Fuel 89 (2010) 40494052

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Fuel
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Short communication

Bagasse from the mezcal industry as an alternative renewable energy produced in arid lands
L. Chvez-Guerrero *, M. Hinojosa
Km 10 de la Nueva Carretera al Aeropuerto Internacional de Monterrey, C.P. 66600, Apodaca, Department of Nanotechnology, Centre of Innovation Research and Development on Engineering and Technology, UANL, N.L., Mexico Av. Universidad s/n, Cd. Universitaria, San Nicols de los Garza N.L. C.P. 66450, Facultad de Ingeniera Mecnica Y Elctrica, Universidad Autnoma de Nuevo Len (UANL), Nuevo Len, Mexico

a r t i c l e

i n f o

a b s t r a c t
In the mezcal industry, the xerophyte Agave salmiana is used to produce mezcal, and neither the plant nor its residues have been studied before as an alternative source of fuel. Bagasse and wasted bers samples from alcoholic beverage production were collected in order to nd out their properties as fuel. Another sample consists in pyrolyzed bagasse at 450 C to produce carbon. DSC results revealed differences in the heat of combustion values, where pyrolyzed bagasse (19.36 MJ/kg) had a higher value than bagasse (9.55 MJ/kg) or the ber (8.4 MJ/kg). SEM images showed the morphological changes in the bers after their processing. TGA analysis showed the presence of different alcohols impregnated on the bagasse, which allows for an increase in heat of combustion. With these preliminary results it can be seen that it is possible to use the byproducts generated by the alcoholic beverage production as an alternative source of fuel. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 10 September 2009 Received in revised form 21 June 2010 Accepted 15 July 2010 Available online 27 July 2010 Keywords: Agave salmiana Mezcal Bagasse Biofuel Xerophytes

1. Introduction Production of alternative sources of energy is a topic of high importance, because they can be utilized to substitute partially the fossil fuels in order to decrease compounds such as COx, NOx and SOx in the atmosphere [1]. Another reason is that fossil fuels are limited, and it is necessary to develop different kinds of renewable energy while use of fossil fuels is still economically viable. Energy crops have been used to produce biofuels, which have played an important part in the clean energy supply [2]. Fertile lands are commonly used to grow these crops, but this is a problem due to the fact that the production of grains for human consumption can be reduced. It can also cause deforestation and a higher use of pesticides and most of the time these processes consume as much energy as is produced [3]. There is a large quantity of arid and semi-arid lands around the world, furthermore, every year this amount increases because of the desertication and the abandoning of agricultural lands by farmers [4]. These lands are able to produce crops that can be used to generate fuels, bers, food, chemicals and other products [5],

* Corresponding author. Address: Av. Universidad s/n, Cd. Universitaria, San Nicols de los Garza N.L. C.P. 66450, Facultad de Ingeniera Mecnica Y Elctrica, Universidad Autnoma de Nuevo Len (UANL), Nuevo Len, Mexico. Tel.: +52 (81) 8329 4020x5770; fax: +52 (81) 83294020. E-mail address: leonardo.chavezgr@uanl.edu.mx (L. Chvez-Guerrero). 0016-2361/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2010.07.026

and then plants that grow in those environments can be used as biomass. Some of the resistant plants that grow in dry soils are called xerophytes, where Agave plants are a part of this group. There are almost 300 Agave species, all native to the American continent. Most of the species are found in Mxico [6]. The Agave plant has been used for 10,000 years to produce food, beverages and bers [7]. In Mxico, the production of distilled alcoholic beverages using agave is a tradition since the XVII century [6]. These beverages have different names, depending on the region of production; the most popular being tequila and mezcal. The mezcal is produced using raw materials such as Agave salmiana, Agave angustifolia and Agave potatorum [6,8]. The mezcal production process includes ve steps: cooking, milling, fermentation, distilling and aging [8]. The average production of these beverages in 2007 was 9400 L/ month [9]. The process to obtain the alcoholic beverages generates a main byproduct in the form of bagasse. For every liter of mezcal, 15 kg of bagasse on wet basis are produced [6]. Then 141 tons of bagasse are produced monthly, this byproduct can be used as a fuel in the mezcal factories and the surroundings, where most of the time mezcal production is the only viable economic activity. Due to the fermentation process, the bagasse is continuously in contact with the products, it means that it is impregnated with alcohols that could increase the heat of combustion of the bagasse when used as an alternative fuel. The main products in the fermentation process are: methanol, ethanol, n-propanol, 2-butanol and acetic

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L. Chvez-Guerrero, M. Hinojosa / Fuel 89 (2010) 40494052

Fig. 1. SEM images showing a smooth ber of Agave salmiana (a and b) and a bagasse ber showing holes due the process (c and d).

