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Songklanakarin J. Sci. Technol.

30 (3), 393-404, May - Jun. 2008
http://www.sjst.psu.ac.th

Original Article

Product yields and characteristics of rice husk, rice straw and corncob
during fast pyrolysis in a drop-tube/fixed-bed reactor
Janewit Wannapeera, Nakorn Worasuwannarak and Suneerat Pipatmanomai*

The Joint Graduate School of Energy and Environment,
King Mongkut’s University of Technology Thonburi, Bangmod, Tung Kru, Bangkok, 10140 Thailand.

Received 20 November 2007; Accepted 26 June 2008

Abstract

Fast pyrolysis of rice husk, rice straw and corncob were investigated in a newly constructed drop-tube/fixed-bed
reactor, which enables pyrolysis experiments under conditions closely simulating those occurring in commercial gasifiers
such as fluidised-bed gasifiers. Biomass samples were pyrolysed with a fast heating rate (i.e. > 1,000oC s-1), up to 850oC and
holding times ranging from 1 to 10,800 seconds. Within 1 second after the biomass was injected into the reactor, consider-
able weight loss occurred instantaneously, leaving only a small amount of char, i.e. ~10-30 %. For all three samples, the
weight loss continued throughout the range of holding times used but at an extremely slow rate, i.e. 1.3 % hr-1. The weight
loss rates observed for the three biomass samples were affected by the proportion of the biomass chemical components
as well as the metal species contents. Corncob, which had the lowest lignin content but highest cellulose content, had the
highest pyrolysis weight loss rate. On the other hand, rice husk containing a relatively high lignin content, had the lowest
pyrolysis rate. The metal species (Na, K, Ca and Mg) were found to increase devolatilisation yield depending on their
contents in biomass. The influence of the metal species was the most pronounced for rice straw, having the highest total
metal species content. As the pyrolysis progressed, each biomass exhibited different char characteristics. Scanning electron
microscopy (SEM) pictures clearly showed the individual changes in geometry for all biomass-derived chars as well as
their decrease in combustion reactivities. The gas formation profiles for all three biomass samples showed almost the same
trend, with CO contributed by cellulose decomposition as the major gas product.

Keywords: fast pyrolysis, biomass, drop-tube/fixed-bed reactor, char, metal species

1. Introduction al., 2007). Particularly, three agricultural residues including
rice husk, rice straw and corncob are statistically shown to
Due to environmental concerns over excessive fossil have high resource potential in Thailand. Another study by
fuel usage, biomass has increasingly become of interest as a Thailand Research Fund (2007) reported similar results in
promising renewable energy source to mitigate global warm- terms of annual production; the estimated maximum produc-
ing (Rosillo-Calle et al., 2000). In Thailand, well-recognized tion of rice husk, rice straw and corncob were 6.2, 32.2 and
as one of the first rank exporters of agricultural and food 1.8 million tonnes per year, respectively. However, the
products, biomass, including abundant by-products from potential of un-utilised rice husk and corncob at the national
agricultural process industries as well as residues from post level was reported to be rather low due to extensive utilis-
harvest such as bagasse, corncob, coconut shell, etc., is largely ation for both energy and non-energy purposes. On the other
available for use as alternative energy source (Utistham et hand, as much as 12.9 million tonnes per year of rice straw
remain un-utilized. Despite these findings, it is believed that
rice husk and corncob still have potential at the local level
*Corresponding author.
Email address: suneerat_p@jgsee.kmutt.ac.th
for small-scale or decentralized systems.

