Fuel Processing Technology 101 (2012) 3543

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Fuel Processing Technology

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Analysis of products from pyrolysis of Brazilian sugar cane straw

Maria Silvana Aranda Moraes a, Fernando Georges b, Suelen Rodrigues Almeida b, Flaviana Cardoso Damasceno a, Gabriela Pereira da Silva Maciel a, Claudia Alcaraz Zini a, Rosngela Assis Jacques a, Elina B. Caramo a, b, c,
a b c

Programa de Ps Graduao em Qumica, Instituto de Qumica, Universidade Federal do Rio Grande do Sul (UFRGS), RS, Brazil Programa de Ps Graduao em Cincia dos Materiais, Instituto de Qumica, Universidade Federal do Rio Grande do Sul (UFRGS), RS, Brazil INCT E&A: Instituto Nacional de Cincia e Tecnologia em Energia e Ambiente, RS, Brazil

a r t i c l e

i n f o

a b s t r a c t
The main objective of this work is to investigate the chemical composition of the volatile compounds produced during the pyrolysis of sugar cane straw (SCS). The pyrolysis was conducted in a vertical furnace using a quartz reactor at a temperature of 700 C (7 g of SCS, heating rate of 60 C/min, ux of 1 mL min 1 of N2 and 5 min of hold time at the nal temperature). Pyrolysis products (solid residue and bio-oil) were analyzed. The original biomass and the residual solid phase were characterized by Thermogravimetric Analysis (TGA) and Infrared Spectroscopy (FTIR). The biomass showed a TGA prole similar to cellulose and, according to FTIR analysis, it was rich in oxygenated compounds. The FTIR analysis of solid residue indicated that it was composed mainly by silica. Comprehensive two dimensional gas chromatography with time of ight mass spectrometry detector (GC GC/TOFMS) was applied in the identication and semi-quantication of main compounds in bio-oil, allowing the identication of 123 compounds, mainly oxygenated (acids, ethers, aldehydes, ketones and phenols) with a predominance of furfural and hexenoic acid. The GC GC/TOFMS allowed a group type classication of the compounds and a spatial organization that facilitated the identication of the main compounds in the 2D diagram. 2012 Elsevier B.V. All rights reserved.

Article history: Received 19 June 2011 Received in revised form 27 December 2011 Accepted 11 March 2012 Available online 26 April 2012 Keywords: Bio-oil Sugar cane straw Pyrolysis Gas chromatography GC GC/TOFMS

1. Introduction Biomass is the most common form of renewable energy and widely considered to have a major potential for renewable energy for the future. Pyrolysis is a thermo-degradation technique which is used for transforming the biomass in a more valuable material (bio-oil). Over the last 2 decades, a special attention has been done to the conversion of residual biomass and renewable materials into bio-oil [1,2]. Pyrolysis allows the conversion of biomass into a liquid product, named bio-oil, which can be used as feedstock for fuels and valuable chemicals [36]. Bio-oil is a very complex mixture containing many organic compounds formed by the thermal degradation of cellulose, hemicellulose, lignin and other bio-molecules originally present in vegetable biomass. According to Strezov et al. [7], thermal pyrolytic conversion is one of the promising methods for biomass conversion. The pyrolysis, mainly when developed at medium temperatures (550 C) leads to the production of a pyrolysis gas composed by H2 and CO [8,9]. But this reaction is accompanied by the formation of