acid [10]. The use of residual agave as a solid fuel has many advantages: (1) such as it does not come from alimentary crops (corn, soybean), (2) it is an industrial residue, (3) there is no need to watering the agave and the most important (4) it can grow in arid lands under extreme conditions. The objective of this paper is to show the potential of disposal waste from the alcoholic beverage industry as a solid fuel, testing the ber, bagasse and pyrolized bagasse through DSC analysis to obtain the combustion heat. 2. Experimental 2.1. Pyrolized bagasse The bagasse and the ber were directly collected as residues from the processing at the IPIA S.A de C.V. mezcal factory in San Luis Potos, Mxico. The bagasse was put in plastic bags and stored in a refrigerator for subsequent analyses. A Barnstead 2100 tubular furnace was used to heat the bagasse at 450 C in order to produce pyrolized carbon, 5 g were put into a quartz tube, and then the tube was placed in the furnace for 30 min. The samples were isolated from the environment by passing an argon ow through the quartz tube at 0.5 L/min. The water loss percentage of the samples was obtained using porcelain crucibles heated in a furnace at 110 C. 2.2. Electron microscopy studies The samples were glued to aluminum holders, sputter-coated with gold (Cressington Sputter Coater 108 Auto) using 40 A for 20 s under argon atmosphere. The morphology of the samples was determined using a Scanning Electronic Microscope (FEI XL 30 SFEG), with 57 kV at different magnications. 2.3. DSC and TGA analysis A Differential Scanning Calorimetry DSC 60 Shimadzu was used with a N2 atmosphere (100 mL/min) in the range of 25500 C,

during 5200 s. DSC curves were obtained using around 1.8 2.6 mg. The TGA curves were obtained using around 4 mg as initial sample mass. The bagasse was tested in a TGA Thermo Cahn model Versatherm, with temperature range of 251000 C and heating rate of 10 C/min in N2 atmosphere.

Fig. 2. The thermal analysis made by TGA of the bagasse is shown. Two peaks can be appreciated at 303 and 397 C in (a). This prole shows a zoom in the range 29 200 C where the evaporation of volatile compound could be correlated (b).

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Table 1 Show the different compounds founded in the mezcal. The temperature showed (C) indicates the boiling point (BP) and the possible correspondence in the curve obtained by the TGA analysis (TGA). Name BP TGA Methanol 64.6 60 Ethyl acetate 77 68 Ethanol 78.5 80 n-Propanol 97.2 99 2-Butanol 99.5 99 2-Methyl-propanol 108 112 Acetic acid 117.9 125 2-Methyl-1-butanol 128 136 High alcohols 137157 149

Fig. 3. DSC results for agave samples named SB for bagasse, SC for carbonized bagasse and SF for raw ber. The heat of combustion of the samples is calculated using the area under the curves.

3. Results and discussion 3.1. SEM images of the bers The differences between the A. salmiana bers and bagasse can be seen in Fig. 1. The image in Fig. 1(a and b) shows the natural ber which looks smooth, while in Fig. 1(b and c), the ber taken from the bagasse has holes and cracks due to the mezcal production process, where sugar is used by micro-organisms and converted into different substances (mainly alcohols). The bers have different lengths and diameters due the heterogeneity of the sample, which can be considered a composite material (bermatrix). The SEM characterization of the samples was needed, because there is not enough published information comparing agave before and after the mezcal production process. 3.2. Thermogravimetric analysis (DSC, TGA) As can be seen in Fig. 2 the TGA curve of the bagasse showed three mass loss stages. The rst stage occurred at temperatures up to 200 C and was attributed to alcohol and moisture elimination. The second stage occurred at 303 C and represented the release of organic compounds like fats, waxes, etc. The third stage occurred at 397 C and was caused by the decomposition of, the lignin, hemicellulose and cellulose that produce CO2. Fig. 2(b) corresponds with the zoom of the prole (Fig. 2(a)) within the range of 29200 C, where different peaks can be seen indicating the boiling

