Fuel 96 (2012) 161167

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Improvement of charcoal yield by two-step pyrolysis on eucalyptus wood: A thermogravimetric study

Khalid Elyounssi a,, Franois-Xavier Collard b, Jean-aim Ngollo Mateke b, Jol Blin b,c
a

Centre de Recherche Forestire, Avenue Omar Ibn El Khattab, BP 763 Agdal, Rabat, Morocco Biomass Energy & Biofuels Laboratory (LBEB), International Institute for Water and Environmental Engineering, 01 BP 594 Ouagadougou, Burkina Faso c Biomass Energy Unit, French Agricultural Research Centre for International Development (CIRAD), TA B-42/16;73, rue jean Franois Breton, 34398 Montpellier Cedex 5, France
b

a r t i c l e

i n f o

a b s t r a c t
In previous work, we showed that two-step biomass pyrolysis, consisting of a rst low temperature step (T = 360 C, so a low actual heating rate) until the mass loss of the solid reached approximately 50%, followed rapidly by a high temperature step (T > 600 C, so a high actual heating rate) led to optimize charcoal yields with values of up to 40%. In this paper, we describe thermogravimetric analysis studies on eucalyptus wood and its three constituents, i.e. cellulose, xylan and lignin, in order to explain the phenomena behind these results. Two-step pyrolysis experiments were conducted in a TGA oven up to 900 C with a rst slow pyrolysis step at a low heating rate of 2 C min1, followed by a fast pyrolysis step with a heating rate of 100 C min1. Char yields from eucalyptus wood were increased from 18.8%, for the simple 2 C min1 pyrolysis, up to 22.8% when the heating rate change was operated at a temperature of 360 C. Char yield from cellulose was also increased, though only very slightly, when the heating rate was changed in the 330360 C temperature range. Conversely, char yield obtained from xylan and lignin in two-step pyrolysis was always lower than that obtained by simple 2 C min1 pyrolysis. It appeared from this work that two-step pyrolysis of the eucalyptus sample could not be regarded and described as the result of the sum of the pyrolysis of its constituents. There was a matrix effect with interactions that promoted char formation during two-step pyrolysis. 2012 Elsevier Ltd. All rights reserved.

Article history: Received 18 February 2011 Received in revised form 12 January 2012 Accepted 16 January 2012 Available online 3 February 2012 Keywords: Two-step pyrolysis Char yield Eucalyptus Wood constituents Interaction

1. Introduction Charcoal, an end-product of the carbonization process, is continuing to arouse growing interest worldwide. In developing countries, it is a vital and very appreciated source of energy, while in developed countries it is seen, in addition to its habitual use for barbecues, as an alternative to coal as a source of reductant for the industrial reduction of metallic dioxide (steel, silicon industries). To that end, the Norwegian ferrosilicon industry consumed more than 70,000 tons of wood charcoal in 1998 to reduce silicon dioxide to silicon [1]. Moreover, in order to reduce pollution and greenhouse gas emissions, the concept of using wood to make iron in a charcoal blast furnace is currently being applied in Brazil [2,3]. In this context, research work has been undertaken by several teams in order to optimize charcoal yield [1,48]. At the moment, charcoal yield from carbonization processes under atmospheric pressure (earthmount kilns, metallic kilns, and industrial processes) rarely reach 30% [1,4]. However, better yields, reaching 40%, have been obtained by carbonizing biomass feed stock in

Corresponding author. Tel.: +212 537666405; fax: +212 537671151.

