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WMR0010.1177/0734242X14539787Waste Management & ResearchUzun and Kanmaz

Original Article

Catalytic pyrolysis of waste furniture sawdust for bio-oil production

Waste Management & Research 2014, Vol. 32(7) 646­–652 © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav DOI: 10.1177/0734242X14539787 wmr.sagepub.com

Bas¸ak B Uzun and Gülin Kanmaz

Abstract In this study, the catalytic pyrolysis of waste furniture sawdust in the presence of ZSM-5, H-Y and MCM-41 (10 wt % of the biomass sample) was carried out in order to increase the quality of the liquid product at the various pyrolysis temperatures of 400, 450, 500 and 550oC. In the non-catalytic work, the maximum oil yield was obtained as 42% at 500oC in a fixed-bed reactor system. In the catalytic work, the maximum oil yield was decreased to 37.48, 30.04 and 29.23% in the presence of ZSM-5, H-Y and MCM-41, respectively. The obtained pyrolysis oils were analyzed by various spectroscopic and chromatographic techniques. It was determined that the use of a catalyst decreased acids and increased valuable organics found in the bio-oil. The removal of oxygen from bio-oil was confirmed with the results of the elemental analysis and gas chromatography-mass spectrometry. Keywords Catalytic pyrolysis, sawdust, ZSM-5, H-Y, MCM-41

Introduction Pyrolysis oil can be used as a fuel. Moreover, it can act as a source for the production of valuable chemicals such as food aromas, adhesives, fuel enhancers, speciality chemicals, fertilizers, etc. However, it is not as physically and chemically stable as conventional fuels due to its having a high water content, as well as containing oxygenated and heavy organic compounds, having a high viscosity, a low pH, etc. One of the most commonly studied methods of the stabilization of bio-oils has been that of their upgrading in the presence of a catalyst. A number of studies in this field show that catalytic reactions usually lead to additional water and coke production and to less organic products. In recent years, the search for a suitable catalyst for the pyrolysis process has become a very challenging research goal, since it would make the pyrolysis process more economically feasible. The selected catalysts would have to work satisfactorily under certain pyrolysis conditions, such as the necessity to favor the production of desirable products and to inhibit any undesirable reactions (Bridgwater, 1996; Nilsen et al., 2007). Many catalytic applications in biomass conversion and the upgrading processes involve very acidic and shape-selective zeolitic materials (Antonakou et al., 2006; Bridgwater, 1996; Iliopoulou et al., 2007; Jackson et al., 2011; Mihalcik et al., 2011; Nilsen et al., 2007; Pütün et al., 2009; Torri et al., 2009; Uzun and Sarıoğlu, 2009; Wang et al., 2010a; Williams and Horne, 1995). Upgrading technologies that favor pathways towards reducing the oxygen content are very necessary (Nilsen et al., 2007). Among these technologies, the incorporation of catalysts into the pyrolysis reaction, in situ, to reduce the more reactive

oxygenated compounds appears to be the most practical method. Moreover, zeolite catalysts have been shown to be effective in the selective deoxygenation of pyrolytic vapors, resulting in the formation of aromatics, effectively increasing the C/O ratio and promoting cracking reactions, especially for the zeolites that have a high Si/Al ratio (Mihalcik et al., 2011). The pore size and silica alumina ratio of the zeolite catalysts strongly affect product yields and compositions. The catalysts used in this study were selected according to their frameworks and acidities. Although there are many studies concerning the catalytic pyrolysis of sawdust with zeolites, there is no study within the literature that compares the effects of well-known zeolites (ZSM-5, H-Y and MCM-41) on bio-oil yields and compositions. In the present work, the catalytic and non-catalytic pyrolysis of waste furniture sawdust was investigated at the various pyrolysis temperatures of 400, 450, 500 and 550oC with a reaction time of 5 min, a heating rate of 300oC min−1, a nitrogen flow rate of 400 cm3 min−1 and with a particle diameter (Dp) range of 0.85 > Dp > 0.425 mm. For the catalytic pyrolysis of waste furniture sawdust, ZSM-5, H-Y and MCM-41 (10 wt % of raw material) was used as the catalyst. The obtained pyrolysis oils were characterized by using various spectroscopic and chromatographic analysis Department of Chemical Engineering, Faculty of Engineering, Anadolu University, Eskisehir, Turkey Corresponding author: Bas¸ak Burcu Uzun, Department of Chemical Engineering, Faculty of Engineering, Anadolu University, Eskisehir, Turkey. Email: [email protected]

