Bioresource Technology37 ( 1991 ) 1-6

Organosolv Pulping V: Formic Acid Delignification of Eucalyptus globulus and Eucalyptus

grandis
Jaime Baeza, a Silvio Urizar, a N o r m a de Magalh Eckhard Schmidt & N e l s o n DurAn b es Erismann, b Juanita Freer, a
~Department of Chemistry, Renewal Resources Laboratory, Facultad de Ciencias, Universidad de Concepci6n, Casilla 3-C, Concepci6n, Chile blnstituto de Quirnica, Biological Chemistry Laboratory, Universidade Estadual de Campinas, C.P. 6154, Campinas, CEP 13081, Silo Paulo, Brazil (Received 12 February 1990; revised version received 14 May 1990; accepted 15 May 1990)

Abstract Organosolv pulping mediated by formic acid was evaluated. Wood of Eucalyptus globulus and Eucalyptus grandis was cooked with formic acid under different conditions of solvent ratio (formic acid:water), catalyst concentration, temperature and time of treatment. For E. globulus, the best results for sawdust samples were obtained at 90C after 90 rain of cooking, with a solvent ratio of 80:20 (vv- 1), a charge (wood:solvent ratio) of1:30 and 0.44% (wv -1) of catalyst. In the case of E. globulus chips, the concentration of catalyst used was 0"22%, the charge was 1:10, and soaking and preheating were used. For a sample of E. globulus soaked in water for 72 h, the pulp yield was 56%, Kappa number 22 and reject content 1"6%. E. grandis wood needed more drastic conditions. Cooking of E. grandis chips with formic acid (99%) at 95C, 0.22% catalyst, charge 1:10, resulted in a pulp yield of 43%. The Kappa number was 31, reject content 0.1% and the cellulose and Klason lignin contents were 88% and 8%, respectively. Key words: Organosolv, eucalyptus, delignification.

INTRODUCTION The pulping method using organic solvents (organosolv) involves the selective extraction of lignin from lignocellulosic raw materials. As early as 1931, Kleinert and Tayenthal (1931) proposed
I

the use of aqueous ethanol for the delignification of wood. The most widely used solvents are in fact alcohol-water mixtures (Baumeister & Edel, 1980; Lora & Aziz, 1985). A methanol-water mixture has been used in the presence of alkali earth metal salts for successful softwood delignification (Paszner & Behera, 1989). Recently, other solvents have been used in these processes (Nimz & Caten, 1986; Aziz & McDonough, 1987; Johansson etal., 1987; Aziz & Sarkanen, 1989). Although organosolv pulping by formic acid has been used since 1936 (Freudenberg et al., 1936; Wright & Hibbert, 1937), no systematic studies have been published. Formic acid pulping was patented in 1982 (Jordan, 1982) but no technical description of the process was given (Bucholtz & Jordan, 1983). Since 1986, our group has been working on organosolv pulping (Baeza et al., 1986a, b, 1988; Pedreros et al., 1989). Recently the formic acid lignin from Pinus radiata D Don was characterized (Baeza et al., 1990) and the process of the lignin extraction was optimized (Baeza et al., submitted a). Also, the influence of this pretreatment on enzymatic hydrolysis and mimetic ligninase reaction was studied (Erismann et al., 1990; Baeza et al., submitted b). The interest in organosolv pulping can be attributed to the following factors: (i) low investment cost for a new plant, (ii) low environmental contamination problems, (iii) solvent recovery, (iv) recovery of carbohydrates and lignin, which are by-products with potential as chemical feedstocks. Besides these advantages, formic acid is a low cost

Bioresource Technology 0960-8524/91/S03.50 1991 Elsevier Science Publishers Ltd, England. Printed in Great Britain