E-mail address: k.younssi71@gmail.com (K. Elyounssi). 0016-2361/$ - see front matter 2012 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2012.01.030

the laboratory and in a pilot plant at a pressure exceeding 1 MPa [1,48]. The technological level required and the production costs for charcoal produced by processes at such a pressure constitute an obstacle when the charcoal is produced for energy use. It has been reported in the literature that charcoal yield depends on several process parameters: the nal temperature, the particle size of the biomass, the heating rate value and the reaction atmosphere [4,9]. All of the last three parameters affect the pyrolysis process by inuencing the residence time of volatiles in the charring residue. In fact, the larger the particle size of the material, or the lower the heating rate, or the more conned the reaction environment is, the longer the volatile residence time will be, which promotes secondary reactions responsible for char formation. In this respect, it has been emphasized in previous published works [5,10,11] that obtaining high charcoal yields by pyrolysis under pressure is notably due to the fact that the volatiles are held captive in the biomass. However, in earlier work carried out by the authors [12], a study of the charcoal production process based on changes in xed-carbon yield as a function of time and heating rates, revealed a regime that enabled high quality charcoal yields of up to 40% from eucalyptus wood under atmospheric pressure. This regime consisted of a two-step pyrolysis process: a low temperature step

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(T = 360 C, so a low heating rate) until the mass loss of the solid reached approximately 50%, followed rapidly by a high temperature step (T > 600 C, so a high heating rate). The two-step pyrolysis mechanism responsible for increased char yield was not clear and called for an in-depth study to assess it. In fact, the char residue at a 50% yield stage was a solid matrix in which cellulose and hemicelluloses had undergone substantial decomposition, but a major share of the initial lignin had yet to decompose. A rapid rise in the temperature of such a residue in the second step seemed to promote char formation reactions. In the work described here, we undertook a thermogravimetric analysis to show the existence of a two-step pyrolysis scheme giving higher charcoal yields than those obtained by simple slow pyrolysis. In addition to understanding any individual contribution made by the different wood constituents (hemicelluloses, cellulose and lignin) to this increase in char yield, the aim was to determine the temperature at which the switch to the second step could be recommended. The ultimate goal was to investigate the possibility of improving char yield merely by adjusting the temperaturetime prole of the thermochemical conversion process under atmospheric pressure.

2.2. Thermogravimetric analysis A Setaram Setsys Evolution 16 thermogravimetry analyzer (TGA) was used to carry out the experiments. An argon ow of 20 mL min1 was used as an inert purge gas. All experiments were performed from the ambient temperature up to a value of 900 C with an isothermal plateau of 10 min at that temperature. An isothermal plateau of 10 min at 105 C was also applied to dry the material before actual pyrolysis began. Sample masses of approximately 18 mg were used in the experiments. The TG curves obtained gave the normalized mass (%) as a function of temperature. In previous work [12], the authors reported that two-step pyrolysis (a low heating rate step followed by a rapid rise in the charring material temperature to values exceeding 650 C) increased the nal char yield. That increase was greatest when the high heating rate (the rise in temperature) was applied to samples which approximately reached 50% mass loss from the original feedstock. In this work, two-step pyrolysis experiments were carried out to corroborate these results through TGA analyses; an initial slow pyrolysis step used a low heating rate of 2 C min1 whilst, during the second step, the heating rate was changed to 100 C min1. Furthermore, in addition to the aforementioned 50% mass loss of the solid sample at which the change to high heating rate was found to maximize char yield, the inuence of the heating rate change was also tested for values of 40%, 60% and 70% mass loss. In this respect, the rst TGA experiments with a 2 C min1 heating rate were performed in order to evaluate which temperature (called Ti) corresponded to the selected mass losses. Mass loss values of 40%, 50%, 60% and 70% were obtained at 300 C, 330 C, 360 C and 400 C respectively. Different pyrolysis runs with different temperature patterns were carried out for this purpose: Two simple runs with a constant heating rate of 2 C min1 and 100 C min1, respectively, from 105 C to 900 C. The 2 C min1 run was considered as traditional slow pyrolysis and its char yield was used as a reference for comparison with the other runs. Two-step runs, with a rst step at a 2 C min1 heating rate from 105 C to Ti, followed by a second step with a 100 C min1 heating rate from Ti to 900 C (see Fig. 1). On the other hand, in order to investigate the respective contribution of each wood constituent to the increase in char yield when two-step pyrolysis was applied on eucalyptus wood, the same set of runs was also conducted for the cellulose, xylan and lignin samples. Runs with empty crucibles were used as blank curves to be subtracted from all the sample curves. Each pattern was repeated three times for the eucalyptus samples, in order to have reliable results. The results showed good repeatability with standard deviations in the range of 0.010.67 (see Table 2).