Corresponding author at: Programa de Ps Graduao em Qumica, Instituto de Qumica, Universidade Federal do Rio Grande do Sul (UFRGS), RS, Brazil. Tel.: + 55 51 3308 7213. E-mail address: elina@ufrgs.br (E.B. Caramo). URL: http://www.inct.cienam.ufba.br (E.B. Caramo). 0378-3820/$ see front matter 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.fuproc.2012.03.004

other gases and particularly of tars, essentially composed by hydrocarbonaceus material, which are undesirable once they can block the furnace by condensation [10]. A large portion of bio-oil (about 55%) is composed by semi-volatile products which are analyzable through GC/qMS [11,12], while the remaining solid residue can be carbon rich charcoal or, depending on the pyrolytic conditions, formed by silica. Originally the main product of interest was the charcoal [13], but more recently, pyrolysis has been considered as a technology suitable for re-using of agricultural waste for the energy conversion [6,7,14] and also for producing important raw material for the chemical industry, like phenols and other oxygenated compounds [1519]. The thermochemical transformation (gasication and pyrolysis) represents certainly more than 95% of the energetic valorization of biomass. The composition of both phases (vapor and bio-oil) depends on numerous parameters: the raw material (elemental composition, humidity, size) and the operating conditions as temperature, humidity and residence time [11]. Brazil is the largest producer of sugarcane of the world, generating 400 million tons per year, on average [20,21]. The crop of sugarcane is initiated with the burn of the sugar cane plantations, for productivity reasons and safety, but this practice produces a great amount of particulate material (black soot's cane) and toxic gases. This burn is made in situ, on a controlled way, in small and delimited areas, with the

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objective of quickly eliminating the leaves and pointers, so that the stem of the cane it is not burned [21,22]. The main proposals for the reduction and/or elimination of the burning of the cane in Brazil are regulated by two Laws, one Federal (no. 2.661/98) and another of the So Paulo State (no. 11.241/ 2002), which have the objective of promoting a gradual reduction of the sugar cane burning, until its totality in 2031 [21,23,24]. The pyrolysis is an alternative of the burning, producing bio-oil, bio-gas, ashes, charcoal and aggregating value to this material. The use of the sugarcane straw for production of energy appears as an alternative and environmental friendly use of this material, once it is an agricultural residue, that doesn't have another important use [21]. The development of a viable biorenewable agro-industry needs to integrate all of the co-products of pyrolysis in the process [22]. Bio-gas and bio-oils are attractive co-products of pyrolysis and they are possible energy carriers and feedstock for bio-diesel and petrochemicals. The complex nature of bio-oil requires the use of high resolution chromatographic techniques, mainly if coupled to mass spectrometry

detection [2527]. More recently, the development of the multidimensional chromatography, specially the GC GC/TOFMS emerged as a powerful tool in this eld. Many works had been published applying the GC GC/TOFMS in the resolution of complex mixtures, like crude oils, environmental samples and fragrances. Several reviews have also been published in GC GC showing the advantages of this technique in terms of separation capacity, resolution, sensitivity, selectivity, [2833]. Recently, Sfetsas et al. [25] describe the analysis and quantication of three different bio-oils by GC GC/FID and GC GC/TOFMS showing the identication of more than 230 compounds in each oil. Marsman et al. [34,35] also describe the application of GC GC/FID in the group type classication of the compounds of bio-oils. Fullana et al. [36] compared the efciency of GC GC and 1D GC in the characterization of bio-oils and found that around 70% of total chromatogram peaks could be identied with GC GC but only 47% with conventional GC. Beside the high separation capacity of GC GC/TOFMS for qualitative purposes, the quantitative analysis has also been used [25,30] coupled to statistical tools [37,38].

Fig. 1. Equipment for the pyrolysis of sugar cane straw: (a) complete system, (b) vertical furnace and reactor; and (c) dimensions of reactor.

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Fig. 2. Thermogravimetric curves of SDS.