point of the compounds contained in the bagasse. Table 1 shows the different compounds that make up the mezcal [1012]. Also, this table shows the temperatures at which the compounds can be found through the TGA prole (Fig. 2(b)). The residue on the TGA test was 16% of the initial mass and consisted of inorganic compounds in the form of oxides and carbonates (CaCO3). These results show that the bagasse is still impregnated with alcohols and the presence of these compounds may increase the efciency of the biomass as a fuel for heat applications. Preliminary DSC results are shown in Fig. 3, where the prole SF (ber), SB (bagasse) and SC (carbon) represent the raw ber, the bagasse and the pyrolyzed bagasse (450 C). It was found that the heat combustion values were 8.4 MJ/kg for the ber, 9.55 MJ/ kg for the bagasse and 19.36 MJ/kg for pyrolyzed bagasse (carbon). In relation to the pyrolyzed bagasse the heat combustion was increased two times, plus liquid fuels and various sub products were obtained. The area under the curves (A) in Fig. 3 was obtained using the software of the DSC, which corresponded with heat combustion levels. (Q) and Table 2 contains the necessary values to get the Qc. Therefore if 141 tons of bagasse (9.55 MJ/kg) are produced in 1 month, then 1346 GJ can be produced if the waste material from the mezcal industry are exploited. These values can be compared with bagasse from different resources, like cane which has values around %811 MJ/kg [13,14] with a moisture content of around 50% and ash content in the range of 45%. Proposed future work includes: (1) testing the bagasse using a calorimetric bomb to characterize the thermal behavior of the material in order to obtain the heat of combustion of the bagasse and its liquid sub products. (2) Testing the A. salmiana leaves which are cut from the plant before the cooking process and wasted, using fast pyrolysis at different temperatures in order to produce char samples. (3) Analysing the pyrolysis sub products (gasliquid) to get different fuels contained in the bio-oil (CO2, CO, CH4, H2, C2H6, C2H4) [15,14]. (4) Finally, testing the pyrolysis sub products as a feedstock to produce hydrogen. 4. Conclusions These preliminary results have generated substantial information supporting the viability of the bagasse as a solid fuel, mainly due to its level of heat combustion and the considerable amount of byproduct that can be produced. The heat combustion (Qc) values of 8.4 MJ/kg for the ber, 9.55 MJ/kg for the bagasse, 19.36 MJ/kg for pyrolyzed bagasse and the total amount of bagasse produced monthly (141 tons) show that bagasse from mezcal production has potential as a solid fuel.

Table 2 Some values from the DSC experiments are shown, which are necessary to calculate the combustion heat of the samples. Moisture % SF SB SC 11.28 6.52 7.39 Mass 103 (g) 2.20 2.60 1.80 DT (k) 552.65 571.67 661.68 Area 103 (mW s) 18.47 24.84 34.85 Q (J) 18.47 24.84 34.85 c (J/g K) 15.19 16.71 29.26 Qc (kJ/g) 8.39 9.55 19.36

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L. Chvez-Guerrero, M. Hinojosa / Fuel 89 (2010) 40494052 [5] Wiley Hinman C. New crops for arid lands. Science 1984;225:14458. [6] Colunga-Garcia P, Larqu A, Eguiarte L, Zizumbo-Villarreal D. En lo ancestral hay futuro: del tequila, los mezcales y otros agaves. CONABIO, Mxico; 2007. p. 304. ISBN: 978-968-6532-18-0. [7] Kuttruff Jenna T, Gail DeHart S, OBrien Michael J. 7500 Years of orehisotic footwear from Arnold research cave, Missouri. Science 1998;281:725. [8] de Len-Rodriguez Antonio, Escakante-Minakata Pilar, Barba de la Rosa Ana P, Blaschek Hans P. Optimization of fermentation conditions for the production of the mezcal from Agave salmiana using response surface methodology. Chem Eng Process 2008;47:7682. [9] National Institute of Statistics and Geography (INEGI). Bebidas destiladas de Agave/Tequila/volumen, Mxico. <http://dgcnesyp.inegi.org.mx/cgi-win/ bdieintsi.exe/NIVC100640055003300090010003000090#ARBOL> [accessed 03.23.10]. [10] de Len-Rodrguez Antonio, Gonzlez-Hernndez Lidia, Barba de la Rosa Ana P, Escalante-Minakata Pilar, Lpez Mercedes G. Characterization of volatile compounds of mezcal, an ethnic alcoholic beverage obtained from Agave salmiana. J Agric Food Chem 2006;54:133741. [11] The Merck Index. 11 ed. Rahway, NJ, USA: Merck and Co.; 1989. s chemical engineers handbook. 7th [12] Perry Robert H, Green Don W. Perry ed. USA: McGraw Hill; 1999. [13] Moth Cheila G, de Miranda Iara C. Characterization of sugarcane and coconut bers by thermal analysis and FTIR. J Therm Anal Calorim 2009;97:6615. [14] Teixeira Ernesto Vvian AR, Ribeiro Clvis A, Hojo Ossamu, Fertonani Fernando L, Spirandeli Crespi Marisa. Thermal characterization of lignocellulosic residue from different sugarcanes. J Therm Anal Calorim 2009;97:6536. [15] Onay O, Gaines AF, Kockar OM, Adams M, Tyagi TR, Snape CE, et al. Comparison of the generation of oil by the extraction and hydropyrolysis of biomass. Fuel 2006;85:38292.

The results also show that due to the process used in mezcal production, the bagasse is impregnated with different compounds, which can help in the efciency when used as a solid fuel. Lastly the work shows the potential of the agave plants to produce renewable energy in a sustainable way, because these plants can grow in arid lands and abandoned elds. Acknowledgements This work was supported by the Universidad Autnoma de Nuevo Len (UANL), the Consejo Nacional de Ciencia y Tecnologa (CONACyT) and the IPICyT. L.C.G. thanks for the Retention Scholarship #92991. References
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