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Uzun and Kanmaz Table 1.  Properties of the biomass sample. Proximate analysis (wt %, as received) Moisture Volatiles Fixed carbon Ash Elemental analysis (wt %, d.a.f. basisa) Carbon Hydrogen Nitrogen Oxygen (by difference) Empirical formula H/C molar ratio O/C molar ratio Higher heating value (MJ kg−1) Component analysis (wt %, as received) Extractives Holocellulose Hemicellulose Cellulose (by difference) Lignin Oil aDry

  9.60 80.80 9.22 0.38   59.72 5.98 1.40 32.90 CH1.20N 0.02O0.41 1.20 0.41 22.90   6.04 71.24 23.10 48.14 26.52 3.50

and ash free.

techniques and the obtained results were compared to those of previous studies.

Experimental study Raw material The sample of pine sawdust used in this study has been supplied by a furniture company based in Bursa, located in the Marmara region of Turkey. The main characteristics of waste furniture sawdust are given in Table 1. Air-dried sawdust was ground in a high speed rotary cutting mill and screened to obtain seven different particle sizes (Dp), namely, 1.8 > Dp > 1.25 mm; 1.25 > Dp > 0.85 mm; 0.85 > Dp > 0.6 mm; 0.6 > Dp > 0.425 mm and 0.425 > Dp > 0.224 mm. The average particle size was found to be 0.752 mm. Proximate analysis was performed on the sawdust sample to determine the weight fractions of moisture, volatiles, ash and fixed carbon contents. The ASTM Standard Test Method for Proximate Analysis of Wood Fuels (E 870-82) was used. Then, the fixed carbon was obtained by subtracting the percentages of volatile matter, moisture and ash from 100%. The average bulk density of this raw material was found to be 0.1658 kg m−3 according to ASTM E873-82. The ash content of sawdust was found to be 0.38 wt %, which is very low when compared with conventional fuels (Uzun et al., 2007a). The feedstock moisture was 9.60 wt %. It consisted of 71.27% holocellulose, 26.52% lignin and 6.04% extractives (Li et al., 2004). Ultimate analysis was also performed on the sawdust samples to determine their elemental composition. Using the elemental analysis results the calorific value of sawdust was calculated to be 22.90 MJ kg−1.

For the evaluation of the thermal behavior of the raw material, thermal gravimetric analysis (TGA) was applied using a LINSEIS Thermowaage L 81 thermogravimetric analyser coupled with differential thermal analysis (DTA). The sample, weighing approximately 20 mg, was heated to 900oC with a heating rate of 10oC min−1 under the nitrogen atmosphere (100 cm3 min−1). The experiments were repeated at least three times.

Catalyst The MCM-41 catalyst employed in the present study was supplied by Sigma Aldrich and Zeolyst International. The H-Y and ZSM-5 catalysts were provided by Zeolyst International, USA. Prior to their use, the catalysts were heated to 550oC in 1 hour to eliminate the water present both as humidity and as water bonded to the crystals. In this study, the catalysts were used once.

Apparatus The pyrolysis experiments were conducted under a nitrogen atmosphere in a well-swept and high-speed, heated, fixed-bed batch reactor with a length of 90 cm and an inner diameter of 2.5 cm made of 310 stainless steel. The reactor was heated directly by AC voltage; therefore there was no furnace. This provides quick heating and cooling. During the experiments, the heating rate and the pyrolysis temperature was controlled with a proportional-integral-derivative (PID) controller. The flow of the released gas was measured by using a Rota meter. The experimental set-up is shown in Figure 1. The detailed explanations of the experimental set-up and the procedure can be found in previous studies (Kanmaz, 2011; Uzun and Kanmaz, 2013). As it can be seen, the temperature measurements were taken above the bed with the thermocouple in the middle of the tubular reactor in order to control the reactor temperature. A 316 stainless steel swage lock needle valve was used for the fine control of the nitrogen flow rate before entering into the reactor.