This work explores the production of bio-oils from the pyrolysis of SCS and its characterization by chromatographic methods, mainly GC GC/TOFMS. The solid residue of the pyrolysis was also characterized by FTIR Spectroscopy and Scanning Electron Microscopy (SEM). 2. Experimental 2.1. Samples and materials Dichloromethane (DCM), anhydrous Na2SO4, NaOH and HCl, p.a. grade, were purchased from Merck (Darmstadt, Germany). DCM was bi-distilled to prevent interference in the analytical process. The chromatographic standards were purchased from Supelco (Supelco Park, PA, USA). The sugar cane straw sample was kindly provided by the alembic Dom Braga, located in the city of Dois Irmos, southern Brazil). The sample was triturated in a mill (Wiley Mill Model no. 2, Arthur H. Thomas, Philadelphia, USA) to produce a sub-sample at 0.830 mm. 2.2. Thermogravimetric Analysis (TGA) TGA analysis was conducted in a Thermal Analyzer Instruments (SDT Q600 V20.9 Build 20) operating at a heating rate of 10 C/min from 25 C to 900 C in an alumina sample vial with N2 ux of 10 mL/min. The TGA was conducted with approximately 7.3 mg of the sample [39]. 2.3. Infrared Spectroscopy (FT-IR) The FT-IR spectrum of biomass (SDS) and its pyrolytic products (bio-oil and solid residue) was obtained using a VARIAN 640-IR spectrometer in the IR range of 4004000 cm 1 using the KBr pelleting method, with a resolution of 4 cm 1 with 200 and 100 scans performed for the background and sample spectra, respectively. 2.4. Pyrolysis process The procedure of pyrolysis was based in the work of Tsai et al. [17] and Quiang et al. [40]. The pyrolysis was conducted in a vertical furnace, using a quartz reactor, both were home made. Fig. 1 shows the illustration of the furnace and the reactor with the specication

of each part of them. The bio-oil was collected at the top with a help of a condensator. The conditions of the biomass pyrolysis were previously optimized and the following conditions were used: temperature = 700 C, heating rate = 60 C min 1, nal time= 5 min and N2 ow = 1 mL min 1. A weighed amount of SDS (about 7 g) was introduced into the quartz reactor (Fig. 1) in the pyrolysis oven and the apparatus was uxed with a nitrogen stream at 1 mL min 1 for 5 min and the sample was heated from 25 C to 700 C (set temperature) at 60 C min 1 and remains at this temperature for 5 min (till no more vapors are formed). After each pyrolysis, the reactor and all the connections were cleaned with acetone and were dried accurately with a hot air stream at 150 C prior to a new analysis. 2.5. GC GC/TOFMS analysis The GC GC/TOFMS Pegasus-IV system (LECO, St. Joseph, USA) equipped with cryogenic modulator and CTC Combi Pal auto sampler was used. The separation was carried out at a constant ow of 1.0 mL/min, using Helium (Linde Gases, Canoas, Brazil, 99.999% purity) as carrier gas. All samples were introduced using the split mode with a split ratio of 10:1. The injector was kept at 275 C. The columns set used were: DB-5 (30 m 0.25 mm 0.25 m) and DB-17 ms (1.2 m 0.18 mm 0.18 m), both acquired from Agilent Technologies J&W Scientic, Folsom, CA, USA. The modulator was a cryogenic quadjet refrigerated with liquid nitrogen, and the modulation period was 10 s with hot and cold pulse of 0.4 s and 2.1 s, respectively. The temperature program of the rst column started at 40 C for 5 min and reached a nal temperature of 315 C at 3 C min 1, where it was kept for 10 min. The second column temperature was 10 C above the temperature of the main oven. Transfer line was held at 275 C and the electron
Table 1 Thermogravimetric analysis of sugar cane straw. Step Tinitial (C) Tnal (C) 81.8 212.0 370.4 509.6 900.0 Weight loss (%) 8.6 2.0 50.0 7.8 5.8 25.8 Explanation CO2 and water Water Organic volatiles Organic semi-volatiles Organic xed Inorganic residue (ashes)

1 25.0 2 81.8 3 212.0 4 370.4 5 509.6 Residual mass

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Fig. 3. Thermogravimetric curves of cellulose and lignin. Modied from Ref. [42].

impact ionization source operated at 250 C with collision energy of 70 eV. Detector voltage was 1400 V, mass range was 45500 Da and data acquisition rate was 100 Hz. Data processing was achieved using integrated Leco ChromaTOF software, version 3.32. The identication of compounds was performed by comparison with the

library of the equipment, mass spectral examination, retention time and elution order. The bio-oil was previously derivatized with MSTFA providing trimethylsilyl derivatives of phenols, alcohols, and acids for better identication and resolution.