2. Materials and methods 2.1. Plant material Eucalyptus wood was used in this work because of its widespread use as feedstock for bioenergy applications and is deemed to give good quality of char. Eucalyptus trees grow quickly and are suitable for many types of soil quality, even partially degraded. The material used was milled and sieved between 212400 lm. It was then dried in a ventilated oven at 105 C and stored for the thermogravimetric analysis. The particle size adopted was relatively high given that the goal of this work was to approach the conditions of macro-particle pyrolysis, characterized by temperature gradients within the biomass particle due to internal and external heat transfer control [13]. Table 1 shows the principal constituents (summative), determined using the protocol detailed in Ref. [14], and the ultimate and proximate analysis of the eucalyptus wood used. In order to assess their individual pyrolysis behavior, the commercial chemical constituents of the wood obtained from SigmaAldrich in France, namely microcrystalline cellulose (Ref. K39709730 920), xylan from beech wood as a representative of hemicelluloses (Ref. X4252-25G) and lignin alkali (Ref. 370959-100G), were also studied.

Table 1 Proximate, ultimate and constituents analysis of eucalyptus wood. Ultimate analysis Carbona Hydrogena Nitrogena Oxygena Proximate analysis Moisture Volatile mattera Fixed carbona Asha Constituents analysis Extractives Hemicelluloses Cellulose Lignin
a

Percentage 51.22 5.86 <0.3 41.72 9.40 80.81 18.62 0.57 2.2 27.3 34.7 35.8

Weight percentage on dry basis. Fig. 1. A temperature pattern of two-step pyrolysis.

K. Elyounssi et al. / Fuel 96 (2012) 161167 Table 2 Char yields at 900 C obtained from eucalyptus wood, cellulose, xylan and lignin. Material Eucalyptus Run Elow E400 E360 E330 E300 Ehigh Llow L400 L330 L300 Lhigh Xlow X300 X230 Xhigh Clow C360 C330 C300 Chigh Experimented (%) 18.8 20.9 22.8 22.2 21.8 21.7 43.6 41.9 41.1 39.7 37.9 23.7 21.5 19.9 16.2 14.1 14.4 14.5 10.1 4.6 Standard deviation 0.10 0.01 0.25 0.16 0.67 0.09 Calculated (%)

163

100 90 80
Eucalyptus xylan cellulose Lignin

Lignin

Xylan

Cellulose

27.0 25.9 25.6 25.6 23.6 19.5

Normalized mass %

70 60 50 40 30 20 10 0 100 200 300 400 500 600 700

800

900

Temperature (C)
Fig. 2a. TG curves of eucalyptus wood, cellulose, xylan and lignin at 2 C min1

Mass losse rate dm/dt (mg/min)

For clarity, each pyrolysis run was referred to by the rst letter of the material involved, followed by the temperature at which the heating rate was changed. Thus, ETi (or CTi, XTi and LTi) referred to the pyrolysis run for eucalyptus wood (or cellulose, xylan and lignin) with a heating rate change at temperature Ti. In particular, the 2 C min1 and the 100 C min1 runs were referred to as Elow and Ehigh for eucalyptus wood (Clow and Chigh for cellulose, Xlow and Xhigh for xylan and Llow and Lhigh for lignin). For all the experiments, the char yields obtained after the isothermal plateau of 10 min at 900 C were used to compare the efciency of the different runs. Char yield Yi (where i stands for wood, cellulose, xylan or lignin) is dened as