Structural analyses Proximate and elemental analyses (Carlo Erba EA 1108) were carried out on the bio-oil samples. The analyzed oil was obtained at the pyrolysis temperature of 500oC. The elemental composition and calorific value of the bio-oils were determined. The Fourier transform infrared (FT-IR) spectra of the oils were recorded using a Jasco FT-IR-300 E Model Fourier transform infrared spectrophotometer. The gas chromatography (GC) analysis of the liquid samples was performed using a 6890 Model gas chromatograph and a mass selective detector (HP, USA); a thin film (30 m × 0.32 mm, 0.5 µm film thickness) HP-5 MS capillary column supplied by Hewlett-Packard was used. Helium was used as the carrier gas, with a flow rate of 1 cm3 min−1. The temperature program was 35oC for 3 min followed by a rise to 270oC, using a heating rate of 10oC min−1. The 1H-NMR (nuclear magnetic resonance) spectrum of the bio-oil was recorded using a Bruker DPX-4000 and 400 MHz high performance digital

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Figure 1.  Experimental set-up.

FT-NMR instruments. The samples were dissolved in deuterated chloroform containing Tetramethylsilane (TMS) as a standard.

Results and discussion Thermal behavior

Experimental procedure

The devolatilization stage plays an important role in the conversion processes. Thermogravimetric analysis (TGA) is one of the major thermal analysis techniques used to study the thermal behavior of carbonaceous materials. Particular attention is paid to the light hydrocarbons produced as a consequence of the thermal degradation of the raw material or intermediates (Uzun et al., 2007b). The results of TGA, derivative thermogravimetric analysis (DTG) and differential thermal analysis (DTA) of the sample are given in Figure 2. The TGA of the furniture sawdust revealed an initial weight loss (6.17 wt %) between 80 and 220ºC. This could be due to the elimination of physically absorbed water resulting in the moisture content of the sample. Devolatilization begins at about 220ºC and the removal of volatiles completes at about 650ºC. After this temperature is reached, there is no further loss of weight. The total weight removal of volatiles is 77.50%. The main devolatilization process takes place between 150 and 500ºC and peaks at 367.47ºC. This implies that the main pyrolysis reactions including depolymerization, decarboxylation and cracking took place over the given temperature range. The lower temperature of the DTG peak at 90.18ºC for the sawdust mainly represents the moisture, while the higher temperature of the DTG peak (starting at 220ºC and ending at 390ºC) represents the degradation of hemicelluloses and cellulose. The decompositions of cellulose and hemicellulose cause the formation of organic volatiles, whereas the devolatilization of lignin enhances the formation of char. The lignin decomposition occurs throughout the temperature range of 220–650ºC, but the main area of weight loss occurs at higher temperatures. These results can be further

The previous part of this study includes the rapid pyrolysis of waste furniture sawdust under various conditions to achieve maximum oil yields (Uzun and Kanmaz, 2013). The optimum conditions were determined at a reaction time of 5 minutes (raw material retention time at reaction temp.), a pyrolysis temperature of 500oC, a heating rate of 300oC min−1 and in the particle size range of 0.85 > Dp > 0.425 mm under the nitrogen flow rate of 400 cm3 min−1. Details about the results of the pyrolysis experiments and the description of the study were given in our previous studies (Kanmaz, 2011; Uzun and Kanmaz, 2013). Apart from the reaction temperature, the experimental conditions of the reactor were kept constant in the present study to understand the effects of the catalyst type and temperature. The catalyst temperatures were varied in the reactor in order to understand the effect of the parameter on the catalytic pyrolysis product yields and compositions. In the first part of the experiments, they were performed at the various temperatures of 400, 450, 500 and 550°C with the addition of the catalysts (ZSM-5, H-Y and MCM-41) into the raw material (10 wt % of raw material). Prior to the pyrolysis experiments, samples of the sawdust and catalysts were mixed homogeneously. After the pyrolysis reaction, due to the difficulty of the separation, the percentages of char and coke are given together. The same procedure was repeated as in the previous part. In this study, all the yields were expressed on a dry ash-free (d.a.f.) basis and the average yields are obtained from at least three experiments.