Fig. 4. Comparison between the FTIR spectra of (A) SCDS, (B) py-SCS and BO (C).

Fig. 5. Two dimensional color diagram of GC GC/TOFMS of the bio-oil with marked apices.

M.S.A. Moraes et al. / Fuel Processing Technology 101 (2012) 3543 Table 2 Identication and semi quantication of the compounds in bio-oil of SDS. Peak 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 RT 1D (min) 6.5 7.5 7.5 8.0 8.3 9.2 9.3 9.7 9.7 10.5 10.5 11.0 11.0 11.7 12.8 13.0 13.2 13.2 13.2 13.7 13.7 14.0 14.2 14.5 14.5 14.5 14.8 15.5 15.8 15.8 16.3 16.5 16.5 17.3 17.3 17.7 17.8 17.8 18.0 18.2 18.7 19.2 19.7 19.7 19.7 19.7 20.7 21.7 21.8 21.8 22.2 22.3 23.0 23.2 23.3 23.5 23.7 24.2 24.5 24.7 25.2 25.2 25.7 26.7 27.5 28.0 28.3 28.3 28.3 28.8 29.0 29.0 29.2 RT 2D (s) 3.5 3.0 5.0 2.9 5.6 6.1 6.4 2.8 6.5 4.1 5.3 6.0 6.2 7.2 6.2 3.4 6.2 9.5 9.9 3.6 6.6 3.0 6.9 3.1 5.6 8.5 3.8 6.8 6.7 7.2 3.4 6.5 8.8 6.4 7.3 3.5 3.8 7.5 3.5 6.3 7.7 7.7 3.7 6.6 6.7 7.9 4.0 8.9 3.3 4.1 3.0 6.5 7.0 2.8 9.2 7.5 5.2 3.9 4.7 3.9 4.0 5.3 4.0 4.2 4.1 5.0 3.1 5.5 5.7 6.4 3.0 5.7 4.0 Namea Toluene Propenoic acid Cyclopentanone Propanoic acid Furfural (isomer 1) Furfural (isomer 2) C1 furan Butanoic acid Cyclopentenone C2-benzene Furanmethanol C2 furan Furanone Cyclopentenedione C1 cyclopentenone (isomer 1) Butenoic acid Furanyl ethanone Dehydro-furanone C1 furanone (isomer 1) Butenone, hydroxy (isomer 1) Cyclopentenone, hydroxy Pentanoic acid (isomer 1) Cyclohexenone Pentanoic acid (isomer 2) C2 cyclopentenone (isomer 2) C1 furanone (isomer 2) Butenone, hydroxy (isomer 2) Cyclohexanodione (isomer 1) C1 furfural C1 Cyclopentenone (isomer 2) Pentenoic acid (isomer 1) C1 Furanyl hydroxy ketone C1 Furanone (isomer 3) C2 Cyclopentenone (isomer 3) Pyranodione Pentenoic acid (isomer 2) Furanyl methoxy C2 Dihydro furanone Pentenoic acid (isomer 3) Furanyl propanone Cyclohexanodione (isomer 2) Cyclohexenedione (isomer 1 Pentenoic acid (isomer 4) C1 furan, acetyl C2 cyclopentenone (isomer 1) Cyclohexenedione (isomer 2) Phenol C1 hexenone Hexanoic acid (isomer 1) Furancarboxylic acid (isomer 1) Etanediol Phenol, methoxy C2 cyclohexenone Decane Levoglucosenone Maltol Furanmethanol (isomer 1) Hydroxy butanoic acid Furanmethanol (isomer 2) C1 phenol (isomer 1) C1 phenol (isomer 2) Furanmethanol (isomer 3) C1 phenol (isomer 3) C3 furan Furancarboxylic acid (isomer 2) Sorbic acid Propanedioic acid Hexenoic acid (isomer 1) Hexenoic acid (isomer 2) Benzofuran, dihydro Hexanedioic acid Uracil C2 phenol (isomer 1) Area %b 2.02 1.04 0.54 4.39 0.69 18.05 2.38 0.12 0.07 0.25 0.08 0.07 0.38 0.31 0.81 0.28 0.94 0.14 2.87 0.59 0.34 0.05 0.25 0.10 0.08 0.75 2.04 0.05 1.20 0.29 0.34 0.07 0.38 0.04 0.19 0.54 4.25 0.29 0.73 0.09 0.06 0.17 0.53 0.07 0.27 0.07 1.87 0.18 0.10 0.07 2.85 0.06 0.05 0.05 0.34 0.25 0.87 1.20 0.09 0.71 0.63 0.08 1.75 1.68 0.10 3.55 0.10 0.11 9.64 0.14 0.15 0.87 0.24 Formula C7H8 C6H12O2Si C5H8O C6H14O2Si C5H4O2 C5H4O2 C5H6O C7H16O2Si C5H6O C8H10 C5H6O C6H8O C4H4O2 C5H4O2 C6H8O C7H14O2Si C6H6O2 C4H6O2 C5H6O2 C7H14O2Si C2H6O2 C8H18O2Si C6H8O2 C8H18O2Si C7H10O C5H6O2 C7H14O2Si C6H6O2 C6H6O2 C6H8O C8H16O2Si C6H6O3 C5H6O2 C7H10O C5H4O3 C8H16O2Si C8H14O2Si C6H8O2 C8H16O2Si C7H8O2 C6H6O2 C6H6O2 C8H16O2Si C7H8O2 C7H10O C6H6O2 C9H14OSi C7H12O C9H20O2Si C8H12O3Si C8H22O2Si2 C7H8O2 C8H12O C11H24 C6H6O3 C6H6O3 C8H14O2Si2 C8H18O3Si C8H14O2Si C10H16OSi C10H16OSi C8H14O2Si C10H16OSi C7H10O C9H14O3Si C9H16O2Si C9H20O4Si2 C9H18O2Si C9H18O2Si C8H8O C12H24O4Si2 C7H12N2O2Si C11H18OSi