J. Baeza, S. Urizar, N. de Magalh6es Erismann, J. Freer, E. Schmidt, N. Durfn

case of chips, the residual wood was divided into pulp and rejects (% of wood basis). The rejects were discarded and the pulp analyzed. Determination of cellulose (Pereira & Sardinha, 1984), Klason lignin (ASTM D-1106-56), Kappa number (Berzins, 1966), and extractives (ASTM D-1105-56) were carried out as described in the literature. The standard deviations (S) of the results shown in the tables are, for the whole extraction process, as follows: residual wood: S = _+3"0%, reject: S = _2.3%, yield: _+1.1%, formic lignin: S= -+1"5%, Klason lignin: S--_+1.6%, cellulose: S--_+3.1% and Kappa number S = _+8.3. Although the cellulose content determined by the method of Pereira and Sardinha (1984)(based on the solubilization of lignin and hemicellulose with an acetic/nitric acid mixture) provided higher values (53.1% for E. grandis ground wood, Table 1) than that by ASTM D-1103-60 method (44.3% for the same sample of E. grandis, Table 1), the former method was chosen since it is easier and
Table 1. Chemical composition of E. globulus and E. grandis wood
E. globulus (%) Extractive Cellulose t Lignin Hemicellulose 2.4 58.3 22.4 ~ 19.0 b E. grandis (%) 5.8 53.1 (44.3 ') 24.8 a 22.1 b (28.6 ~)

chemical, and the process can be carried out at low temperature and atmospheric pressure for the pulping (Baeza et al., submitted a ). This paper reports the organosolv pulping of Eucalyptus globulus and Eucalyptus grandis using formic acid as solvent. These forestry species responded differently to the pulping conditions due to their different chemical and anatomical properties (Bamber, 1985).

METHODS

Wood samples of E. grandis (7 years old) and E. globulus (9 years old) were chipped and a fraction was ground to 40-60 mesh. The E. globulus samples were extracted with ether and ethanol and then analyzed. The delignification was studied in sawdust and in chips (15 mm x 10 mm x 2 mm) with formic acid treatment on a small scale. Two grams of wood were used in each experiment with sawdust and 2 g or 10-15 g of E. grandis or E. globulus chips, respectively. The formic acid extractions were performed in a three necked flask equipped with a condenser to prevent solvent loss. After the addition of wood, solvent (formic acid-water) and catalyst (HCI), the mixture was continuously stirred. The rod and blade of the mechanical stirrer was of steel for E. grandis and of glass and teflon for E. globulus. The temperature was controlled by a water bath. Figure 1 illustrates the whole formic acid process utilized for both Eucalyptus species. The yield (initial wood basis), the percentage of extracted formic lignin (initial wood basis) and the residual wood composition were considered in the evaluation of the delignification process. In the
Wood
Extraction HCOOH

l Pereira and Sardinha (1984). %.1% soluble lignin (Bland & Menshun, 1971) in 72% sulfuric acid. hObtained by difference. 'ASTM-D-1103-60. 'ZKlason lignin. eObtained by difference of ASTM D-1104-56 for holocellulose and ASTM D-1103-60 for cellulose.

[
Residual wood

Filtration Formic solution ( i ) Evaporation

I
Pulp

Rejected wood
Precipitation

(ii) H20/precipitation

(iii) Filtration

Formic lignin

HCOOH

HzO

,L

Carbohydrates

Fig. 1.

Flowchart of the formic acid treatment.

Fom~ic acid delignification o f Eucalyptus

requires less time (only 30 min). Therefore, the cellulose contents listed in the tables may contain some hemicellulose and they will be considered for comparison. RESULTS AND DISCUSSION The chemical composition and anatomy of E. globulus and E. grandis is different (Table 1 ). E. globulus appears to be more favorable for pulping because of its higher cellulose and lower lignin content. Anatomical differences, primarily the larger vessel diameters which facilitate the penetration of pulping media into Eucalyptus, favor the pulping of E. globulus (170 /~m) over E. grandis (155 /zm). Also, a larger proportion of rays at the parenchyma in E. globulus (16%) than E. grandis (4%) favors the lateral movement of