and to produce electricity. Hayashi et al. study as the model components.. Therefore. applications and the production of electricity for small scale 2007). although biomass gas.. 2002.394 J.. 2007. 1993. To investigate the effect of the chemical and Skorupska.. Hayashi and Although there have been a number of studies of the Miura. only the production of heat in large scale particle residence time (Hayashi et al. 2008 Various thermo-chemical processes have been devel.. a drop-tube/fixed-bed reactor was con- ification has been studied for decades. These were ground and sieved influence of pyrolysis parameters on the char yield as well as to a diameter less than 75 µm. The biomass samples used for this study were rice mines the overall gasification rate. while corncob contains almost no ash. which is comparable to or even higher than the gas behaviour was also investigated with a focus on the four . etc (Rosillo-Calle et al. 1993). The use of drop-tube or free fall reactors could role of inherent metal species in the primary reactions during overcome the heating rate limitation.e. reactors. Not only the weight microscope. which is samples. it deter. 1993). possible cata- particles is determined based on the terminal velocity of lytic effect of the metal species on biomass pyrolysis particles. Gani are different. The relative combustion reactivities of the char volatiles are released leaving the solid char. allow rapid heating Fischer-Tropsch process). In the presence were determined using a thermogravimetric analyser and of reactive agents. The drop-tube/fixed-bed high quality can be used as an intermediate for other value. In this study. 1997. including cellu- Several investigations on biomass pyrolysis have lose. The product gas from gasification defined time-temperature profiles under high heating rate can be used for various purposes. there is no significant difference in the volatile matter these reactor configurations limit the attainable heating rates contents and elemental contents among the three biomass to a relatively slow range. in Table 2. Fixed-bed re. 2000. peak temperature and trial purposes. Therefore. 2000). Technol. especially tar. 2004. rice (compared to fossil fuel technologies) as well as for straw and corncob. 2004. Although Tsai et al. develop.. The effects of pyrolysis temperature and holding time on the Similar to other thermal conversion processes. the interdependency of heating rate. been carried out using various apparatuses. i. structed for investigation of the behaviour of three selected ments for more effective and reduced cost technologies agricultural residues available in Thailand. to date. the samples were the reactivity and morphology of the recovered chars is dried in a vacuum oven at 70oC for 24 hours before the necessary to explain the reaction behaviour and to predict experiments. under fast pyrolysis conditions simulat- advanced technologies like biomass-to-liquid (BTL) are still ing those occurring in commercial fluidised bed gasifiers. especially for kinetic studies. including fuel for direct conditions as well as minimising secondary cracking re- combustion to produce heat.. weight loss of solid fuels during the entire gasification pro- cess. Rice husk has the highest ash content. The proximate and ultimate analysis results are the fate of char undergoing the gasification step. 2007). hemicellulose. 2005. rice straw and corncob. given in Table 1 and chemical components. the weight losses and characteristics of char and gases were initial step of gasification is pyrolysis. Experimental which char is formed also have significant effects on the char characteristics and hence the reaction rate of char in the 2. Sánchez et al. Wannapeera et al. / Songklanakarin J.. Sigma Aldrich] were used in the and consequently reduce the yield of volatiles. during which the investigated. a challenge. applications are seen in real practice. However. none have been atmosphere inside the reactor. rice husk. the variation of their chemical components can be far from the conditions in commercial reactors (Carpenter clearly observed. and the heating rate of carried out on biomass pyrolysis. less than 100oC min-1. The product gas with due to the very diluted gas phase. cold a rapid pyrolysis of brown coals and lignites (Kershaw et al. the oped and implemented worldwide. Since the gasification rate of char is much slower compared to the pyrolysis rate. but their ash contents widely used (Caballero et al. i. Although wire-mesh reactors enable well- conversion technology.1 Biomass samples and sample preparation subsequent gasification step. for use in gas engines or gas actions. 2000). While direct combustion time-temperature history cannot be defined accurately due to of biomass has widely been used for household and indus. All three types of biomass have similarly high volatile matter actors and thermogravimetric analyzers (TGA) have been contents and low fixed carbon contents. 30 (3). 393-404. a commercial micro- volatiles and chars or entrainment of volatiles in the vicinity crystalline cellulose powder [Sigma Aldrich] and organic- of the heated coal/char enhance secondary cracking reactions solved lignin [20-100 µm. operational conditions during the pyrolysis step in 2.. and Naruse. Moreover. Li et al. Cao et al. However. lignin and extractive matters. Kumabe et al.. the volatiles and char are further reacted the char morphology examined using a scanning electron and converted into the final products. biomass gasification is becoming an attractive holding time. velocity (Carpenter and Skorupska.. Sci. studying the husk. significantly (Carpenter and Skorupska. particles are rapidly heated as they drop into the hot 2000. 2004). Pütün et al. while the gas composition was analysed using losses due to pyrolysis can reach as high as 70 % of the total a mass spectrometer. In these reactors. the analysis of product gas composition is impossible turbines. Therefore. as well as an exact determination of the temperature and However. After that. which integrate the desirable features of the drop- added chemical syntheses such as synthetic diesel (via tube reactor and the fixed-bed reactor.e. almost 20 %. interactions between the components present in the biomass.

2 Drop-tube/fixed-bed reactor Untreated biomass A drop-tube/fixed-bed reactor was constructed in this Ash content 17. after which the meter (ICP-MS) technique.5 Demirbas (2004) Table 3.5 47.0 50.09 0.03 0. reactions. The reactor Ca 0. rice straw and corncob Rice husk Rice straw Corncob Proximate Analysis (% dry basis) Volatile Matter 72.01 0. which was pressurised with nitrogen to K 0. Content of ash and metal species in untreated and metal species in the treated and untreated biomass are given acid treated rice husk. Mg. 30 (3).6 28. rice straw and corncob in Table 3.7 78. rice straw and corncob Biomass Hemicellulose Cellulose Lignin Extractive matter Reference Rice husk 28. Wannapeera et al.76 rapid heating rate conditions as well as an exact determina- Mg 0.29 0.800 seconds).0 22.9 0.48 1.02 about 0. 40-50 mg of the sample was Na 0. Technol.37 16.04 schematic diagram of the reactor is shown in Figure 1. 393-404.0 3. Proximate and ultimate analysis of rice husk.2 16. Prior to an experiment.2 6.5 H 6.1 0. 2008 395 Table 1.7 32.1 47. These alkali metal species were analysed temperature was maintained to ensure uniform gas atmos- by means of the inductively coupled plasma-mass spectro. particles were left on the quartz wool to undergo further 2006).00 of the inner tube.3 10. Chemical components of rice husk.9 study based on the configuration developed by Hayashi et al. The volatiles able metal species from the biomass. This type of reactor combines the desirable features (mgion gsample-1) of the drop-tube reactor and the fixed-bed reactor to allow Na 0.21 1.1 8.79 7.4 18.67 4. (1999) Rice straw 35.4 Di Blasi et al. The biomass sample was treated sample was injected into the inner tube by an instantaneous with 0. Sci.6 24. Metal ion content (2002).9 10. After a desired holding time after sample injection MS for analysis of metal species.2 Ash 17.3 O (by difference) 44. while the char samples have been presented elsewhere (Vamvuka et al.0 Xiao et al.58 1. / Songklanakarin J. release of the pressure in the sample holder.84 0.0 Table 2.0 diameter of ¾ inches.5 15.03 0.2 N 0.5 MPa above the atmospheric pressure.8 1. The Acid treated biomass reactor consists of an inner quartz tube with the inside dia- meter of ½ inches and an outer quartz tube with the inside Ash content 18.9 Ultimate Analysis (% dry-ash-free basis) C 48.05 tion of the temperature and particle residence time..2 45.00 was purged with nitrogen at 400 ml min-1 and the reactor temperature was raised by an external heater to the desired major metal species typically found in biomass. Rice husk Rice straw Corncob 2.1 M HCl aqueous solution to extract the ion-exchange. The contents of ash and (in a range from 1 to 10.07 0.00 0.000oC s-1.8 74.5 6.08 filled in the tubular sample holder positioned at the top end Mg 0. J. the reaction was . (2001) Corncob 31. Approximately 30 minutes holding time at the Na. including temperature. The Ca 1.3 15. Details of the preparation of acid treated inner tube by the continued nitrogen flow.1 0. The lower end of the inner tube was Metal ion content fitted with a perforated plate on which quartz wool was (mgion gsample-1) placed. The heat- K 5.26 ing rate was estimated to be higher than 1. The acid washed samples were also subjected to ICP.01 0.00 0.8 0.7 Fixed Carbon 9.9 45. K and Ca. phere and temperature inside the reactor.9 10. while maintaining the and product gases formed were immediately swept from the sample structure.

