THERMAL BEHAVIOR OF SCOTS PINE (PINUS SYLVESTRIS) AND SILVER BIRCH (BETULA PENDULA) AT 200-230°C Postgraduate Student Raimo Alkn Professor and Risto Kotilainen Postgraduate Student Department of Chemistry, Laboratory of Applied Chemistry University of Jyvaskyla, PO. Box 35, FIN-40351 Jyvaskyla, Finland (Received April 1998) ABSTRACT Scots pine (Pinus sylvestris) and silver birch (Betuln pendula) were heated for 4-8 h in a steam atmosphere at low temperatures (200-230°C). The birch feedstock decomposed slightly more exten- sively (6.4-10.2 and 13515.2% of the initial DS at 200°C and 225"C, respectively) than the pine feedstock (5.7-7.0 and 11.1-15.2% at 205°C and 230°C. respectively). The results indicated that the differences in mass loss between these feedstocks were due to mainly the fact that carbohydrates (cellulose and hemicelluloses) were more amenable to various degradation reactions than lignin in intact wood. The degradation reactions were also monitored in both cases by determining changes in the elemental composition of the heat-treated products. Keywords: Heat treatment, carbohydrates, lignin, extractives, Pinus sylvestris, Betula pendula. INTRODUCTION content of hemicelluloses (25-30% of DS) In our previous experiments (AlCn et al. than hardwood (lignin and hemicelluloses are 2000), the thermal degradation of the structur- usually in the range 20-25 and 30-35% of al constituents (lignin and polysaccharides, DS, respectively). On the basis of these facts, i.e., cellulose and hemicelluloses) of Norway the thermal behavior of softwood and hard- spruce (Picea abies) was established under wood can be expected to be different, even at conditions (temperature range 180-225"C, low temperatures. Clearly, a better understand- heating time 4-8 h) relevant to the industrial ing of these differences will be of benefit to process of stabilizing wood against fungal at- the development of heat-treatment processes. tack (Dirol and Guyonnet 1993; Viitaniemi The primary aim of this study was to find and Jiimsa 1996). Hawever, the lignin and out what differences exist in the thermal be- hemicelluloses present in softwood differ havior of Scots pine (Pinus sylvestris) and sil- slightly chemically from those in hardwood ver birch (Betula pendula) under conditions (Fengel and Wegener 1989; Sjostrom 1993). similar to those of our earlier experiments In addition, softwood generally contains more (AlCn et al. 2000). The study focused on the lignin (25-30% of dry solids (DS)) and lower changes occurring in the chemical composi- tion of these feedstocks during heating at 200- ' Present address: Worsley Alumina Pty. Ltd.. Gastalbo road, Wonley, Western Australia. P.O. Box 344. Collie, i300c with particular On polysac- WA 6225, Australia. charide degradation. W,x~dand Fihrr S<,r,z<r.32(?), 2000, pp. 138-143 0 ?O(X) by the Socrety of Wood Sclence and Technology Zaman et a1.-THERMAL BEHAVIOR OF SCOTS PINE AND SILVER BIRCH 139 TABLE1. Some characteristic.^ of the wood feedstocks sample first with acetone (4 h) and then with used (% of DS). dichloromethane (4 h) in a Soxhlet apparatus. Relat~vecompo5it1on Pine Birch The elemental analysis (carbon, hydrogen, and of the main component\ (Pinu5 s?lr~esrri~) (Befula pendula) nitrogen) was performed using a micro-ele- Carbohydrates* 72.3 75.6 mental analyzer (LECO CHN-600). The 0x.y- Lignin 24.5 21.8 gen content was calculated by difference Extractives 3.2 2.6 (100% - C% - H% - N%). The amount of Elemental analy\,i DS was measured by drying a sample at 105°C Carbon 47.8 47.3 for 12 h. Hydrogen 6.7 6.4 Nitrogen 0.1 0.1 The composition of monosaccharides in the Oxygen* 45.4 46.2 hydrolyzate obtained from the lignin detler- * Calculated by difference mination was analyzed on the basis of their per(trimethylsily1)ated derivatives by C;C (Biermann and McGinnis 1989). A J & W EXPERIMENTAL DB-1701 fused silica capillary column (60 m Wood material and the heat treatments X 0.32 mm with a film thickness of 0.17 pm) was employed. The temperature program was The wood feedstocks used were air-dried 2 min at 100°C, 2°C min-* to 185'C, 15 nun and bark-free Scots pine (Pinus sylvestris) and at 185"C, 39°C min-I to 300°C, and 5 rnin at silver birch (Betula pendula). The basic char- 300°C. Hydrogen as a carrier gas (1.6 ml acteristics of these wood samples are present- rnin') and xylitol as an internal standard were ed in Table 1. used. The temperature of both the injection The heat treatments were carried out at VTT port and the detector was 300°C. The relative (Technical Research Center of Finland), in the retention times for the different anomers of the Section