pulping liquor (Bamber, 1985). Production of high quality chemical and semichemical pulp depends on soaking, during which pulping liquor penetrates into the wood. The delignification process (Table 2) on sawdust previously extracted from E. globulus required 90 min of treatment with 80% formic acid and 0.4% HC1, for a good yield of residual solid material with a high cellulose content and low Klason lignin (assay no. 9). No significant changes were observed when the concentration of HCI was decreased (assay nos 10 and 11). For 0.44% hydrogen chloride and 98% formic acid (assay no. 4), a high degree of delignification was obtained, but considerable carbohydrate degradation (only 33% pulp yield) occurred. At 90C a higher delignification than that at 80C was obtained. The temperature effect is greater at lower formic acid concentrations. Higher formic

Table 2. Delignification of E. globulus sawdust

Assay no. 1 Conditions Time(min) Temp.(C) HCOOH(%v) H C l ( % w v -j ) Results (%) Yield Formic lignin Klason lignin Cellulose 2 3 4 5 6 7 8 9 10 11 a 12 13 14

15 90 80 -99.6 2.5 15"6 61"7

15 90 80 0"4 84.1 6.8 14.4 69.4

30 90 80 0"4 69.9 15.2 11"9 83"3

30 90 98 0"4 32.8 25.7 3'5 96"7

30 90 98 -66.6 18.0 8"3 73.5

30 90 98 0"2 58"5 21.7 4.8 89'2

45 90 80 0"4 64.3 15.2 9.6 89-9

60 90 80 0"4 61.9 17.8 8"5 92-9

90 90 80 0"4 58.5 17-8 4.7 97"3

90 90 80 0"2 64.7 18.3 7"7 91.4

90 90 80 0"2 60.7 13.2 6"0 88.1

90 90 98 0"2 40.0 32.4 4"2 98.0

30 80 80 0"4 88.5 5.7 15"2 67"1

30 80 98 0"2 53.1 19.9 5-1 91'2

Solvent: HCOOH-water, 40-60 mesh, charge 1/30 (g wood ml- 1), stirring 2300 rpm. "Unextracted wood. Table 3. Pulping of E. globulus wood chips. Effect of impregnation at room temperature
Assay no. 1 Conditions Time (min) Time max t ~ Temp. max C Impregnation Time (h) Results Residual wood (%) Reject (%) Yield (%) Kappa number 2 3 4 5 6 7 8 9

190 100 90 Liquor 24 62.1 11"7 50-4 33"5

173 100 90 H,O 24 56.7 1.6 55-1 22"0

155 100 90 NaOH 24 65'5 8"6 56"9 26"1

170 100 90 Liquor 48 62.1 25"3 36"8 30"4

180 100 90 He O 48 61.0 9"7 51.3 28"9

175 100 90 NaOH 48 63.8 7.3 56'5 19"6

183 100 90 Liquor 72 62"5 7.0 55'5 30"5

180 100 90 H,O 72 59"0 2"6 56.4 22-4

165 100 90 NaOH 72 62.0 7.3 54.7 18"2

Solvent: H C O O H 80%, catalyst 0'22% (wv- l), charge 1/10 (g wood ml- 1), stirring 2000 rpm.

J. Baeza, S. Urizar, N. de Magalhfzes Erismann, J. Freer, E. Schmidt, N. Durfn

acid concentrations markedly increased the delignification process. The extractives present in the wood produced a lower yield of pulp and smaller extension of formic acid lignin extraction. For the chip delignification (Table 3 and Fig. 2) the best conditions obtained with sawdust were initially selected. For E. globulus chips, a charge of 1/10 g wood (ml liquor) -~ wood and 0"22% (wv -1) of HC1 as catalyst was used. The high reject contents in the first assays (not shown) were diminished by chip impregnation at room temperature with pulping liquor, 1% NaOH solution or water. Pre heating and longer pulping times were necessary to increase the efficiency. It can be concluded from assays no. 2 and 8, that this process is comparable with other organosolv