0.0
Eucalyptus

-0.2

xylan cellulose

-0.4

Lignin

-0.6

-0.8

-1.0

Yi Mci=Mi 100

-1.2

where Mi and Mci are the dried mass of material i and the mass of its char, respectively. It is important to note that all yields discussed in this study were obtained at 900 C after testing oven TGA, and were thus necessarily lower than those obtained in industrial processes, in which the temperature rarely rises above 600 C. 3. Results and discussion 3.1. General aspects of the thermogravimetric analysis Fig. 2a and 2b show the normalized mass (TG) and the weight loss rate (DTG) curves for the pyrolysis of eucalyptus wood, cellulose, xylan and lignin at the 2 C min1 heating rate (Elow, Clow, Xlow and Llow runs). The curves tally well with those reported in the literature [1517]. The onset temperatures (dened as temperatures corresponding to a weight loss of 5%) for the pyrolysis of eucalyptus wood, cellulose, xylan and lignin were 238 C, 288 C, 183 C and 219 C respectively. The DTG curve for eucalyptus wood in Fig. 2b displayed two signicant peaks (called Th,w and Tc,w respectively): the rst at 268 C and the second at 328 C. These two peaks are generally attributed respectively to the decomposition of hemicelluloses and cellulose present in wood. Indeed, the xylan and cellulose DTG curves at the 2 C min1 heating rate (Xlow and Clow runs) in the same gure show a signicant peak, each centred on the temperature of 272 C and 315 C respectively, which tallied with the range of values reported in the literature for low and moderate heating rates: 260299 C and 315355 C respectively [9,10,1520]. The lignin DTG curve displayed a very large

100

200

300

400

500

600

700

800

900

temperature (C)
Fig. 2b. DTG curves of eucalyptus wood, cellulose, xylan and lignin at 2 C min1

and small peak with a maximum value at about 355 C. The peak temperatures of the eucalyptus wood DTG curve deviated slightly from those of commercial xylan and cellulose, by just 4 C and 13 C respectively. This was due in part to the contribution of the lignin DTG curve to the global DTG curve of the eucalyptus wood. In fact, the weighted summative law (Eq. (2)) can be applied to the DTG curves so that the DTG curve of eucalyptus wood is somehow the weighted sum of the DTG curves of its constituents. As a result, the peak temperatures corresponding to cellulose and hemicelluloses observed in the DTG curve of eucalyptus wood are both shifted and lowered in intensity, compared to those obtained from these two constituents separately, due to the contribution of the lignin peak. This was due also to the fact that cellulose is not as crystalline in its commercial form as in wood (the crystallinity degree of cellulose is known to affect its peak temperature) and that xylan is not the only hemicelluloses in eucalyptus, and to the structural arrangement and the chemical bonds of each constituent within the natural precursor [10]. The char yield of the Elow run at 900 C was 18.8%. The yields of Clow, Xlow and Llow were 14.1%, 23.7% and 43.6% respectively. The magnitude of these values also tallies well with that reported in the literature [15,1720]. Cellulose gives the lowest char yield, followed by xylan, while lignin gives the highest value.

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Fig. 3 shows the TG curves for the pyrolysis of eucalyptus wood using the different patterns described in Section 2.2. All the TG curves with two-step pyrolysis show a delay at the beginning of the second step (i.e. when the heating rate was changed from 2 C min1 to 100 C min1). This is displayed in Fig. 3 by the encircled lower area in the case of the E300 curve. This delay resulted from the thermal lag that may have existed between the sample temperature and that measured by the oven thermocouple, a phenomenon that amplies as the heating rate increases [1,10,11,21]. It is mainly due to heat transfer limitations at low temperatures, especially in the case of samples with large sizes like ours. This phenomenon could easily be seen in the Ehigh run (as shown by the upper encircled area) as its TG curve shifted to the right compared to that of the Elow run. Indeed, the pyrolysis onset temperature of the former was delayed to 306 C while it was only 242 C for the latter. As the temperature rose, heat transfer by radiation became determinant and the thermal lag lowered. The delay then decreased, as found for the E360 and the E400 runs. These remarks were also true for the cellulose, xylan and lignin runs.