char reactivities in this study. 1999). Prior to the test. 30 (3). The total weight loss was determined by the chosen to ensure that the combustion would take place difference between the weight of quartz wool with sample under the kinetic and not the mass transfer control regime before and after the pyrolysis experiment. 28. around 5 mg of the char samples were loaded onto the TGA sample pan. / Songklanakarin J. Rmax. Wannapeera et al. until the sample completely became ash. the flow of nitrogen was information on pyrolysis product characteristics which switched to air (Air Zero). were continuously monitored and and W is the instantaneous weight of sample. and 44 representing H2.3.3 Scanning Electron Microscope (SEM) 2. respectively. The temperature was kept constant benefits the subsequent utilisation. 2. The sample was initially heated up 2. Omistar).3.3 Analytical methods under the flow of nitrogen (99. No weight change of quartz experiment was dried in the vacuum oven at 70oC for 24 wool was observed. The residual char particles were collected for thermal condition in air at 500oC. The maximum relative The compositions of the obtained product gases were combustion reactivity.3. which Rmax max (1) was heated to 200oC to prevent the condensation of product W0 dt gases. The relative combustion reactivities of the pyrolysis. 15. The m/z of 2. As soon as the the following analytical methods in order to obtain the desired temperature was reached.. 2008 Figure 1.e. For the measurement of the relative combustion re- within 1% experimental error. W0 is the initial weight of sample CO and CO2. Technol. 393-404. The test temperature was further analyses. as shown in Equation 1. the gas concentrations obtained by standard gas calibration. The total weight losses were found to be hours. Schematic diagram of the drop-tube/fixed-bed reactor setup for pyrolysis experiments quenched by cutting the external heat supply and the system derived chars were measured in a standard thermogravi- was cooled down by the flow of cold nitrogen blowing down metric analyzer [Pyris 1 TGA. Perkin Elmer] under an iso- the inner tube. activity. The MS was connected to the exit of the 1 dW drop-tube/fixed bed reactor by a 1-meter transfer line.999 % purity) at 50 ml min-1 to 110oC to remove the remaining moisture and then to 500oC Pyrolysis chars and gases were further analysed using at a constant heating rate of 10oC min-1. quartz wool without sample) were conducted under collected from the drop tube/fixed bed reactor after the the range of conditions studied. was taken as the indicator for analysed by on-line mass spectrometer (Pfeiffer vacuum. Sci. The combustion re- activity was calculated by taking the first derivative of the 2. where t is the reaction time. CH4. MS. JSM-6400] was used to examine the morphology of samples . A series of blank (Messenböck et al.2 Isothermal thermogravimetric analyser (TGA) The scanning electron microscope (SEM) [JEOL. the pyrolysis char runs (i.1 On-line mass spectrometer (MS) obtained weight profile normalized to the initial weight of sample.396 J.

for rice husk. is thought to be responsible for the addi.1 g of the char sample was pretreated generally implies that. 2. rice straw and corncob at the (Gani and Naruse. in the commercial gasification pro- by drying under nitrogen atmosphere for around 5 hours to cesses. the weight 3. N2 was used as the adsorption gas. It can also be observed from Figure 2 that. Technol. 393-404. Below 300oC. the weight losses apparently reached pyrolysis step. Excess amount of the sample was removed by blow- ing with the air spray. which decomposes quickly the major weight loss occurred immediately after the sample at 200-400oC (Gani and Naruse. However. after which ing rate and high temperatures. This measurement. / Songklanakarin J. 2008 397 including both raw biomass and char particles derived from the pyrolysis experiments. which was the maximum pyrolysis temperature rate than rice husk and rice straw. The effect of holding time the weight loss rate was much slower.. the devolatilisation rate of corncob accelerated at temperatures above 350oC giving Fast pyrolysis experiments of rice husk. The results are shown in Figure 3 for release of volatiles starts at temperatures as low as 200oC the weight losses of rice husk. as soon as biomass particles are exposed to the high remove the remaining moisture. the weight loss due to pyro. It is noticed that. BEL JAPAN. however. tional small increase in the weight loss at high temperatures. 2007. INC) at -196oC. was injected into the reactor. Prior to the lysis accounted for 70-90% of the total weight loss. Worasuwannarak interesting for the investigation of the weight loss behaviour et al. This is typical for was then investigated at 700-850oC.e. Figure 2. Total weight losses from pyrolysis of rice husk. respectively. Wannapeera et al. 2007). which are within the lignocellulosic materials for which the devolatilisation rate range of temperatures encountered in commercial biomass depends strongly on the reaction temperature and the rapid fluidised bed gasifiers. 1999. Effects of temperature and holding time on the slight difference. JFC- 1100E Ion] and then transferred into the JEOL sample chamber for the analysis.800 seconds. continued throughout the range of holding times used but at . rice straw a higher weight loss than for rice straw and rice husk. i. Sci. The adhered sample was then coated with gold powder using the sputtering device [JEOL. The decomposition of lignin. Although pyrolysis temperatures above 700oC were Previous studies (Gani and Naruse. within the first second. ing time. the weight losses were 71.e. One minute holding time was used to ensure their maxima under the specified heating rate and holding a uniform temperature. leaving a small amount of char. corncob pyrolysed at a faster At 850oC. rice straw and corncob. 2007. 2003).8%. around 0. a temperature range of 200-850oC was used in order to suffi. the weight loss of corncob pyrolysis weight loss was found to be the lowest. 2003). Vam.000 time magnification was selected. while corncob exhibited a 3. i. J... The accelerating voltage was set at 15-40 kV and 2. The sample powder was sprinkled as a thin layer on an adhesive tape placed on the brass sample holder. The specific surface area of temperature inside the reactor. This is likely due to the impact of holding times ranging from 1 to 10. which is slower but spans over leaving a small amount of char. As shown in Figure 2. additional weight loss obtained at sufficiently weight losses were observed for all three biomass samples long holding times can be expected. at tem- ciently demonstrate the weight loss behaviour of the entire peratures above 700oC. 30 (3). 2007) have similarly found that the maximum decom- under the circumstances in biomass fluidized bed gasifiers.5% and 89. The and corncob at 200-850oC with 1 min holding time in specific surface area was measured by a sorption analyzer the drop-tube/fixed-bed reactor (BELSORP-mini with BELPREP-flow. rice straw which reflect the char active sites and its reactivity. they are rapidly heated up the sample was then calculated using the standard BET and the majority of the volatiles are immediately released method (Yang.. the decomposition of cellulose. The pyrolysis weight loss used in this set of experiments. Uzun et al. content.4 Sorption Analyzer The specific surface areas of the biomass samples as well as the biomass-derived char samples from the pyrolysis experiments were measured to examine the pore structures.3. At 850oC with 1 second hold- the entire range of temperatures (Orfão et al. In all cases. 2007). position rate of cellulose was at 350-400oC. especially at high heat- studied at temperatures between 200 and 400oC. at the same temperature. 77.3% vuka et al. This and corncob were carried out in the drop-tube/fixed-bed rapid increase in the weight loss of corncob is likely attri- reactor to investigate the effects of temperatures and holding buted to the decomposition of its considerable cellulose times on the pyrolysis weight loss. Results and Discussions loss of rice straw was always higher than that of rice husk over the entire temperature range. almost double that of rice husk and rice straw.1. For all three samples. significant time.

