). Ferraz A, Mendon a R and Silva FT, Organosolv delignication c of white- and brown-rotted Eucalyptus grandis hardwood. J Chem Technol Biotechnol 75:1824 (2000). Ferraz A, Rodrguez J, Freer J and Baeza J, Formic acid/acetone organosolv pulping of white-rotted Pinus radiata softwood. J Chem Technol Biotechnol 75:11901196 (2000). Bierman CJ (ed.), Essentials of Pulping and Papermaking. Academic Press, New York (1993). Chai XS, Zhu JY and Li J, A simple and a rapid method to determine hexenuronic acid groups in chemical pulps. J Pulp Paper Sci 27:165170 (2001). Ferraz A, Baeza J, Rodrguez J and Freer J, Estimating the chemical composition of biodegraded pine and eucalyptus wood by DRIFT spectroscopy and multivariate analysis. Bioresource Technol 74:201212 (2000). 14 Mendon a R, Ferraz A, Kordsachia O and Patt R, Alkaline c sulte/anthraquinone pulping of pine wood chips biotreated by Ceriporiopsis subvermispora. J Chem Technol Biotechnol 79:584589 (2004). 15 Li J and Gellerstedt G, The contribution to kappa number from hexenuronic acid groups in pulp xylan. Carbohydr Res 302:213218 (1997). 16 Chai XS, Luo Q, Yoon SH and Zhu JY, The fate of hexenuronic acid groups during kraft pulping of hardwoods. J Pulp Paper Sci 27:403406 (2001). 17 Pedroso AI and Carvalho MG, Alkaline pulping of Portuguese Eucalyptus globulus: effect on hexenuronic acid content. J Pulp Paper Sci 29:150154 (2003). 18 Vuorinen T, Fagerstrom P, Buchert J, Tenkanen M and Teleman A, Selective hydrolysis of hexenuronic acid groups and its application in ECF and TCF bleaching of kraft pulps. J Pulp Paper Sci 25:155162 (1999).

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