of Building Technology. The treat- pyranoid and furanoid wood monosaccharides ment system consisted of a temperature-con- compared with the internal standard were de- trolled tube furnace in which pine and birch termined by model compounds. For the quan- wood boards (22 mm X 100 mm X 1500 mm) titative calculations, the response factors be- were positioned so that each board had suffi- tween the internal standard (1.00) and the cient space around it and maintained in a peaks derived from arabinose, xylose, galac- steam atmosphere under the conditions shown tose, glucose, and mannose were 1.25, 1.22, in Table 2. Before the heat treatments com- 1.19, 1.17, and 1.26, respectively. menced, the boards were stabilized at 65% RH and had a moisture content about 11%. For the chemical analyses, the untreated and RESULTS AND DISCUSSION treated wood samples were ground in a Cy- Table 1 shows the chemical composition of clotec 1093 sample mill (Tecator, Inc.) and the softwood and hardwood feedstocks used. sieved through a round-holed screen using the Although not analyzed in detailed here, it is < 1 mm fraction. well known (Fengel and Wegener 1989; Sjo- strom 1993) that pine contains more gluco- Analytical determinations mannans (15-25% of DS) and less xylans (5- The analysis of the untreated and treated 10% of DS) than birch, the average content of wood samples was based on well-established glucomannans and xylans in birch is 2-5% of methods in wood chemistry. The lignin con- DS and 15-30% of DS, respectively. tent was determined as the sum of acid-insol- In contrast to the variation in hemicellulose uble Klason lignin (TAPPI T-249 cm-85) and content, it can be assumed that both feedstocks acid-soluble lignin (TAPPI UM-250). The ex- have an equal cellulose content (about 40% of tractive content was determined by extracting DS). There are also some characteristic chem- 140 WOOD AND FIBER SCIENCE, APRIL 2000, V. 32(2) TABLE2. MUSSloss of the wood ,feedstocks during heat treatments (% of initial). Plne (Ph~8.5~rl~,elrrr) BII-ch (Betula pmdulrr) Heat treat~nent Total mas Ins\ Heat treatment Rltal mass Ios* ("Ch) Total ma\\ lo\\ ot carbohydrates ("ch) Total ma% lo\\ of carbohydrate5 ical differences between softwood and hard- structures of the hemicelluloses had an impor- wood hemicelluloses. Furthermore, softwood tant influence on the thermochernical behavior and hardwood lignins and the fractions of the of the feedstocks studied. For example, it has extractives in softwood and hardwood differ been shown (Radlein et al. 1991; AlCn et al. typically from each other (Fengel and Wege- 1995a) that xylans (rich in birch) degrade on ner 1989; Sjostrom 1993). heating more easily than glucomannans (rich The total mass loss of the pine samples dur- in pine). In addition, the monosaccharide con- ing heating at 205OC and 230°C varied in the tent of the heat-treated samples (Fig. 2) sug- range 5.7-7.0 and 11.1-15.2% of the initial gested, as expected, that under the conditions DS (Table 2), respectively, revealing the clear studied, cellulose (a linear homopolysacchar- bearing of temperature on overall mass loss. ide of P-D-glucopyranose moieties) was ther- Furthermore, birch samples decomposed mally more stable than the hemicelluloses. slightly more extensively than the pine sam- During heating, a multitude of chemical re- ples; at 200°C and 225°C the corresponding actions on the part of the individual wood con- mass losses in the birch samples were in the stituents take place (Antal 1983; Shafizadeh range 6.4-10.2 and 13.5-15.2% of the initial 1985; Elder 1991; Radlein et al. 1991; Boon et DS, respectively. This can be explained partly al. 1994; Emsley and Stevens 1994; Ponder and by the fact (AlCn et al. 1995b) that carbohy- Richards 1994; AlCn et al. 1995a). For exam- drates are in general degraded to a greater ex- ple, it should be pointed out that lignin and tent during heating than lignin (cf. the higher carbohydrates are gradually converted into vol- content of carbohydrates in intact birch wood, atile~and "extractive-like material," which in see Table 1) (Fig. 1 and Table 2). However, it turn is partly degraded together with the orig- is also likely that differences in the chemical - - 45 - u 0.85 40 .. Birch y = 2.318~+ 2.5102 a R' = 0.9813 3 5 0.8 Pine zosc Fz 3 % 5 0.75 w Pine 230°C C, '5 0 e A Birch 200°C S..a 30 *a a Birch 220°C m ., 0.7 % 25 < 3 5 0.65 :@20 y = 2.0991~+ 1.0751 - R' 0.6 '9 = 0.9788 '- 15 3 5 7 9 10 Reaction time, h 5 7 l1 l3 l7 FIG.2. Change in mass ratio of [(glucose)/(total car- Total mass loss, % of initial bohydrates)] in the wood feedstocks during the heat treat- FIG.