which may not exactly represent the natural The analysis of the chemical components given in cellulose and lignin in biomass. db] 90 750 C o 90 o (1) 850 C (2) 80 80 70 70 o 700 C o 750 C 60 60 o Rice husk 850 C 50 50 3 3 0 10 20 30 40 50 60 0 2 4 6 8 10x10 10. while rice husk had an almost equal an extremely long holding time at the high temperatures. considered unchanged. Technol. db] Total weight loss [%. the weight loss is was investigated at 850oC as a function of holding time (i. 1-10.8x10 Holding time [s] Holding time [s] (a) 100 100 Total weight loss [%. db] 90 Total weight loss [%. / Songklanakarin J. . db] 90 80 80 70 70 o 700 C (1) o 700 C (2) o o 750 C 60 750 C 60 o Rice straw 850 C Rice straw o 850 C 50 50 3 3 0 10 20 30 40 50 60 0 2 4 6 8 10x10 10.e. However. weight loss Since the cellulose and lignin chemicals were the model compounds. i.398 J. This behaviour was Table 2 shows that the total cellulose content was more than similar to pyrolysis under helium atmosphere in standard the lignin content for all three biomass samples. 30 (3). in which the yields reached the ash level after and 50% cellulose). 2008 100 100 o Rice husk 700 C Total weight loss [%.8x10 Holding time [s] Holding time [s] (c) Figure 3. The experiments were also carried out on cellulose and lignin chemicals under otherwise similar condi- 3. such as the amount of ash. Sci. 1-2 minutes. Wannapeera et al.e.3% hr-1. 393-404. i. db] 90 90 80 80 70 o 70 750 C o 750 C (1) o 800 C (2) o 800 C 60 Corncob o 850 C 60 Corncob o 850 C 50 50 3 3 0 10 20 30 40 50 60 0 2 4 6 8 10x10 10.e. 1. cellulose and lignin.8x10 Holding time [s] Holding time [s] (b) 100 100 Total weight loss [%.800 s holding time in the drop-tube/fixed-bed reactor of (a) rice husk. Total weight loss from pyrolysis at 700-850oC with 1 to 10. db] Total weight loss [%. within the range of holding times in the same order The relationship between the chemical components of magnitude as the typical particle residence times inside and the pyrolysis weight losses of the three biomass samples the fluidised bed reactors. proportion of hemicellulose.800 seconds). The pyrolysis weight losses are presented in Figure 4. (b) rice straw and (c) corncob an extremely slow rate.2 The effect of chemical components on the pyrolysis tions. Corncob TGA tests for both biomass and Thai lignite (the results are had the highest total cellulose content (31% hemicellulose not shown).