than simple slow pyrolysis. To the best of our knowledge, these ndings have not been reported before. The char yield of 21.7% from the Ehigh run was surprising, since it was expected that this rapid heating rate would result in a lower char yield than the 2 C min1 run. This could be attributed to heat transfer limitations at the low temperatures, at the beginning of the experiment, so that the temperature in the sample remained quite low. This led to a relatively slow pyrolysis phase at the beginning of this run. Consequently, the Ehigh run was quite similar to the other two-step runs and resulted in a char yield of the same magnitude. 3.3. Thermogravimetric analysis of the pyrolysis of wood constituents The fact that the maximum char yield in two-step pyrolysis of eucalyptus was obtained when the heating rate was changed from 2 C min1 to 100 C min1 precisely at a temperature of 360 C, at which cellulose decomposition had already reached its maximum, suggests the possible role of that wood constituent in the pyrolysis process as a whole. In fact, the individual behavior of the three wood constituents when the whole eucalyptus wood sample underwent two-step pyrolysis is not known. This increase in char yield from eucalyptus wood might result either from the individual increase of char yield from certain constituents, or may be due to certain interactions between constituents during decomposition. To investigate this point, the same set of runs was applied to xylan, cellulose and lignin. Fig. 4 shows the TG curves for the cellulose pyrolysis runs. From this gure, it can be seen that the temperature pattern had an important effect on char yield at 900 C. The value of the char yield decreased substantially from 14.1% to 4.6% when the heating rate increased from 2 C min1 (Clow) to 100 C min1 (Chigh). This was largely expected since there are many reports in the literature of an inverse correlation between the nal char yield from cellulose pyrolysis and the heating rate [1,4,10,11,2126]. According to the widely-accepted Waterloo mechanism of cellulose degradation, the slow heating rate of 2 C min1 provided sufcient time for the sample to undergo dehydration at temperatures lower than 300 C which, in addition to secondary reactions favoured by long volatile residence times, promoted char formation [27]. As for eucalyptus wood, the temperature Ti inuenced char yield changes from the CTi runs. The C300 run gave a char yield of 10.1%, which was between those of the Chigh and Clow runs. The C330 and the C360 runs resulted in almost equal char yield values: 14.5% and 14.4% respectively, which were slightly higher than that of the Clow

3.2. Thermogravimetric analysis of wood pyrolysis As shown by Fig. 3, the different patterns of eucalyptus wood pyrolysis resulted in different char yields (see Table 2). The Elow run provided the lowest char yield at 900 C with a value of 18.8% compared to the other runs. Indeed, the char yield from the ETi runs increased, compared to the Elow run, when the heating rate was changed, at a temperature Ti within the pyrolysis process, from 2 C min1 to 100 C min1. It reached 21.8%, 22.2%, 22.8% and 20.9% for the E300, E330, E360 and E400 runs respectively. It appeared that the value of temperature Ti played an important role in the changes in char yield from the ETi runs and that the change in heating rate at a Ti value in the 330360 C range (i.e. 50% mass loss) resulted in the highest char yields. It is clear from Fig. 2a that this range of temperatures corresponded to the pyrolysis stage at which cellulose decomposition reached and exceeded its peak and the eucalyptus mass loss was approximately 50%. This is in perfect agreement with the results reported by the authors [12]. This remark was true for the three replicate runs. On the other hand, it has been stated that a low heating rate over the whole pyrolysis process favors a high char yield [1,4]. In that case, the Elow run would have resulted in the highest char yield. However, the experiments carried out here showed that two-step pyrolysis (ETi runs) resulted in even higher char yield

100 90 80 Normalized mass ( %) 70 60 50 40 30 20 10 0 100 200 300 400 500 600 700 800 900 Temperature (C)
E.low E.high E300

100 90 80 Normalized mass (%) 70 60 50 40 30 20 10 0 100 200 300 400 500 600 700 800 900 Temperature (C)
C.low C.high C300 C330 C360

E330 E360 E400

Fig. 3. Effect of the temperature pattern on char yield from eucalyptus wood.

Fig. 4. Effect of the temperature pattern on char yield from cellulose.