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Chemical class Hydrocarbon Acid Ketone Acid Aldehyde Aldehyde Ether Acid Ketone Hydrocarbon. Alcohol Ether Ketone Ketone Ketone Acid Ketone Ketone Ketone Ketone Ketone Acid Ketone Acid Ketone Ketone Ketone Ketone Aldehyde Ketone Acid Ketone Ketone Ketone Ketone Acid Alcohol Ketone Acid Ketone Ketone Ketone Acid Ether Ketone Ketone Phenol Ketone Acid Acid Alcohol Phenol Ketone Hydrocarbon Other Other Alcohol Acid Alcohol Phenol Phenol Alcohol Phenol Ether Acid Acid Acid Acid Acid Ether Acid Other Phenol (continued on next page)

40 Table 2 (continued) Peak 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 Area Area Area Area Area Area Area Area
a b

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RT 1D (min) 29.2 29.3 29.8 29.8 30.2 30.2 30.3 30.8 31.0 31.8 32.0 32.7 32.7 32.8 33.2 33.3 33.7 33.8 33.8 34.3 34.8 35.7 35.8 37.0 37.2 37.3 37.5 37.7 37.7 39.8 39.8 39.8 40.0 40.2 40.7 41.7 42.5 43.2 43.3 43.3 43.5 44.0 44.0 44.7 45.8 47.8 48.2 49.7 51.2 51.3 % % % % % % % % acids alcohols aldehydes ethers hydrocarbons ketones others phenols

