21st World Hydrogen Energy Conference 2016. Zaragoza, Spain.

13-16th June, 2016

Hydrogen and organic acids production from sugarcane juice and

sucrose in thermophilic anaerobic fluidized bed reactor
T.B. Ferreira1, G.C. Rego1, A.G.O. Paranhos2, L.R. Ramos2 and E.L. Silva2*
1 Department of Hydraulics and Sanitation, School of Engineering of So Carlos, University of So Paulo, Av. Trabalhador So-carlense, 400, 13566-590, So Carlos, So Paulo, Brasil
2Departament of Chemical Engineering, Federal University of So Carlos, Rod. Washington Luis, km 235, 13565-905, So Carlos, So Paulo, Brazil

(*) edsilva@ufscar.br

The growing worldwide demand for energy and the the future depletion of fossil fuel reserves, make it necessary to
obtain energy from other sources, with strong appeal to clean and renewable energy, focusing on the environmental
aspects accompanying this process. The Brazilian sugar and ethanol industry is an example of this trend. It is the result
of an energy self-sufficiency policy of the 70s, showing solid results in time of wealth and even in economic regression.
The industry is currently undergoing restructuring to increase its production portfolio and consequent production and
energy efficiency. The production of hydrogen and organic acids by biological process is a relatively new line of
research, however, that may represent an alternative for this sector, maximizing energy production and production of
high added value products. The objective of this study was to evaluate the influence of hydraulic retention time (HRT)
(ranging from 8 to 1h) in the hydrogen and organic acids production from sucrose and sugarcane juice at 5,000 mg
COD L-1 in thermophilic anaerobic fluidized bed reactor operated at 55 C.

Material and methods

The inoculum used in the anaerobic fluidized bed reactors (AFBR) was methanogenic sludge obtained from a
thermophilic anaerobic upflow sludge blanket (UASB) used in the treatment of vinasse. The substrates used as carbon
source was sugarcane juice and sucrose. The support material used for biomass immobilization in AFBR was expanded
clay, in thermophilic conditions (55 C) temperature. The substrate had 5,000 mg COD L-1 and pH operation was 4,
respectively. The HRTs applied ranged from 8 to 1 hour. The parameters analyzed were soluble carbohydrates [1],
chemical oxygen demand (COD), suspended solids - [2], volumetric biogas production was measured using a reversed
graduated cylinder [3] and biogas composition was performed by gas chromatography (Shimadzu GC-2010), soluble
metabolites were measured by high performance liquid chromatography (HPLC, Shimadzu).

Results and discussion

Initially, the reactors were operated in batch mode until consumption of 80% of total carbohydrates. This
adaptation step lasted 8 days for the reactor fed with sucrose (RS) and 10 days for sugarcane juice (RC). Then the
operation in continuous mode was applied. The operation starting from HRT of 8 hours, which was reduced when the
reactor reached stable biogas production. The maximum carbohydrate conversion was 56.6% in RS operated at HRT of
4 hours and 69.2% in RC operated at HRT 8 hours. Values lower than 95% obtained by [4], operating a AFBR (45 C)
with sucrose (20.000 mg COD L -1). [5] operated a CSTR (35 C) where used sugarcane juice (25,000 mg COD L-1) as
the substrate and Clostridium butyricum as inoculum. These authors reported similar behavior of reduced the conversion
with the decrease of HRT, with maximum conversions (72%) in HRT of 6 hours, an amount higher than in the RS and
similar to RC. The maximum composition of
H2 in the biogas was 63.2 in RS operated at
HRT of 1h and 46.8% in RC, operated at 2h.
[6] mentioned that a maximum concentration
of H2 (46.1%) when operated in HRT 2h,
representing a behavior similar to this work -
increasing H2 composition with the decrease
of HRT - despite reporting values lower than
that ones in this study. Hydrogen production
rate (HPR) and the organic loading rate (OLR)
profiles are illustrated in Figure 1. The
behavior of the two reactors was similar
HPR increased with lower values of HRT.
However, it is clear from the HRT of 4h the
RC had higher productivity RS for the same
HRT values. The highest values were 262.33
and 563.39 ml H2 h-1 L-1 for RS and RC,
Figure 1. HPR and OLR values from AFBR feeds by sucrose and
respectively, and they were obtained when
sugarcane juice at the 5 different HRTs.
 21st World Hydrogen Energy Conference 2016. Zaragoza, Spain. 13-16th June, 2016
HRT 1h. [6] operated a AFBR (40 C) with sucrose (5,000 mg COD L-1) reported its maximum HPR (370ml H2 h-1 L-1)
when submitted to TDH 2h. These values are higher than the values of RS, however, lower than values obtained by
RC. [5] reported similar behavior; increasing HPR when the HRT has been reduced, achieving maximum HPR (3.38
mmol H2 h-1 L-1) in the HRT of 4h. This value
is lower than the maximum obtained in RS
(9.39 mmol H2 h-1 L-1) and RC (20.17 mmol
H2 h-1 L-1). The hydrogen yield (HY) profile
obtained for RS and RC as function of HRT
are illustrated in Figure 2. The HY profile
was similar to the HPR RC had a
production advantage under lower values of
HRT when compared to RS increasing HY
with the reduction of HRT until 4 hours.
where was the peak of HY, 1.93 and 1.99 mol
H2 mol-1sucrose, for the RS and RC
respectively. HRTs below this (4h) caused the
decrease of HY in both reactors, however, RS
has more susceptible when compared to RC.
[6] using sucrose AFBR (40 C) reports its
Figure 2. Behavior of RS and RC for hydrogen yield, during the 5 HRTs. maximum HY (3.36 mol H2 mol-1sacarose)
when operated at HRT of 6 hours. This value
is higher than the maximum HY achieved by both reactors - RS and RC. [5] operated a CSTR (35 C) with C. butyricum
fed sugarcane juice (25,000 mg COD L-1) obtained 1 mol H2 mol-1hexose as maximum HY, when submitted to HRT of
4 hours. HY similar to values obtained in the same TDH for this work - 1.99 mol H2 mol-1sacarose - given that the
difference of carbohydrate unit. The metabolites present dissolved in the effluent of the reactors are represented in a
mostly acetic acid and propionic acid to the RS and acetic acid, propionic acid, and succinic acid to RC.

Conclusion

Based on the data obtained, it can be said that both reactors proved productive for the operating conditions tested,
however, the best performance was achieved for the RC. These results may represent an alternative for diversification
of the production of sugar and alcohol sector.

References
[1] M. Dubois, K.A.Hamilton, P.A. Rebers, F. Smith, Anal. Chem. 28 (1956) 350-356.
[2] APHA, AWWA, WEF, Standard methods for the examination of water and wastewater, 22th ed., American Public Health
Association, 2012.
[3] M. Walker, Y. Zhang, S. Heaven, C. Banks, Bioresour. Technol. 100 (2009) 6339-6346.
[4] K.S. Lee, P.J. Lin, J.S. Chang, Int. J. Hydrogen Energy. 31 (2006) 465-472.
[5] S. Pattra, C.H. Lay, C.Y. Lin, S. O-Thong, A. Reungsang, Int. J. Hydrogen Energy. 36 (2011) 8697-8703.
[6] C.N. Lin, S.Y. Wu, J.S. Chang, J.S. Chang, Bioresour Technol. 100 (2009) 3298-3301.