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165

run. It is worth noting that the peak temperature for maximum cellulose pyrolysis (called Tc) was 315 C. We can thus conclude that the char yield from cellulose was optimum if a low heating rate was conserved up to Ti = Tc. When the heating rate was changed (from 2 C min1 to 100 C min1) at a temperature Ti lower than the peak temperature Tc (Chigh and C300 runs), the char yield obtained was smaller than that of Clow run. Indeed, the C330 and C360 runs increased the char yield to more than the Clow yield, but that increase was not signicant enough to state that the increase in char yield obtained from E330 and E360 runs, compared to the Elow run, was due to a char yield increase from the cellulose present in eucalyptus wood. On the other hand, Figs. 5 and 6 show the TG curves for the xylan and lignin pyrolysis runs. Xylan and lignin seemed to behave exactly the same with regard to the temperature patterns adopted in terms of the nal char yield changes. In fact, the nal char yield decreased when the heating rate increased, from 23.7% to 16.2% for the Xlow and Xhigh runs respectively, and from 43.6% to 37.9% for the Llow and Lhigh runs respectively. This yield decrease was smaller than for cellulose. Here too, the char yields obtained from the XTi and LTi runs were smaller than for the Xlow (Llow) run when the heating rate was changed (from 2 C min1 to 100 C min1) during the pyrolysis process at a temperature Ti lower than the temperature of the maximum thermochemical degradation Tx = 272 C (TL = 355 C). Moreover, the closer Ti was to Tx (TL), the closer the nal char yield from XTi (LTi) was to the char yield from the Xlow (Llow) run (which became an asymptotic value). The rise in heating rate at a temperature Ti higher than Tx (TL) failed to increase the char yield from XTi (LTi) to values exceeding those for the Xlow (Llow) run. To conclude, we can say that char yields from xylan and lignin pyrolysis could not be increased by two-step pyrolysis to values over those obtained from the Xlow and the Llow runs. 3.4. Role of interaction between wood constituents during pyrolysis in the char increase Two-step pyrolysis of eucalyptus wood, as tested here, increased the char yield obtained at 900 C from the Elow run up to 22.8% when the heating rate change was operated at a temperature just above that of the peak cellulose pyrolysis in wood Tc,w = 328 C. Unexpectedly, two-step pyrolysis of the three individual wood constituents did not result in the same trend. That is, the char yield increase resulting from two-step pyrolysis of cellulose was very small and there was no increase for xylan and lignin, compared to simple 2 C min1 pyrolysis. The increase in char

100
L.low

90 80 Normalized mass (%) 70 60 50 40 30 20 10 0 100 200 300 400 500 600 Temperature (C) 700

L.high L300 L330 L400 L500

800

900

Fig. 6. Effect of the temperature pattern on char yield from lignin.

100 90 80 70
X.low X.high X230 X300

yield from eucalyptus wood cannot therefore be explained by the individual contributions of the constituents. Hence, we must look for what may have differentiated the ETi runs from the Elow run. In fact, the ETi runs and the Elow run had in common the rst 2 C min1 step. For example, the wood samples underwent a slow heating rate pyrolysis step at 2 C min1 over the 105360 C range in both the E360 and Elow runs. During this step, char yields for the two runs are almost the same up to 360 C (see Fig. 3). For the 360 900 C temperature range, the sample in the Elow run continued its slow pyrolysis while that in the E360 run underwent rapid pyrolysis at 100 C min1. The char yields obtained from the two runs at 900 C were dramatically different. The individual contributions of the constituents to the increase in char yield from eucalyptus wood being dismissed, we can conclude that there were certainly some interactions within the carbonaceous residues during the second step (e.g. the 360900 C range), especially between the lignin-derived products and the solid residue (while the mass losses of xylan and cellulose at 360 C were 61.8% and 74.1% respectively, and were converted into solid residue (char) at this temperature), which inhibited char formation at the low heating rate (Elow) and/or promoted it at a high heating rate (E360). The promoting effect of such interactions in the twostep runs were more intensive when the high heating rate was operated at a temperature just above the temperature of peak cellulose pyrolysis in wood (Tc,w = 328 C) . To assess the existence of interactions during wood pyrolysis, tested and calculated char yields from eucalyptus wood were compared. The calculated values were obtained using a weighted summative law of the three constituents according to Eq. (2) [18]:

