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Biohydrogen Production from Cassava Wastewater in an Anaerobic Fluidized Bed Reactor

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Biohydrogen Production from Cassava Wastewater in an Anaerobic Fluidized Bed Reactor Brazilian Journal of Chemical ISSN 0104-6632 Printed in Brazil Engineering www.abeq.org.br/bjche Vol. 31, No. 03, pp. 603 - 612, July - September, 2014 dx.doi.org/10.1590/0104-6632.20140313s00002458 BIOHYDROGEN PRODUCTION FROM CASSAVA WASTEWATER IN AN ANAEROBIC FLUIDIZED BED REACTOR N. C. S. Amorim¹, I. Alves¹, J. S. Martins¹ and E. L. C. Amorim1* 1Technology Center, Federal University of Alagoas, Av. Lourival Melo Mota, s/n, Cidade Universitária, CEP: 57072-900, Maceió - AL, Brazil. E-mail: [email protected] (Submitted: December 19, 2012 ; Revised: May 19, 2013 ; Accepted: September 5, 2013) Abstract - The effect of hydraulic retention time (HRT) and organic loading rate (OLR) on biological hydrogen production was assessed using an anaerobic fluidized bed reactor fed with cassava wastewater. The HRT of this reactor ranged from 8 to 1 h (28 to 161 kg COD/m3-d). The inoculum was obtained from a facultative pond sludge derived from swine wastewater treatment. The effluent pH was approximately 5.00, while the influent chemical oxygen demand (COD) measured 4000 mg COD/L. The hydrogen yield production increased from 0.13 to 1.91 mol H2/mol glucose as the HRT decreased from 8 to 2 h. The hydrogen production rate significantly increased from 0.20 to 2.04 L/h/L when the HRT decreased from 8 to 1 h. The main soluble metabolites were ethanol (1.87-100%), acetic acid (0.00-84.80%), butyric acid (0.00-66.78%) and propionic acid (0.00-50.14%). Overall, we conclude that the best hydrogen yield production was obtained at an HRT of 2 h. Keywords: Anaerobic fluidized bed reactor; Dark fermentation; Cassava wastewater; Hydrogen production; Organic loading rate. INTRODUCTION chemical element in the universe, comprising almost three-quarters of the universe’s entire mass (Das and Global energy demand is rising to meet societies’ Verziroglu, 2001). Although abundant, hydrogen is needs in the modern world, with oil and its deriva- often found combined with other elements in the tives representing the most frequently used energy natural environment (Das and Verziroglu, 2001), and sources today. However, the overuse of fossil fuels a range of different processes are required to isolate it. could result in the depletion of this energy source The main methods of producing hydrogen em- and negative environmental impacts caused by gases ploy fossil fuels, water and biological processes. generated during its combustion (Kapdan and Kargi, However, hydrogen production from fossil fuels by 2006). steam reforming, or from water by electrolysis and Due to pressing environmental issues and in- thermochemical decomposition, may not be envi- creasing energy demand, the search for alternative – ronmentally friendly and can also be uneconomical i.e., renewable and less polluting – energy sources (Amorim et al., 2009). has gained prominence. Hydrogen is an alternative The fermentative biological process is a means to source of energy that could replace petroleum-based produce hydrogen sustainably because it can use fuels because water and energy are the only byprod- various types of carbohydrate-rich industrial and ucts of its combustion with oxygen (Van Ginkel et domestic waste as its substrate, thereby mitigating al., 2001). Moreover, hydrogen is the most abundant problems caused by the inappropriate disposal of *To whom correspondence should be addressed 604 N. C. S. Amorim, I. Alves, J. S. Martins and E. L. C. Amorim these materials (Reis and Silva, 2011). The use of aim of this investigation was to study an AFBR us- agro-industrial residues in biological hydrogen pro- ing cassava wastewater for hydrogen production. duction has also been investigated for the same rea- son (Luo et al., 2010a; Cappelletti et al., 2011). Cassava is a typical Brazilian agricultural product EXPERIMENTAL PROCEDURE that is widely used in the production of flour and starch (Cappelletti et al., 2011; Wosiacki and Cereda, Inoculum and Fermentation Medium 2002). In some of Brazil’s northeastern states, cas- sava is cultivated in small plantations by traditional The inoculum used in this experiment was ob- farming means. Cassava is processed either by hand tained from a facultative pond sludge derived from in small flourmills and cake factories or by mecha- swine wastewater treatment. The sludge was sub- nized units. During the production of flour, cassava jected to 10 min of heat treatment at 90 ºC to inacti- undergoes a pressing process, and the wastewater de- vate the H2 consumers and harvest endospore-form- rived from the pressing is called cassava wastewater. ing anaerobic bacteria (Maintinguer et al., 2008). Cassava wastewater has high energy content – The medium used for H2 fermentation contained approximately 20-40 g of carbohydrate per liter – cassava wastewater and the following nutrients with high potential for pollution if improperly