a significant .. Mg. 2007). Total weight losses from pyrolysis of rice husk. Cellulose 80 Rice straw decomposed much faster than lignin. 50 3 3 it is more difficult for lignin to decompose than cellulose. 2008 399 100 100 Total weight loss [%. rice straw Figure 5. which had the 80 highest cellulose content. (b) rice potassium. As shown in Table 3. ~30 %. daf] Total weight loss [%. Sci. 60 a significant further weight loss. 393-404.8x10 3 Holding time [s] 3. 0 2 4 6 8 10x10 3 10.8x10 50 3 3 0 2 4 6 8 10. The functional group analysis by FT-IR (the results acid treated and untreated biomass are presented as a func- are not shown) also confirmed that acid washing removed tion of holding time on the dry-ash-free basis in Figure 5. The profile of corncob. The profiles of bio. Technol. 2004. / Songklanakarin J.e. Total weight losses from pyrolysis of acid treated and un- had the highest contents of all four metal species of interest. 100 corncob. which have higher Holding time [s] chemical bond energies than the polysaccharide structures of (b) cellulose consisting mostly of a series of glucose molecules (Sharma et al. All the metal species were also the acid have no effect on either the quantity of ash present in biomass soluble species. daf] cellulose and lignin. Generally. straw and (c) corncob bustion than the other two samples.6%:Lig24. especially the abundant in the drop-tube/fixed-bed reactor: (a) rice husk. tend to cause more fouling problems during com. This 60 clearly confirms that the proportion of chemical components in biomass is one of the important parameters to evaluate the 50 pyrolysis behaviour. but closer to the former. while rice husk having the lowest cellulose content and the highest lignin content exhibited the opposite. treated biomass at 850oC with 1 to 10. 0 2 4 6 8 10. with almost all the possible weight loss of cellulose occurring within the first 70 second after the sample injection.8x10 10x10 Lignin consists of more aromatic groups.4% Lignin100% 60 60 Cellulose100% 50 3 3 0 2 4 6 8 10x10 10.800 s holding time in the drop-tube/fixed-bed reactor Total weight loss [%.800 s holding time These metal species in rice straw. ash contents of treated and untreated samples were almost The total weight losses from pyrolysis at 850oC of identical. the metal species of concern (Na. was the closest to the profile of 70 cellulose. the and interact with tar during pyrolysis. biomass samples. however. J.3 The effect of metal species on the pyrolysis weight loss (c) Among the three biomass samples studied. Ca and K) from the Similar to the pyrolysis of untreated biomass. which are likely to evolve from the biomass or the biomass structural properties.8x10 10x10 Holding time [s] Holding time [s] (a) Figure 4. Yang et al. 100 mass decomposition were found to lie between those of Total weight loss [%. daf] 90 Acid-washed rice straw the results are expressed on a dry-ash-free basis. Wannapeera et al. 30 (3). Lignin decomposition during the heat-up period was also considerable. which was shown to remained unaltered. As described in the experimental section. while the other structural properties of biomass samples were treated by acid washing.5%:Lig15% Acid-washed rice husk Rice straw: Cel32%:Lig22. rice straw. cellulose and lignin at 850oC with 1 to 10. i. continued as the holding time proceeded but at a much slower rate. This may be 90 due to the higher proportion of cellulose than lignin in these Corncob Acid-washed corncob biomass samples.3% 80 80 Rice husk 70 70 Rice husk: Cel28. daf] 90 90 Corncob: Cel50.

(2000) suggested that the metal species disfavor the which may be explained by the more rapid devolatilisation cross-linking reactions which reduce the char formation.800 second hold) Figure 6. 30 (3).7% and 90.1%. 2000).. less than 1 second) for the treated biomass. At seen as a smooth surface with some distributed pores. For all three samples. became slightly swollen and more porous. SEM photomicrographs of raw biomass samples and their chars obtained from pyrolysis at 850oC with 1 and 10.4 Char reactivities and their morphological changes char. The extensive widening of pores and changes in particle geometry were clearly observed for the corncob 3. These behaviours are likely due to the significantly low during pyrolysis lignin content but high cellulose content in corncob. each sample 91.7%. exhibited qualitatively different char morphologies.e.. particles have quite similar appearances. Figure 6 Moreover.2%. which was also consistently could be due to the immediate release of the volatiles from observed by other researchers (Kershaw et al. all the biomass cell wall rendering the particle rupture (Saka. Wannapeera et al. Hayashi et al. rice straw and corncob were were subjected to heat and decomposed rapidly. These observed developments of . the original biomass (i. respectively. The morphological change of corncob in the case of rice straw. Rice 86. Hayashi et al. After 1 second holding time. straw. 2000.. Li et inside of the particles under a rapid heating up. 92. the weight losses on a dry-ash-free only 1 second pyrolysis during which the biomass samples basis of the treated rice husk. rice straw. The low lignin content is responsible for the weak structure of the As biomass is being pyrolysed to form char.5% and 91. corncob and high devolatilisation rate of corncob leading to the fragmen- their respective chars prepared in the drop-tube/fixed-bed tation of its char particles. the high cellulose content results in a relatively shows the SEM pictures of rice husk. 2008 Rice husk Rice husk char (1 second hold) Rice husk char (10.800 second hold) Corncob Corncob char (1 second hold) Corncob char (10. et al.1% for the untreated samples.400 J. of rice straw resulting in more extensive volatile explosion This could also explain the largest difference in weight loss and pores creation. 393-404. Suelves was more pronounced for rice straw compared to rice husk. This effect al.800 s holding time in the drop-tube/fixed-bed reactor weight loss took place immediately after the sample injection reactor at 850oC. characteristics of the samples change progressively. This the enhanced tar formation. 2000. However.. 2002). / Songklanakarin J. which has the highest content of the char was clearly different from those of rice husk and rice metal species. 2000. The increased husk and rice straw char. Technol.800 second hold) Rice straw Rice straw char (1 second hold) Rice straw char (10. Sci. which could be the weight losses of treated biomass were always higher. compared to 88. while retaining their particle geo- weight loss by the removal of these metal species is due to metries.