Ye H% Yh C% Yc L% Yl

Normalized mass (%)

60 50 40 30 20 10 0 100 200 300 400 500 600 700 800 900 Temperature (C)

Fig. 5. Effect of the temperature pattern on char yield from xylan.

where H%, C% and L% are the percentages of hemicelluloses, cellulose and lignin in the precursor, which were represented by the three commercial constituents studied in this work (Table 1), and Yh, Yc and Yl are their respective individual char yields. Based on this equation, calculated char yields from the experiments carried out in our work are shown in Table 2. As some experiments were not performed for individual wood constituents, and in order to obtain calculated values from the ETi runs for which there was no corresponding constituent char yield (XTi, CTi), the immediately lower value of the char yield was adopted. For example, char yield from X360 was given the value of the X300 yield. Also, Table 3 shows the respective contribution of each constituent to the char obtained in term of weight fraction within the eucalyptus wood char for Elow,

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Table 3 Evaluated respective contribution of each constituent to eucalyptus wood char synthesis. Run Elow E300 Ehigh
a

CC%a 18.1 14.8 8.1

CX%a 24.0 24.9 22.6

CL%a 57.9 60.3 69.4

Calculated yield (%) 27.0 23.6 19.5

In weight fraction as dened by Eq. (3).

E300 and Ehigh runs. The respective contribution of constituent j (where j stands for cellulose, xylan or lignin) is dened as:

Cj% J% Yj=Ye

where J%, Yj and Ye are the percentage of the constituent j in wood, its respective individual char yield and the calculated char yield of eucalyptus wood as dened in Eq. (2) respectively. The calculated char yield from the Elow run was 27.0% at 900 C, which was much greater than the experimental yield at 18.8%. Cagnon et al. [18] reported the same result with four precursors: coconut shells, plum stones, treated olive stones and soft wood at a heating rate of 5 C min1. The calculated char yields (30.8%, 31.1%, 29.1% and 24.9% respectively) were higher than the experimental yields (25.6%, 24.6%, 27.4% and 21.3% respectively). However, the calculated char yield from a mixture of hemicelluloses, cellulose and lignin having a similar composition to coconut shells was very close to the experimental yield: 33.5% instead of 32.7%. These constituents in a mixture seemed to behave individually during pyrolysis, leading to an experimental char yield for the sample mixture that is very close to calculated yield. The absence of interactions during pyrolysis of the three constituents in a mixture was also conrmed by Yang et al. [19], who carried out pyrolysis at 10 C min1 for 15 different mixture compositions. In the same way, from Table 3, we can see that if the constituents within eucalyptus wood behaved individually during the Elow run as if they were in mixture, the experimental char yield would equal the calculated value, which was, as seen above, much greater than the experimental one. These results demonstrate that during slow pyrolysis of wood, there are indeed interactions between the three constituents that inhibit some of the char formation reactions, especially after the cellulose decomposition stage (e.g. during the 360900 C range), probably due to the matrix effect (polymer linkage, presence of salts). This meant that it was not possible to obtain char yield values from slow pyrolysis of wood that were as high as the calculated values. Conversely, at a high heating rate of 100 C min1 (Ehigh), the calculated and the experimental char yields were very close: 19.5% and 21.7% respectively. The high heating rate throughout the wood pyrolysis process seemed to enhance interactions that promoted char formation during the lignin decomposition stage. In absence of those interactions at 100 C min1, the experimental char yield from the Ehigh run would be even lower than the calculated one as in the case of the Elow run, but it does not appear to be the case here. For the E360 run, the application of the 100 C min1 heating rate at T = 360 C seemed to change the nature of interactions over the 360900 C temperature range, resulting in char yield value greater than that from the Elow run. This was also true for all the other ETi runs since their char yield values were greater than that of the Elow. According to this fact (i.e. interactions that promote char formation are enhanced by high heating rate over the Ti900 C temperature range), it may be expected that the wider the Ti-900 C temperature range, over which pyrolysis occurred at the 100 C min1 heating rate, is, the higher the char yield from the ETi run will be, and vice versa. But this was not true since the