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Figure 2.  TG, DTG and DTA of waste furniture sawdust. 45

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Figure 3.  Effect of temperature on liquid yields of noncatalytic and catalytic works.

clarified by the DTA results. Thus, the removal of water adsorbed to the structure by an endothermic reaction can also be seen in the DTA curves. The peak at 367.47ºC shows the decomposition of hemicellulose and cellulose by endothermic reactions.

Results of non-catalytic and catalytic pyrolysis The catalytic (ZSM-5, H-Y and MCM-41) and non-catalytic pyrolysis of waste furniture sawdust was performed at four different temperatures, ranging from 400oC to 550oC (50oC apart), while the other parameters were kept constant (a pyrolysis reaction time of 5 min, a heating rate of 300oC min−1, a particle size range of 0.85 > Dp > 0.425 mm and a N2 gas flow rate of 400 cm3 min−1). Pyrolysis liquid yields are given as a function of temperature in Figure 3. As the pyrolysis temperature increases from 400oC to 550oC, the biooil yield – the condensable phase of the pyrolysis vapors – maximizes at 450–500oC and then decreases at the higher temperatures. This could be explained by the greater primary decomposition of the biomass sample at a high temperature (Sınağ et al., 2010; Uzun et al., 2007b). The maximum oil yield achieved was 42% in

0 350

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Figure 4.  Effect of temperature on gaseous yields of noncatalytic and catalytic works

the non-catalytic work. The use of catalysts in this study causes a severe reduction of the liquid yields. This could be explained by the catalytic cracking reactions that occur over the acidic zeolites. Excluding MCM-41, the maximum oil yield is obtained as 37.48 and 30.89% at 500oC in the presence of ZSM-5 and H-Y, respectively. While using MCM-41, the temperature decreases to 450oC and the optimum oil yield is obtained as 33.19%. Antonakou et al. (2006) also studied the catalytic conversion of the biomass pyrolysis product by Al-MCM-41 materials. They found that the production of the total liquid product is decreased in comparison to the non-catalytic run (15 wt %). This is explained by the fact that very high surface areas of the catalyst strongly favor the secondary cracking of the primary produced bio-oil vapours and therefore the respective experiments resulted in less liquid products. The gaseous yields are represented in Figure 4 for the catalytic (ZSM-5, H-Y and MCM-41) and non-catalytic pyrolysis of waste furniture sawdust at four different temperatures ranging from 400oC to 550oC. As the pyrolysis temperature increases from 400oC to 550oC, the gaseous product yield – the non-condensable phase of the pyrolysis vapors – maximizes by increasing the pyrolysis

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Figure 5.  Effect of temperature on solid yields of noncatalytic and catalytic works.

temperature. The degradation of the components of the pyrolytic liquid with higher molecular weights by both thermal and catalytic cracking is the possible reason for the improvement of gas yields with an increasing temperature (Seo et al., 2003; Wang et al., 2010a). Among the catalysts used, the most acidic catalyst is H-Y and therefore, this catalyst produced the maximum gas yields. All catalysts improved gasification and caused higher gaseous product yields compared to non-catalytic work. Catalytic cracking also increased gas yields compared to the gas yields obtained by thermal cracking. The solid (char for non-catalytic work and char + coke for catalytic work) yields are represented in Figure 5 for the catalytic (ZSM-5, H-Y and MCM-41) and non-catalytic pyrolysis of waste furniture sawdust at four different temperatures, ranging from 400oC to 550oC. As the pyrolysis temperature increases from 400oC to 550oC the char yield diminishes. The coking of the catalyst or the aromatization reactions over zeolites causes a higher amount of solid yield. Due to high pore sizes, MCM-41 and H-Y have a higher tendency for coking reactions, which prove the activity of the catalyst to be effective. As is well known, coke deposits cover the active sites of the catalysts and reduce the activity of catalysts. A large pore size would allow for more hydrocarbons to enter through the pore system, which leads to more coke deposition. Therefore, more aromatics were produced with a catalyst that has a large pore size to form coke, which contributed to the fact that the coke formation on the H-Y catalyst was higher than that of the ZSM-5 catalyst (Pütün et al., 2009; Uzun and Sarıoğlu, 2009). The water content of bio-oil varies between 10 and 15% without a catalyst in the temperature range of 400–550oC. Increasing the temperature caused the reduction of the water content of biooil. The use of a catalyst causes a reduction of the water content of bio-oil from 11.56 to 5.63% in the temperature range of 400– 550oC for the ZSM-5 catalyst. Similar trends were determined for the other catalysts used.