42 203. rice creased. 2008 401 Table 4.73 1 1.800 1. As suggested in the previous section. This decrease could be current setup. 0. Under the sive reduction of the char surface area due to the pore over. Among the three biomass samples studied. the maximum evolution rates in reduced carbon reactivity. Although analyses were not enlarged and finally merged lowering the char surface area.89 - 10. J. showed that the surface area of the pyrolysis char reached The relative combustion reactivities and N2-adsorp. the straw and corncob in the drop-tube/fixed-bed reactor at blocked pores are opened up and new micropores are created 850oC with the holding times ranging between 1 and 10. the evolution trends of each gas species could still ing or the loss of char active sites due to a long-time exposure be interpreted with reasonable accuracy.23 - 3. espe.58 - 10.15 1 1. The thermal annealing from the heat treatment results from isothermal pyrolysis at 850oC. while rice husk chars were the least reactive.26 Rice straw 0 (original) . The rates are presented in the reduction of carbon structural defects. 5. Maximum char combustion reactivities determined using a standard TGA under an isothermal condition at 500oC and the N2 adsorption BET surface area of biomass-derived chars prepared in the drop-tube/fixed-bed reactor under fast pyroly- sis at 850oC Biomass char Holding time (s) Rmax BET surface area (min-1. Helium gas was used instead of N2 in order to prevent the cially cellulose and lignin. This evolution of the product gases was also found within 60 sec- . resulting the fast heating rate condition. corncob chars 3. 30 (3). Sci. surface areas) and pyrolysis conditions can be observed.800 0.53 Corncob 0 (original) . / Songklanakarin J. to high temperatures.72 1 0. those pores are later seconds are presented in Table 4.20 105.94 94. The effect of high-temperature anneal. The other reason is the progres. overlapping of the peaks representing the gas species of the Char reactivities generally decreased with an increase same molecular weight.52 600 0.600 0. These defects per gram of sample. However. Figure 7 shows the instantaneous evolution rates as a ing has been studied and well explained by Marsh and Kuo function of time of the product gases H2.800 increasing the surface area. the estimated signal delay was around 5 explained by the following reasons. Technol. The study of biomass pyrolysis by Liu et al. chars.600 0. conducted on the chars prepared at all conditions due to the This latter implication is evidently supported by the decrease insufficiently small amount of the resulting char samples. with the in the holding time during pyrolysis. One is the char anneal. CO and CO2 (1989). as will be discussed later. a maximum at the conversion of around 0. conditions used and the current setup. CH4. daf) (m2 g-1) Rice husk 0 (original) .71 - 3.800 0. seconds. CO and N2. 0. Due to the rapid evolution of gases by are normally where the main active sites are located. 393-404.5 Composition analysis of pyrolysis product gas were generally the most reactive.03 the char structure were confirmed by the significant increase could also lower the intrinsic reactivity of the pyrolysis in the surface area of chars from those of their original bio.600 0.g.23 42. They also explained that during the initial step. Although. (2008) mass at all preparation conditions. of all gases were approximately at the same time.28 600 1.92 99. the of the N2-adsorption surface areas with conversion at the relationships between char characteristics (reactivities and extended holding times (see Table 4). the The derived product gas from the reaction zone was difference in biomass reactivities could be due to the swept into a mass spectrometer for a real-time gas analysis. Wannapeera et al.35 and then de- tion surface areas of chars prepared from rice husk.98 - 10. proportion of chemical components of each biomass.53 72. e.21 600 0.83 - 3. almost complete lapping and pore widening as the conversion proceeds.

e. 2007). can play a role as that cellulose decomposition produces significantly higher nature-existing catalysts in biomass. CO had the highest evolution rate for all three biomass samples. Previous studies have shown 0 10 20 30 40 50 60 Time [s] that CO is formed during the primary decomposition of hemicellulose and cellulose with a smaller proportion of CO Figure 7. in addition to the biomass chemical tion from cellulose and lignin pyrolysis carried out under components. Technol. 1981.. the inorganic matters. 6 H2 Among the four gas species of interest. CH4. CO and CO2 against time coming from lignin by the cracking of carbonyl (C-O-C) and during pyrolysis at 850oC of rice husk. Other gases. Wannapeera et al. exhibit similar evolution rate profiles for rice husk and corncob. rice straw. Sci. These gas yield trends are in tion of gas and char. Evolution rates of H2. while depressing the formation of liquid. CO is the main 2 product of cellulose decomposition. . corncob 2007). especially the metal otherwise similar conditions. 2008 -3 -3 14x10 50x10 Gas evolution rate [mol/(min g-sample)] Gas evolution rate [mol/(min g-sample)] CO o o Pyrolysis at 850 C Pyrolysis at 850 C 12 40 Cellulose Rice husk 10 CO H2 30 8 CO2 CH4 6 CH4 20 CO2 4 H2 10 2 0 0 0 10 20 30 40 50 60 0 10 20 30 40 50 60 Time [s] Time [s] -3 -3 14x10 50x10 Gas evolution rate [mol/(min g-sample)] Gas evolution rate [mol/(min g-sample)] o Pyrolysis at 850 C Pyrolysis at 850 C o 12 Rice straw 40 CO Lignin 10 30 8 CO2 H2 6 CH4 20 CO2 4 H2 CO 10 2 CH4 0 0 0 10 20 30 40 50 60 0 10 20 30 40 50 60 Time [s] Time [s] -3 14x10 Figure 8. As can be seen in Figure 8. Yang et al. 393-404. Bridgwater et al. CH4 and CO2. the effect of could be explained by the considerably high cellulose and the metal species could not be eliminated. CH4. CO and CO2 against time Gas evolution rate [mol/(min g-sample)] o 12 Pyrolysis at 850 C during pyrolysis at 850oC of cellulose and lignin Corncob 10 CO good agreement with other studies on pyrolysis experiments on different types of biomass (Graboski. the effect of chemical components in observed among the three biomass samples studied. after which the gas evolution was while the CO2 evolution rate is double that of H2 and CH4 for insignificant. including H2. as shown in Figure 8. The CO 4 CH4 evolution is thought to mainly come from the decomposition of cellulose. This positions could be clearly observed. 30 (3). while the majority of 0 product gases from lignin is H2. rice straw and carboxyl (C=O) in biomass (Fitzer et al. (2003) suggested that..402 J. This favours the forma- gas yield compared to lignin. confirm species which are abundant in biomass. < 1 % of the total gas formed. Corncob biomass on the pyrolysis gas yields as well as the gas com- gave higher gas evolution than rice husk and rice straw. i. Worasuwan- CO2 8 narak et al. hemicellulose contents in corncob. However. Different gas evolution behaviours were clearly From this study. onds for all three samples. The results of gas evolu. 1971. / Songklanakarin J. Evolution rates of H2.