processes (Johansson et al., 1987; Paszner & Cho, 1989). Pulping yield (Fig. 2) was similar for water and NaOH soaking for 24 h. Reject and Kappa number in water were significantly lower than NaOH and liquor also for 24 h. Pulping of E. grandis wood under conditions similar to those used for E. globulus chips (80% formic acid, 0.22% (wv -L) catalyst, charge 1/30 g wood (ml liquor) -~ did not lead to an effective delignification (not shown). Results obtained using 86% formic acid gave no significant improvement (Tables 4 and 5). Most of the assays were carried
Table 4. Pulping of E. grandis sawdust and a pulp previ-

ously treated with formic acid

Ia 2h

100

80

60

Conditions Time (rain) Temperature (C) H C O O H (%)(v v-t) HCI (%)(w v-1) Charge (g ml-t) Results Residual wood (%) Yield (%) Formic lignin (%) Klason lignin (%) Cellulose (%) Kappa number

90 90 86 0.22 1/30 62.2 62.2 14.9 19.7 73.6 --

90 90 86 0.22 1/30 52.8 42-2 16.8 15.1 87.2 47.4

20

~
SOAKING TIME (h)

8o

Fig. 2. Effect of soaking time on pulp yield, Kappa number and reject: Pulp yield (o), Reject (t~) and Kappa number ( zx ), In water ( ), in NaOH ( - - ' - - ) and liquor ( - - - ) . Conditions are described in the experimental part.

"Sawdust. hChips previously treated with formic acid at the described condition and then the pulp obtained again treated with formic acid, in these same conditions (total time 180 rain).

Table 5. Pulping of E. grandis chips (86% formic acid)"

Assay no. 1 Conditions Time (min) Impregnation (h) lmpregnant Temperature (C) HCl (%) (w v- ~) Results (%) Residual wood Reject Yield Formic lignin Klason lignin Cellulose Kappa number
90 2 Liquor 90 0-11 77.0 53.4 23.6 4-9 23.7 66.9 94.8

2
90 3 Liquor 90 0.18 -34.6 --22.1 72-4 100-0

3
90 3 Liquor 90 0.22 59.2 1.9 57-3 14-8 19.6 79"0 78.4

4
90 3 Liquor 90 0-44 58.6 0.7 57-9 11-6 24.7 77.4 98.8

5
90 --90 0.22 68"3 29.8 38-5 8-6 18"5 75.4 72.4

6b
90 --90 0-22 69.0 28-2 40.8 10.6 20.7 73.0 84.6

7
180 --90 0"22 62'8 5'8 57-0 13"4 18.5 77.1 74.0

"Unextracted wood, 86% HCOOH, charge 1/30 (g wood ml-t), vigorously stirring. Klason lignin, cellulose and Kappa refer only to pulp analysis. hCharge 1/20 (g wood ml- i).

Formic acid delignification of Eucalyptus

Table 6. Pulpingof E. grandis chips (99% formic acid)~

Assay no. 1 Conditions Time (min) Impregnation (h) Impregnant Temperature (C) Results Residual wood (%) Reject (%) Yield (%) Formic lignin (%) Klason lignin (%) Cellulose (%) Kappa number 2 3 4 5 6 7

60 . . 95 57.9 22.4 35.5 18-6 10.4 84.4 38"0

90 . . 95 54.5 5.2 49.3 20-6 11.2 83.7 42.0 . .

120 . . 95 50-8 3"1 47.7 21"1 10.5 85.8 39-8

180 . . 95 48-3 0.5 47.8 22.0 12.2 84.7 39.4

90 90 57-8 4.1 53.7 15.6 12.5 82.1 46-8

90 50 H20 90 58.4 3.9 54.5 13.8 16-2 77.6 58.7

60 reflux 61.2 30.5 30.7 15.6 11.7 84.1 40'7

"Unextracted wood, 99% HCOOH, catalyst 0.22% (w v-~), charge 1/30 (g wood ml-~), vigorously stirring. Klason lignin, cellulose and Kappa refer only to pulp analysis.