Structural analysis The results of the elemental analyses of bio-oils, as C, H and O contents, are given in Figure 6. As can be seen, the C and H

0

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ZSM-5

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MCM-41

Figure 6.  Results of elemental analysis.

Figure 7.  FT-IR spectra of bio-oils non-catalytic (a) and MCM-41 (b), H-Y (c), ZSM-5 (d).

content of oil increases, whereas the O content decreases after catalysis. Here the action of the zeolites in removing the oxygen from the pyrolysis oil is evident. After catalysis the oxygen content of bio-oils were found to be less than that of pyrolysis without using a catalyst. Therefore, catalytically upgraded oil has higher calorific values than that of non-catalytic work. The high heating value of the bio-oil from non-catalytic work is 19.27 MJ kg−1, which is increased to 35 MJ kg−1 after catalytic work. Moreover, the calorific values of bio-oils are very close to those of petroleum products. When the H/C ratios of bio-oils are observed, the H/C ratio of bio-oil obtained by catalytic pyrolysis is higher than that of the non-catalytic work and is increased from 1.52 to ~1.73 after catalytic application. Pyrolysis oils contain a very wide range of complex organic chemicals. The FT-IR spectra indicate the functional groups of bio-oils and are given in Figure 7. Because they have the same functional groups, the obtained spectra are very similar to each other. The O–H stretching vibrations between 3600 and 3400

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Uzun and Kanmaz Table 2.  1H-NMR results of the bio-oil (percentage hydrogen total). Hydrogen type

Chemical shift (ppm)

Bio-oil

Bio-oil obtained by ZSM-5

CH3 γ or further from aromatic ring and paraffinic CH3 CH3, CH2 and CH β to aromatic ring CH2 and CH attached to naphthenes CH3, CH2 and CH α to aromatic ring or acetylenic Total aliphatics Hydroxyls, ring-joining methylene, methine or methoxy Phenols, non-conjugated olefins Aromatics, conjugated olefins

1.0–0.5





1.5–1.0 2.0–1.5 3.0–2.0 3.0–0.5 4.0–3.0

10.44 — 38.08 48.52 14.81

5.04 — 23.68 28.72 11.59

6.07 — 48.24 54.98 10.16

3.99 — 29.71 33.70 7.03

6.0–4.0 9.0–6.0

25.81 10.86

44.84 14.86

25.89 9.24

47.11 12.16

cm−1 of the bio-oil indicate the presence of phenols and alcohols. In particular, the OH peak at around 3396 cm−1 is wider in the spectrum of bio-oil from non-catalytic pyrolysis. The symmetrical and asymmetrical C–H stretching vibrations of the aliphatic CH3 and CH2 groups (2942 cm−1) and the C–H bending vibrations between 1310 and 1513 cm−1 indicate the presence of alkane groups in the pyrolysis bio-oil derived from waste furniture sawdust. The C=C stretching vibration band was observed at 1606 cm−1. The C–H stretching vibrations between 2849 and 2856 cm−1 and the C–H deformation vibrations between 1375 and 1465 cm−1 indicate the presence of alkanes. The presence of the C=O stretching vibrations between 1720 cm−1 and 1770 cm−1 is compatible with the presence of ketone and aldehyde groups. The peak at 1310 is due to the presence of primary, secondary and tertiary alcohols, and the phenols reveal the C–O stretching and O–H bending. The presence of an aromatic ring (900–700 cm−1) and C=O stretching, as well as C–O stretching, indicate the presence of aromatic esters. Wang et al. (2010b) studied the non-catalytic and catalytic pyrolysis of corncob using a thermogravimetry analyzer coupled with Fourier transformation infrared spectroscopy (TGA/FTIR). The effects of MCM-41 on the formation characteristics and composition of pyrolysis vapor were studied. In the presence of MCM-41, the composition of pyrolysis vapor changes slightly; the carbonyl compounds molality decreases, while the molality of phenols and hydrocarbons increases; the increase of phenols exhibits in a wide temperature range; the deoxygenation of oxygenated compounds is accelerated mainly via decarbonylation and a decarboxylation reaction. 1H-NMR band assignments corresponding to the structural features of the obtained bio-oils are given in Table 2. According to this scheme, bands between 0.5 and 3.0 ppm have been identified as aliphatics. The signal range of 4–6 ppm, due to the oxygenated phenols, is broadened. Resonances between 6 and 9 ppm were assigned to aromatic structures. The aliphatic content of bio-oil (non-catalytic work) is decreased from 48.52% to 28.72% and to 33.70% in the presence of ZSM-5 and MCM-41, respectively. However, the H-Y catalyst has a positive effect on aliphatic content enhancement. The phenolic content of the catalytic