Li. 2000.W. Kristiansen.D. 2008 403 However. J. the weight on bio-char yield from pyrolysis of agricultural resi- loss is considered unchanged. A. J-I. 313-322. Piskorz. lose). Meier. The pyrolysis rates were found to be influenced by 243-248. Shimada. Morishita. which could be explained by content on pyrolysis and combustion characteristics thermal annealing as well as the reduction of the surface area for several types of biomass. Kumagai. 2004. 2003. Q. and Naruse. editor. C-Z.... Composition of gases released of milled wood lignins studied by thermogravimetry/ during olive stones pyrolysis. Reactivities as the metal species contents. M. wire-mesh reactor. 393-404. Carbon. E. K. 2002. Corncob.. S.. 1997. M. Hayashi. Understanding Coal Gasification. New York.. Iwatsuki. Li. 84. Kinetics of and Yoshida. Journal of Analy. Energy Technology samples as well as of the cellulose. and Marcilla. T. from the pyrolysis of a Victorian brown coal in a UK. R. Li. F. Fuel. Reactions in brown coal pyro- steam gasification of nascent char from rapid pyroly. Thermal decomposition Tascon. rice straw and Carpenter. C. Physics of Carbon. O. J-I.G. and Chiba. A. and Shen.. J.. 1998. I.. and Li. gave the highest total gas yield. Caballero. Acknowledgements C-Z.M. 83-89. Under the conditions nology. T. 11-84. Doi. Tsutsumi.. pp.R. J-I. A. Hanaoka. Walker Jr. K. into the reactor and accounted for 70-90% of the initial Clemens. Kershaw. Martinez-Alonso. S. Effect of cellulose and lignin reduced the char reactivities. dues. 40-41. 2005. order of magnitude as the typical particle residence time Demirbas. / Songklanakarin J. 1993. and Skorupska. Sathe. Conclusions Pyrolysis. A. Marcel Dekker Ltd. Minowa. IEA Coal Research. no correlation between the metal species content Caballero. 37 (8). 1996. within the range of holding times in the same 10). Bioresource Tech- biomass was focused in this study. New Jersey.L.. pp. Cao. M. C. 1227- (which normally corresponds to the lower content of cellu. lysis responsible for heating rate effect on tar yield. F. 649-661. J-I. and Jakab. Energy & Fuels. > 700oC) fast pyrolysis of lytic behaviour of waste corncob. A. J.. 2000. 1238.. Review No. Energy and Environment (JGSEE) throughout this study is Fuel. The higher the lignin content of some biomass chars in air. Chemistry and metal species in biomass increased the weight loss by en. A. and Radlein. W. CPL Press. 81 (15).F. Blanco. Fuel.. C. Journal of Analytical and Applied Pyrolysis. Wannapeera et al. sis of a Victorian brown coal.. hancing the tar formation as well as depressing the cross. Although the weight loss continued throughout the effect of calcium on the rate and products of steam range of holding times used. T.. Bayarsaikhan. and Matheson. 65. Chiba. Advances in Science of Victo- References rian Brown Coal. considering their organic fractions. A.. Study of the and the gas evolution behaviour was found. Pyrolysis. 1977-1987. Diebold.H. A. Sci. Hayashi. 14 (2). Renewable Energy. Hayashi. 1999. E. Damiano. D. T. 1612-1621. J-I. Pyro- The high temperature (i. Co-gasification of woody bio- . 1971. Journal of Analytical mass spectrometry. and tical and Applied Pyrolysis... 67. A. 2004. 1017-1020. 1997. Takahashi. T. Kumabe.e.e. 1-2 minutes. A..A. occurred within only 1 second after the biomass was injected London. 1996.. 77 (9- Moreover. primary pyrolysis of kraft lignin at high heating rates: yields and kinetics. Xie. 71-186. C-Z.. 2004. 2007. Blanco Lopez. the weight losses from rice husk. D. editor. 94. K. Hayashi.A. Conesa. 32 as the conversion proceeded. T. H. 2002. studied. and Chiba. C-Z. 159-178..M. Li. K. K-C.. 237-383. Czernik. Structure and properties of Victorian brown coal. Fujimoto. J. Roles of inherent metallic species in secondary reactions of tar and char during The studentship from the Joint Graduate School of rapid pyrolysis of brown coals in a drop-tube reactor. 2007.. The presence of Fitzer.. L. J... J. 1. Buonanno. 72. T. Biomass Gasification Principles and CO is the major product gas from pyrolysis of all biomass Technology. Elsevier. London. and Chiba. the rate was extremely slow. Effect of temperature and particle size inside the fluidised bed reactors. Noyes Data Corporation. J. C. Bao. Coal Combus- corncob exhibited similar trends. C-Z. Reed. S-G. and Schaefer. and Marcilla. Tsutsumi. The major weight loss tion-Analysis and Testing. C. 30 (3). Energy & Fuels. T. and Till. the proportion of the biomass chemical components as well Di Blasi. Sathe. T. the lower the pyrolysis weight loss. gratefully acknowledged. The weight. 400-408. P. and Branca. gasification of char from low rank coal. 476-482. 1981. The longer holding times Gani. A.. B. W-R. IEA Pyrolysis kinetics of almond shells and olive stones Coal Research. Sakanishi. linking reaction to form char.. 7. highest cellulose content.A. Mueller. H. C. Bridgwater.. 36 (2).. no. Faix. J. Font. S. 159-175. UK. editor. Fluorescence spectroscopic analysis of tars Fast Pyrolysis of Biomass: A Handbook. Peacocke. Front. B.C.. Hayashi. A. N. Oasmaa... i.M. R. 42 (2). Graboski. Journal of Analytical and Applied and Applied Pyrolysis. T.14 (2).. Journal of Analytical and Applied 4.. Technol. which contains the (4).