OUt with chips, but one was with sawdust (Table 4, assay no. 1). Comparing sawdust with chips (Table 5, assay no. 5) under the same experimental conditions, no significant differences were found in the chemical compositions of the pulp and the treated sawdust. The large reject content found for chips was considerably reduced after chip impregnation with liquor at room temperature. The effect of the catalyst concentration was studied from 0.11 to 0.44% (wv -1 ) (Table 5), confirming a more selective chips delignification with 0.22% (wv-1) of HCI. W h e n a pulp previously obtained with 86% formic acid was again subjected to the same treatment, the extension of delignification increased (Table 4, assay no. 2). This improvement was not due to an increased extraction time (compare with Table 5, assay no. 7). Two treatments with 86% formic acid provide a pulp with the same Kappa number but a smaller yield, than one obtained with one chips treatment with 99% formic acid (Table 6, assay no. 5). Therefore, 99% formic acid was selected as a better solvent for pulping of E. grandis wood under various conditions (Tables 6 and 7). Results for this showed that increasing the temperature of extraction from 90C to 95C slightly improved the degree of delignification. Increasing the temperature further to the reflux temperature (c. 10 7C) did not improve lignin extraction. Increasing time of pulping (Table 6) had a marked effect on reject contents, but did not significantly change the Kappa number of the pulps obtained. As for E. globulus, a low reject content was found for E. grandis, when chips were water-

Table 7. Pulping of E. grandis chips (99% formic acid)a

Assay no.

1
Conditions Charge (g wood ml- l) Results Residual wood (%) Reject (%) Yield (%) Formic lignin (%) Klason lignin (%) Cellulose (%) Kappa number

2 1/20 42.2 0.1 42.1 22.3 8.0 87.7 33"2

3 1/10 42.9 0.1 42.8 23.4 8.4 88.3 31.3

1/30 41.8 0.5 41-3 22.8 11.4 84.8 44.6

a90 min of cooking, 95C, 0.22% HCI. Mechanical stirring with glass rod and teflon blade.

saturated before formic acid extraction, but with a higher Kappa number. Another variable of the process verified was the effect of the mechanical stirrer, used in all formic acid treatments with E. grandis wood (Tables 4-6), on lignin extraction. Substitution of steel for a glass rod and a teflon blade did not modify the process as a whole (see Table 7). However, the reject content and the pulp yield were smaller (compare'Table 6, assay no. 2 and Table 7, assay no. 1). The charge (wood/solvent ratio) effect on the chemical quality of the pulp showed better results at 1/10 g wood (ml liquor)-~ (assay no. 3). This result is economically interesting and was the best result achieved for E. grandis wood;