Bio-oil obtained by H-Y 0.67

Bio-oil obtained by MCM-41 —

pyrolysis oil by MCM-41 is found to be 47%, which is twice as much as that of the non-catalytic work. The ZSM-5 catalyst is favored for aromatization. The fraction of organics soluble in dichloromethane was further analyzed with gas chromatography-mass spectrometry (GC-MS). This is followed by the aqueous phase and consists of water formed during the reactions and organic compounds soluble in water. This fraction was not analyzed any further because of its incompatibility with the existing analytical equipment (Antonakou et al., 2006). The influence of the catalyst can be further represented by the change in the compositions as well as the carbon distribution of the hydrocarbons in the bio-oil. GC-MS was applied to the bio-oil obtained at optimum conditions to separate and identify the composition. The identification of the peaks was made using the WILEY library. The dominated compound found was 2-metoxy-4 methylphenol. In particular, the main components obtained from the pyrolysis oil were: phenols, ketones, carboxylic acids and carbonyls. The phenolic structure mainly consists of alkylated phenols. The use of MCM41 caused a decrease in the fractions of carbonyls, acids and heavy hydrocarbons. Specifically, the acidic content of bio-oil was decreased from 16.38% to 7.54% with the use of MCM-41. It is noticed that H-Y enhances alcohol production compared to the other catalyst. As a conclusion, a wide range of organic compounds were found in the bio-oil produced. Phenols and hydrocarbons are desirable fractions since they are chemicals with high commercial value, while oxygen-containing compounds, such as acids and carbonyls, as well as heavy compounds, are considered as undesirable fractions. A catalyst is used to enhance more desirable and less undesirable fractions. As is well known, the large fraction of oxygenated compounds reduces the calorific value of the liquid as well as its stability. Furthermore, the reduction of acids is an important factor for the quality of the liquid in terms of its corrosivity, the reduction of carbonyls is important for their stability and the reduction of heavy compounds is important for handling and upgrading purposes, all of which are very important factors to be considered in order for the bio-oil to be used as a fuel (Antonakou et al., 2006).

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Conclusions This study involves the use of synthetic zeolites to improve the quality of liquids obtained from the fast pyrolysis of waste furniture sawdust. As is well known, catalyst selection and the evaluation for higher product selectivity are important for industrial applications. The use of a catalyst enhances more desirable (hydrocarbons) and less undesirable fractions (oxygenated groups and heavy organics). The oils obtained commonly included phenols and alkylated phenols. After liquid–liquid extraction, these groups can be recovered and used as a feedstock such as resin production. The yield of phenols, the desired product, is also increased in the presence of a catalyst compared to non-catalytic work. Moreover, catalytic pyrolysis oils with a higher calorific value and stability can be used as a liquid fuel.

Declaration of conflicting interests The authors declare that there is no conflict of interest.

Funding This research received no specific grant from any funding agency in the public, commercial, or not-for-profit sectors.