. effect of mineral matter on the physical and chemical 1219. S.. 55.404 J. 1949- Pütün. 85 (12-13).Final Report prepared at high temperatures. J. Chemical. E. rice husk. Fuel. and Figueiredo. Kershaw. Y. J. 86 (5-6). Hoboken.C.87 (4-5). 1981.. of rice husk: Product yields and compositions. and Khilart. UK. Adsorbents: fundamentals and applications. 87 (4-5). 22-28. 147-153.V. 2004. Sofer and O. C.. D. Y. Fuel. Y-T. Biomass and Bioenergy. Moliner. H. Yang. Journal of combustion reactivity of its chars. 2008 mass and coal with air and steam. 79 (1-2).L. H. Thailand. Vamvuka.. Tanthapanichakoon. H. chars from pyrolysis of lignin. 2000.. 2004. and Arauzo. Research on biomass fast pyrolysis for liquid Utistham. A. editor.G.. Biomass Conversion Processes for rye straw. B. Fast pyrolysis 466. Fuel. and thermal characterizations of alkali-soluble lignin Chemical Engineering Journal. and Zheng.. and hemicelluloses. E.. activation of low rank coal and biomass materials. 2007.J. 26. D. 2000. Lee. cellulose and lignin W. D. 4). H. Tsai.. E. Önal. Suelves. alkaline straw black liquor in nitrogen atmosphere. Wang. resource Technology.H. A.R.. Kinetics and catalysis of carbon Thailand. R. and Pütün. 2007. 98 (1). D. 1812-1822. Introduction to Carbon Science. J. Marsh. and Hajaligol. 78. Fuel. structural. Butterworths & Co. R. and Cellulosic Chemistry. and Kandiyoti. Uzun. 1-6.. 1207. Lee. Yang. Ltd. 86 (11). Fates dues: influences of coal mineral matter and petroleum and roles of alkali and alkaline earth metals during residue mass ratio. Composition of CO2 and steam-gasification in a high-pressure wire. Raveendran. Chan. N. Fuel.. Gea. 1993. G. and Besler. 2000. 307-319. Z.. Energy potential from residual biomasses in Marsh. Zaborsky.. A. Wannapeera et al.L. and Rothman... C-Z. . R. K. fuel.S. 29-41. V. Li.L. Troulinos. and Applied Pyrolysis. New Jersey. in a thermogravimetric analyser and static batch re- Saka. bed pyrolysis of cotton stalk for liquid and solid Vamvuka. 1995. and cellulose from maize stems. 86. / Songklanakarin J. and Pütün. K. Gu. Wang. Fuel Processing Technology. M. S. Sun. 2000. Özbay. W. B. Pütün. 427-438. F. Sharma. J. Fuel. X. Journal of Analytical Sánchez. and Kuo.. F.. 349-358.E. 684. Soontornrangsan. May 23-25. and Wang. J. 1960. and Kastanaki. N. Lin.T. R. Technol. Orfão. editor. The pyrolysis of rice husks London and New York. mass residuals mixtures with lignite.Chen.J. 2007. and La´zaro. Pyrolysis behaviors of rice straw. Influ. New York. Y. Y. 1469-1482. 79 (3.T. E. H.. 2007.. Y. 2nd edition.A. Indus. 552-558. J.F. 393-404. Polymer Degradation and Energy and Fuels. 2001. and Chang.M. Stability. New York.T. Fang. An experimental able Energy Promotion and Energy Efficiency Im- investigation into the gasification reactivity of chars provement in Thailand Project . Sci. K. Sathe. revised and expanded. Li. R. P. Fuel. I.. 1763-1771.K. T. S. 2007.. S. Pyrolysis. Fuel. E. editor. Zhou. Shafizadeh. Sonobe. Journal of Analytical and Applied the pyrolysis of a Victorian brown coal. 2004. Worasuwannarak. 51-82. K. Bio- Luo. Characteristics of hemicellulose. pp. 1989. Fuel. Bilbao. and Cen. T. Fuel. Liao. Pyrolysis kinetics of lignocellulosic materials-three 2003. S. D. J. and Piyakuldumrong P. and Marcel Dekker Ltd. Messenbock..K. W. 1999. Kakaras.B. and rice straw. Shiraishi.. 83. Wood actor. 78 (2). 455-462. S. The products..C. corncob by TG-MS technique. 74. 72 (2). Williams P. Wooten. Fuel. Network of Thailand (ENETT). 1999.R... W. Bajay. Characterization of pyrolysis.. 460. R.M.. Baliga. Kastanaki. 781-793. E.J. T-F. trial Uses of Biomass Energy. Analytical and Applied Pyrolysis. C. Kinetic study of the thermal degradation of Xiao. Plenum Press. Proceedings of the 3rd Energy Technology gasification.. N-S. TG study on teristics. 104 (1-3). Pyrolysis characteristics and kinetics of bio- independent reactions model. Fixed. Dugwell. R. Synergetic ef- 689. 82.P. Wiley-Interscience. 2008. 2005. Yan.. 2008. 256-271. 1781–1788. R. M.. Gonzalo.. 30 (3). 2003.. 1-6. pyrolysis of biomass and its three components under Rosillo-Calle. Bangkok.R. G.E.B. R. Taylor & Francis. ence of mineral matter on biomass pyrolysis charac. and Grammelis. X.. A. Thailand Research Fund. M. and Chen. syngas. products obtained via fast pyrolysis of olive-oil mesh reactor: the reactivity of Daw Mill coal and residue: Effect of pyrolysis temperature. 151-159. Policy Research on Renew- Liu. 74 (12). 2007.. and Pang. 2000. W. B. Hon and N. Fuel. Chemical composition and distribution. 2006. and Sun R-C. H. fects in the co-pyrolysis of coal and petroleum resi- Li. Ganesh. 2007. 78 (3).. Antunes.