dis- (mg/L): CH4N2O, 125; NiSO4·6H2O, 1; FeSO4·7H2O, carded into the environment. However, the energy 5; FeCl3·6H2O, 0.5; CaCl2·6H2O, 47; CoCl2·2H2O, potential of cassava wastewater makes it very attrac- 0.08; SeO2, 0.07; KH2PO4, 85; KHPO4, 21.7; and tive as a substrate for hydrogen production, and its Na2HPO4·2H2O, 33.4 (Amorim et al., 2009). use in this process would reduce the environmental The cassava wastewater used here was produced impact of disposing it without prior treatment by a manioc flour factory in Taquarana, Alagoas, (Cappelletti et al., 2011). Brazil. The main characteristics of the cassava Some studies using cassava wastewater as sub- wastewater were as follows: pH 5.53, total solids strate have already been conducted, and their results 4.45 g/L, volatile solids 3.4 g/L, total carbohydrate indicate that its use in hydrogen production is eco- 37.54 g/L, chemical oxygen demand (COD) 66.19 g nomically viable (Luo et al., 2010a; Cappelletti et al., COD/L, total nitrogen 1.26 g/L. After it had been 2011; Wosiacki and Cereda, 2002; Cheng et al., 2011; collected, the cassava wastewater was stored at 5 °C O-Thong et al., 2011; Luo et al., 2010b). However, before usage. We chose to use the cassava wastewa- these studies all used batch reactors in their experi- ter with COD of 4 g COD/L, because, according to ments. Working from these researchers’ achieve- Amorim et al. (2012), this concentration might favor ments, the main purpose of this study is to produce the production of acetic acid and butyric acid (route hydrogen from cassava wastewater in an anaerobic that favors hydrogen production), whereas higher fluidized bed reactor (AFBR). The employment of substrate concentrations would favor the production the AFBR is justified by its many positive features, of solvents. Furthermore, Cappelletti et al. (2011) such as the accumulation of large amounts of bio- concluded that a lower cassava wastewater COD mass attached to the support medium, high organic produces a large amount of hydrogen. loading rates (OLR), low hydraulic retention times (HRT), and good mixing characteristics, which op- Support Material timize mass transfer between the substrate and mi- croorganisms. In addition, AFBR allows high-speed Particles of expanded clay (2.8–3.35 mm) were stirring in the liquid phase, which favors hydrogen used as the support material for biomass immobili- release at this stage (Wu et al., 2003; Lin et al., zation. The material had an apparent density of ap- 2006; Zhang et al., 2007). proximately 1.06 g/cm3 and a porosity of 23%. Hydrogen production in an AFBR has been stud- ied by some researchers, who were successful in Reactor evaluating this reactor’s usefulness (Amorim et al., 2009; Reis and Silva, 2011; Shida et al., 2009; Barros Figure 1 shows a schematic of the AFBR system et al., 2010). However, the production of bio-hydro- used in this study. The main body of the reactor was gen from actual substrate, such as cassava wastewa- an acrylic tubular section with a 5.3 cm internal di- ter, in an AFBR has not yet been evaluated. These ameter and a height of 190 cm. The reactor has a prior studies concluded that some aspects influencing total volume of 4,192 cm3, and the height of the hydrogen production should be further explored, static bed of support material was 90 cm (2,104 g of especially the use of actual substrate. Therefore, the expanded clay) (Amorim et al., 2009). Brazilian Journal of Chemical Engineering Biohydrogen Production from Cassava Wastewater in an Anaerobic Fluidized Bed Reactor 605 Figure 1: Schematic of the anaerobic fluidized bed reactor. Operating Conditions of the AFBR TG1; Ritter Inc., Germany) was used to measure the amount of gaseous products generated (Amorim et The AFBR was fed with cassava wastewater at al., 2009). 4,000 mg COD/L and 10% v/v of heat-treated sludge. The operation temperature was ambient (28 ± 2 °C). Chemical Analysis For the AFBR system, the total liquid flow rate, Q, was controlled at 128 L/h (bed expansion = 30%) The volatile fatty acid (VFA) and alcohol con- (Amorim et al., 2009). This flow rate produced a su- centrations were measured using a gas chromato- perficial velocity 1.30 times greater than the mini- graph (GC-2010, Shimadzu, Tokyo, Japan) equipped mum fluidization velocity. The bioreactor was ini- with a flame-ionization detector (FID), a COMBI-PAL tially operated in batch mode for 48 h to activate the headspace autosampler (AOC model 5000) and a H2-producing sludge, after which it was switched to Zebron ZB-WAX column (30 m long × 0.25 mm i.d. a continuous mode with a designated hydraulic re- × 0.25 μm film thickness) (Maintinguer et al., 2008). tention time of 8 h. The biogas hydrogen content was measured using a After reaching steady-state operation based on a gas chromatograph (GC-2010, Shimadzu, Japan) with constant volumetric H2-production rate within a a thermal conductivity detector (TCD) with argon variation of 5-10% for 10-15 days, the HRT was as the carrier gas, and the column was packed with decreased progressively from 8 h to 1 h.
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