RT 2D (s) 9.1 4.7 4.1 4.7 4.7 5.1 4.2 4.2 5.3 6.3 4.8 5.3 5.4 8.3 6.7 5.4 3.7 2.8 5.7 5.4 3.8 4.7 5.3 4.5 5.4 3.6 6.0 5.3 5.4 3.6 3.6 5.5 3.7 4.7 5.2 3.6 6.0 4.0 3.4 4.1 5.0 4.1 4.9 3.3 6.0 2.8 4.3 3.5 4.3 4.5

Namea C1 furfural, hydroxy Methoxyphenol (isomer 2) Benzaldehyde, hydroxy (isomer 1) Hexenoic acid (isomer 3) Benzoic acid Cyclohexanoic acid C2 phenol (isomer 2) C2 phenol (isomer3) Heptenoic acid Hexanoic acid (isomer 2) Methoxyphenol (isomer 1) Nitrocatechol Furan acetic acid Acetoxy C1-furfural Methoxy vinyl phenol C1 furan carboxylic acid (isomer 1) Benzenodiol (isomer 1) Tridecane C1 furan carboxylic acid (isomer 2) Octenoic acid Butenedioic acid C2 xanthene Benzaldehyde, hydroxy (isomer 2) Benzaldehyde, methoxy hydroxy (isomer 1) C2 benzaldehyde, trimethoxy Benzenodiol (isomer 2) C2 cyclohexanol Acetophenone, hydroxy (isomer 2) Ketocaproic acid Benzenediol, C1 Phenyl ethanol hydroxy Acetophenone, hydroxy (isomer 2) Ethoxy phenol C3 benzenediol Methoxy phenazine Nonanol Benzaldehyde, methoxy hydroxy (isomer 2) C2 benzenediol Benzenetriol Vanillyl alcohol Benzaldehyde, dimethoxy, hydroxy Benzoic acid, hydroxy C3 phenol Dodecanol Acetophenone, hydroxy (isomer 1) Benzoic acid, bis hydroxy C1 benzoic acid, hydroxy Levoglucosan Hydrocinnamic acid Benzoic acid, methoxy hydroxy

Area %b

Formula

Chemical class Aldehyde Phenol Aldehyde Acid Acid Acid Phenol Phenol Acid Acid Phenol Phenol Acid Aldehyde Phenol Acid Phenol Hydrocarbon Acid Acid Acid Ether Aldehyde Aldehyde Aldehyde Phenol Alcohol Ketone Acid Phenol Phenol Ketone Phenol Phenol Other Alcohol Aldehyde Phenol Phenol Alcohol Aldehyde Acid Phenol Alcohol Ketone Acid Acid Other Acid Acid

0.16 C6H6O3 1.79 C10H16O2Si 1.31 C10H14O2Si 0.03 C8H16O2Si 0.28 C10H14O2Si 0.11 C10H20O2Si 0.04 C11H18OSi 0.05 C11H18OSi 2.10 C10H20O2Si 0.42 C9H20O2Si 0.04 C10H16O2Si 0.11 C6H5NO4 0.26 C9H14O3Si 0.07 C8H8O4 0.07 C9H10O2 2.69 C9H14O3Si 1.40 C12H22O2Si2 0.05 C13H28 0.30 C9H14O3Si 0.21 C11H22O2Si 0.15 C10H20O4Si2 0.03 C15H14O 0.29 C10H14O2Si 0.69 C11H16O3Si 1.81 C12H16O4 0.20 C12H22O2Si2 0.13 C9H18O2Si2 0.05 C11H16O2Si 0.04 C9H18O3Si 0.07 C13H24O32Si2 2.54 C14H22O2Si2 0.10 C11H16O11Si 1.59 C14H26O2Si2 0.09 C13H20OSi2 0.81 C13H10N2O 0.03 C12H28OSi 0.45 C11H16O3Si 0.06 C14H26O2Si2 0.87 C15H30O3Si3 0.06 C14H26O3Si2 0.07 C12H18O4Si 0.06 C13H22O3Si2 0.44 C13H20O2Si 0.03 C12H26O 0.11 C11H16O11Si 0.02 C16H30O4Si3 0.02 C14H24O3Si2 0.48 C15H34O5Si3 0.22 C15H26O3Si2 0.04 C14H24O4Si2 30.07 (35 compounds) 8.47 (10 compounds) 24.81 (11 compound)s 4.36 (6 compounds) 2.38 (4 compounds) 12.55 (31 compounds) 2.87 (6 compounds) 14.50 (20 compounds)