char yield from the E360 run was greater than those from the E300 and the Ehigh runs even though the 360900 C range for the E360 run was narrower than the 300900 C and the 105 900 C ranges for the E300 and Ehigh runs, respectively. Actually, of all the ETi runs, char yield from the E360 run was maximum. The question here is why the experimental char yield values showed a maximum exactly for the E360 run. In fact, the temperature 360 C is slightly higher than the peak cellulose pyrolysis in wood of Tc,w = 328 C. For this run, cellulose pyrolysis in the wood samples underwent complete slow pyrolysis over the 105360 C range and very likely resulted in interesting amount of char, as it would also be the case for the hemicelluloses. The application of the 100 C min1 heating rate at Ti = 360 C produced more char due to the promoting interactions that took place over the 360 900 C range. In contrast, for the E300 run (and to some extent the E330 run), when the sample temperature during pyrolysis at 2 C min1 reached Ti = 300 C (330 C), the cellulose present in wood did not decompose completely at this heating rate value and the application of the 100 C min1 heating rate at this temperature caused the cellulose to undergo rapid pyrolysis and result therefore in a small amount of char at such a high heating rate. The char yield from the E300 (E330) run was then lowered and became smaller than that from the E360 one. The char yield from the Ehigh run was even lower than that from the E300 run for the same reason. In fact, the application of the 100 C min1 heating rate at Ti = 105 C caused both the cellulose and the hemicelluloses in wood to undergo rapid pyrolysis, resulting in an even smaller amounts of char. On the other hand, for the E400 run, cellulose and hemicelluloses in wood underwent complete slow pyrolysis and very likely resulted in amounts of char as high as for the E360 run up to 360 C. The difference between the two runs was the 360400 C temperature range. For the wood sample in the E400 run, there were no promoting interactions over this temperature range since the heating rate was only of 2 C min1. The nal char yield from the E400 run was then smaller than that of the E360 one. The increase in char yield by two-step pyrolysis (especially from the E330 and E360 runs) seems to consist of a compromise: the low heating rate during the rst step gave high char yields from the constituents as if they were individual, while the change in heating rate to 100 C min1, especially when the cellulose and hemicelluloses had almost completely decomposed, inhibited subsequent interactions that decreased char yield or promoted those that increased it.

4. Conclusions The present study offers the following conclusions: (1) Two-step pyrolysis of eucalyptus wood, a low heating rate (2 C min1) step followed by a high heating rate (100 C min1) step, increases the char yield obtained from simple slow pyrolysis (Elow run), which has been recommended until now as giving good char yields from biomass. This increase was greatest when the second step began at a temperature Ti just above the cellulose pyrolysis peak in wood (Tc,w = 328 C). The char yield amounted to 22.8% when the second step began at a temperature of 360 C, while that of the Elow run was only of 18.8%. (2) The increase in char yield from eucalyptus wood cannot be supplely explained by the individual contributions of the constituents; two-step pyrolysis of cellulose seemed to increase very slightly the char yield obtained from simple slow pyrolysis (Clow run) when the second step began at a temperature Ti over Tc = 315 C and char yields from xylan

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and lignin pyrolysis could not be increased by two-step pyrolysis to values higher than those obtained from simple slow pyrolysis (Xlow and Llow runs). (3) The increase in char yield obtained from two-step pyrolysis of eucalyptus wood was certainly due to interactions, during the second step pyrolysis at 100 C/min, between the lignin derived products and the charring residue from cellulose and hemicelluloses from the rst slow pyrolysis step. These interactions were greatest when the second step began at a temperature Ti just higher than the peak cellulose pyrolysis in wood (Tc,w). Then, to optimize char yield, the low heating rate was necessary at the beginning of pyrolysis until the temperature equalled a temperature Ti just above the Tc, w = 328 C to allow char formation from the cellulose and hemicelluloses present in wood. Just after temperature Ti, application of a high heating rate became crucial to increase char yield. Further research works are ongoing to investigate mechanisms of interaction between the degradation products of lignin and char during the second fast pyrolysis step.

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