J. Baeza, S. Urizar, N. de Magalhdtes Emmann, J. Freer, E. Schmidt, N. Durfn

of formic acid delignification on the enzymatic hydrolysis of Pinus radiata D. Don sawdust. AppL Biochem. BiotechnoL Bamber, R. K. (1985). The wood anatomy of eucalypts and paper-making. Appita, 38, 210-16. Baumeister, M. & Edel, E. (1980). Aethanol-wasser Aufschluss. Papier (Darmstadt), 34, V9-V 18. Berzins, V. (1966). Micro Kappa numbers. Pulp Paper Mag. Can., 67,206-8. Bland, D. E. & Menshun, M. (1971). Determination of total lignin and polyphenol in eucalypt woods. Appita, 25. 110-15. Bucholtz, M. & Jordan, R. (1983). Formic acid woodpulping could yield valuable chemical products. Pulp Paper, 57. 102-4. Erismann, N. de M., Fernandez, A. M., Baeza, J., Freer. J.. Mansilla, H. & Durfin, N. (1990). Non-pollutant wood and pulps delignification: biomimetic ligninase system. BiotechnoL Lett., 12,305-8. Freudenberg, K., Janson, A., Knopf, E. & Haag, A. (1936). Zur Kennmis des lignins ( 15 Mitteil.) Ber. 69, 1415-25. Johansson, A., Aaltonenen, O. & Ylinen, P. (1987). Organosolv pulping-methods and pulp properties. Biomass, 13, 45-65. Jordan, R. K. (1982). Formic acid pulping. PCT Int. Patent WO 82/01902. Kleinert, T. N. & v. Tayenthal, K. (1931). Ueber neure Versuche zur Trennung Cellulose und Inbrusten Verschiedener Holzer, Z. Angew. Chem., 44,788-91. Lora, J. H. & Aziz, S. (1985). Organosolv pulping: a versatile approach to wood refining. Tappi J., 68, 94-7. Nimz, H. H. & Caten, R. (1986). Chemical processing of lignocellulosics. Holz. Roh- Werkstoff., 44,207-12. Paszner, L. & Behera, N. C. (1989). Topochemistry of softwood delignification by alkali earth metal salt catalyzed organosolv pulping. Holzforschung, 43, 159-68. Paszner, L. & Cho, H. J. (1989). Organosolv pulping: acidic catalysis options and their effect on fiber quality and delignification. Tappi J., 73, 135-42. Pedreros, A., Durfin, N., Schmidt, E., Freer, J., Aguilera, C. & Baeza, J. (1989). Pulping of Pinus radiata D. Don wood by organic solvent. In Proc. First Brazilian Symposium on Chemistry of Lignins and Other Wood Components, ed. R. A. M. C. de Groote & A. A. S. Curvelo. S. Carlos, S.P., Brazil, pp. 168-73. Pereira, H. & Sardinha, R. (1984). Chemical composition of Eucalyptus globulus Lab. Appita, 37, 661-4. Wright, G. F. & Hibbert, H. (1937). Studies on lignin and related compounds. XXVI. The properties of spruce lignin extracted with formic acid. J. Am. Chem. Soc., 59, 125-30.

providing a pulp with Kappa number, cellulose and Klason lignin content of 31.3, 88.3 and 8.4%, respectively. The pulp yield was 42.8%. In summary, formic acid pulping appears to be an efficient delignification process, with greater potential than other organosolv methods studied in other laboratories.

ACKNOWLEDGEMENTS

Financial support from Direccion de Investigacion, Universidad de Concepcion, FONDECYT (Project 659/89) PNUD (Project CHI/88/012). N.D. acknowledges CNPq, FAPESP and FINEP.

REFERENCES
Aziz, S. & McDonough, T. J. (1987). Ester pulping -- a brief evaluation. TappiJ., 70, 137-8. Aziz, S. & Sarkenen, K. (1989). Organosolv pulping -- a review. TappiJ., 73, 169-75. Baeza, J., Freer, J., Palma, G., Pedreros, A., Rodriguez, J., Rojas, N. & Durfin, N. (1986a). Chemical studies on Pinus radiata D. Don. In Proc. Symposium of Chemistry and Renewal Resources Utilization, Concepci6n, Chile, pp. 63-6. Baeza, J., Freer, J., Pedreros, A., Durfin, N. & Mansilla, H. ( 1986 b). Proc. of First Brazilian Symposium in Bioorganic Chemistry, Florianopolis, S. C., Brazil, pp. 170-5. Baeza, J., Freer, J., Pedreros, A. & Durfin, N. (1988). Delignification of Pinus radiata D. Don wood by organic solvent. In Proc. XVIII Latin American Chemical Congress. Santiago, Chile, pp. 513-14. Baeza, J., Freer, J., Pedreros, A., Schmidt, E., Mansilla, H. & Durfin, N. (1990). Organosolv-I: Formic acid lignin from Pinus radiata D. Don. Bol. Soc. ChiL Quire., 35,331-7. Baeza, J., Pedreros, A., Urizar, S., Freer, J., Schmidt, E. & Dur~in, N. (submitted a). Organosolv-II: Formic acid delignification of Pinus radiata D. Don. Biomass. Baeza, J., Fernandez, A. M., Freer, J., Pedreros, A., Schmidt, E. & Durfin, N. (submitted b ). Organosolv-IlI: the influence