Cx = alkyl chain with x Carbons atoms. % Area = (Ai/Ai) 100, considering only the tentatively identied peaks.

3. Results and discussion 3.1. Initial characterization of the SDS The crude SDS samples contained 0.16 0.01% moisture, determined by the procedure described in the ASTM D 317387 [41]. Fig. 2 shows the TGA curves for thermal decomposition of the sugar cane straw. The main losses are represented in this gure and are registered in Table 1. Till 82 C the losses are due to water and CO2, from this temperature and till 370 C occurs the loss of volatiles and after this and till 500 C all the organic materials are decomposed. At the

end of the process, 26% of inorganic material remains as residual mass in the form of ashes. As can be conclude, the total burning of this biomass can be promoted at temperatures bellow to 700 C. The amount of lignin and cellulose in the biomass is an important factor in the pyrolysis analysis and the simple comparison between the thermogravimetric proles of the biomass and these materials can suggest which is the main constituent of the original biomass [42,43]. Fig. 3 shows the thermogravimetric curve for cellulose and lignin (data modied from Rout et al. [42]) and it is possible to observe that the sugar cane straw has a behavior similar to cellulose, indicating that this is the main constituent of the original biomass [44,45].

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The literature indicates that normally in fast pyrolysis at relatively high temperatures, the nal ash residue of biomass consisted of around 95% silica [4650]. 3.2. Infrared Spectroscopy Fig. 4 shows the infrared spectra of SDS, the solid residue of pyrolysed SDS (py-SDS) and the bio-oil produced (BO). In this gure are also showed all the main functional groups that can be identied in each spectrum. Contrasting with SDS and BO, the py-SDS-FTIR showed a typical prole of silica, that is, an inorganic material, which corroborate with TGA data. On the other hand, the spectra of SDS and BO are very similar. The main difference between them are

in the intensity of the bands, mainly those related to oxygenated compounds (O\H, C\O and C_O). These functional groups are characteristic of ketones, phenols, ethers, esters, acids and aldehydes which are the main compounds described in the literature as typically found in bio-oil from ligneouscellulosic material [18,19]. In general, the spectrum of bio-oil was dominated by peaks at 3300 cm 1, which corresponded to the stretching vibrations of O\H. A sharp peak at 1700 cm 1 represents carboxyl groups and has been attributed to hemicelluloses [51]. These peaks are originated from the stretching mode of carbonyls, mainly ketones and acids [52]. Peaks from 1050 to 1250 cm 1 can represent C\H, O\H, or CH2 bending frequencies [51] and can be indicators of lignin. The large band at ~1050 cm 1 corresponds to Si\O bonds.

Fig. 6. Two dimensional graphics generated from retention time of GC GC/TOFMS data of and classied according the chemical classes of the identied compounds: (a) carboxylic acids; (b) alcohols and ethers; (c) aldehydes; (d) ketones, (e) phenols and (f) other classes.