References Antonakou E, Lappas A, Nilsen MH, et al. (2006) Evaluation of various types of Al-MCM-41 materials as catalysts in biomass pyrolysis for the production of bio-fuels and chemicals. Fuel 85: 2202–2212. ASTM Standard Test Method for Proximate Analysis of Wood Fuels, Easton, M.D., USA, E870–82, (2013). ASTM, Standard Test Method for Bulk Density of Densified Particulate Biomass Fuels, Easton, M.D., USA, E873–82, (2013). Bridgwater AV (1996) Production of high grade fuels and chemicals from catalytic pyrolysis of biomass. Catalysis Today 29: 285. Iliopoulou EF, Antonakou EV, Karakoulia SA, et al. (2007) Catalytic conversion of biomass pyrolysis products by mesoporous materials: Effect of steam stability and acidity of Al-MCM-41 catalysts. Chemical Engineering Journal 134: 51–57. Jackson MA, Compton DL and Boateng A (2011) Screening acidic zeolites for catalytic fast pyrolysis of biomass and its components. Journal of Analytical and Applied Pyrolysis 92: 224–232.

Kanmaz G (2011) Catalytic Pyrolysis of Pine Sawdust and Characterization of Pyrolysis Oils. MSc Thesis, Department of Chemical Engineering, Anadolu University, Eskisehir, Turkey. Li S, Xu S, Liu S, et al. (2004) Fast pyrolysis of biomass in free-fall reactor for hydrogen-rich gas. Fuel Processing Technology 85: 1201–1211. Mihalcik DJ, Multen CA and Boateng AA (2011) Screening acidic zeolites for catalytic fast pyrolysis of biomass and its components. Journal of Analytical and Applied Pyrolysis 92: 224–232. Nilsen MH, Antonakou E, Bouzga A, et al. (2007) Investigation of the effect of metal sites in Me–Al-MCM-41 (Me=Fe, Cu or Zn) on the catalytic behavior during the pyrolysis of wooden based biomass. Microporous and Mesoporous Materials 105: 189–203. Pütün E, Uzun BB and Pütün AE (2009) Rapid pyrolysis of olive residue. 2. Effect of catalytic upgrading of pyrolysis vapors in a two-stage fixed-bed reactor. Energy and Fuels 23: 2248–2258. Seo YH, Lee KH and Shin DH (2003) Investigation of catalytic degradation of high-density polyethylene by hydrocarbon group type analysis. Journal of Analytical and Applied Pyrolysis 70: 383–398. Sınağ A, Uskan B and Gülbay S (2010) Characterization of the pyrolytic liquids obtained by pyrolysis of sawdust. Journal of Analytical and Applied Pyrolysis 51: 48–52. Torri C, Lesci IG and Fabbri D (2009) Analytical study on the pyrolytic behaviour of cellulose in the presence of MCM-41 mesoporous materials. Journal of Analytical and Applied Pyrolysis 85: 192–196. Uzun BB and Kanmaz G (2013) Effect of operating parameters on biofuel production from waste furniture sawdust. Waste Management and Research 31: 361–367. Uzun BB and Sarıoğlu N (2009) Rapid and catalytic pyrolysis of corn stalks. Fuel Processing Technology 90: 705–716. Uzun BB, Putun AE and Putun E (2007a) Rapid pyrolysis of olive residue. 1. Effect of heat and mass transfer limitations on product yields and bio-oil compositions. Energy and Fuels 21: 1768–1776. Uzun BB, Pütün E and Pütün AE (2007b) Composition of products obtained via fast pyrolysis of olive-oil residue: Effect of pyrolysis temperature. Journal of Analytical and Applied Pyrolysis 79: 147–153. Wang D, Xiao R, Zhang H, et al. (2010a) Comparison of catalytic pyrolysis of biomass with MCM-41 and CaO catalysts by using TGA–FTIR analysis. Journal of Analytical and Applied Pyrolysis 9: 171–177. Wang P, Zhan S, Yu H, et al. (2010b) The effects of temperature and catalysts on the pyrolysis of industrial wastes (herb residue). Bioresource Technology 1013: 236–3241. Williams PT and Horne PA (1995) The influence of catalyst type on the composition of upgraded biomass pyrolysis oils. Journal of Analytical and Applied Pyrolysis 31–39.

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Catalytic pyrolysis of waste furniture sawdust for bio-oil production.

In this study, the catalytic pyrolysis of waste furniture sawdust in the presence of ZSM-5, H-Y and MCM-41 (10 wt % of the biomass sample) was carried...
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