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3.3. GC GC/TOFMS of bio-oil The mass yield in bio-oil was 23.9% related to the weight of biomass initially used ( 7 g). The bio-oil produced in the pyrolysis of SDS showed high amount of water ( 97,4%) which implied in extracting the organic phase with dichloromethane and drying it with anhydrous sodium sulfate, before the derivatization and the chromatographic analysis. After the extraction of the excess of water, the bio-oil was derivatized with MSTFA and directly analyzed by GC GC/TOFMS. Fig. 5 shows the color and apex diagram of the GC GC/TOFMS analysis of the derivatized bio-oil produced in the SDS pyrolysis. The apices are signaled in black and those that were tentatively identied, are surrounded by a white circle. This analysis showed a total of 363 compounds of which only 123 were tentatively identied (33.9%). Table 2 shows the tentative identication of the peaks, their Area% ([Ai/i] 100), retention times (1D and 2D) and other characteristics. Only were considered identied (or tentatively identied) those peaks with similarity between the spectra (library and sample) higher than 85%. The Area% was calculated considering the sum of peak areas of all the identied compounds, which corresponds to 42.1% of the total area detected. As can be seen in Table 2 the majority of the compounds tentatively identied belong to the classes of acids, alcohols, aldehydes, ethers, ketones and phenols, among others minoritary (sugars, hydrocarbons, nitrogenated compounds, lactones). The major compound found in the sample of bio-oil was furfural (18.05%) followed by hexenoic acid (9.65%). Twenty ve compounds showed percentages of areas above 1% and the sum of these areas accounted to 76.8% of the total area identied. For a better comprehension of the data and also for promoting the classication and the distribution of the compounds in the sample, it was constructed another graphic (using the software Excel) for each class of compound identied, using the retention times (1D and 2D). Fig. 6 shows all the reconstructed diagrams for each class of identied compounds. Data presented in these diagrams are only qualitative. This form of showing the chromatographic data allows observing the spatial organization of the compound classes in the 2D diagram. This organization is useful in the identication of some compounds and is impossible to observe in one-dimensional chromatography. On the other way, in the original two dimensional diagram (Fig. 5) is difcult to realize this classication due to the high amount of compounds in a little region of the diagram. For this reason the use of Excel facilitates the analysis. In Fig. 6 it is possible to clearly observe the families of saturated, unsaturated and aromatic carboxylic acids (Fig. 6a); furans and benzofurans (Fig. 6b); furfurals and benzaldehydes (Fig. 6c); phenols, methoxy phenols and benzenediols (Fig. 6d) and cyclic unsaturated ketones and acetophenones (Fig. 6e). Shen and Gu [12], discussed exhaustively the thermal decomposition of cellulose and identied considerable amounts of furfural and other phenol derivatives. The literature shows that the primary chemical classication pyrolysis products of cellulosic biomass can be summarized as follows: acids, alcohols, aldehydes, esters, ketones, phenols, guaiacols, syringols, furans, alkanes, alkenes, aromatics, nitrogen compounds, and miscellaneous oxygenates [1519], conrming the identication of the bio-oil studied in the present work. It can be concluded that an industrial pyrolysis process of SDS in Brazil, a major producer of sugar cane in the world, would produce important feedstocks for chemical industry and also for energy purposes.

It could be observed through TGA analysis that the burning of the SDS occurs around 500 C, which allows to use temperatures below 700 C without signicant losses in the yield of bio-oil. The analysis of SDS and BO by FTIR indicated the presence of a great variety of functional groups as phenols, alcohols, acids, alkanes, ketones, ethers and aldehydes while for py-SDS these groups were eliminated during the pyrolysis, resulting in a solid residue rich in inorganic material (silica). The characterization of the bio-oil for GC GC/TOFMS was fundamental for a larger understanding of the composition of the bio-oil, once the sample are composed by a complex mixture of chemical compounds (with high amount of isomers). This technique is more sensitive, selective and with larger resolution power that allowed the identication of the chemical classes. More than 120 compounds were tentatively identied in the bi-oil, mainly oxygenated ones (acids, aldehydes, alcohols, phenols, ethers and ketones). Acknowledgment Authors thank to PETROBRAS, CNPq and FINEP for the nancial support of this work. Also thank to Prof. Dr. Edilson Volmir Benvenutti, from Chemistry Institute, Federal University of Rio Grande do Sul, for the discussion on FTIR results. References
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