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Biogas Production in Relation To PH
Biogas Production in Relation To PH
Biogas Production in Relation To PH
ISSN 0122-5383
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CIBSCOL Latinoamerican journal of oil & gas and alternative energy
BIOGAS PRODUCTION BY
ANAEROBIC DIGESTION OF
WASTEWATER FROM PALM OIL
MILL INDUSTRY
PRODUCCIN DE BIOGS MEDIANTE DIGESTIN ANAEROBIA DE
AGUAS RESIDUALES PROVENIENTES DE LA INDUSTRIA PALMERA
1
Centro de Estudios e Investigaciones Ambientales (CEIAM), Universidad Industrial de Santander,
Bucaramanga, Santander, Colombia
e-mail: dnabarla@uis.edu.co
ABSTRACT
T
he environmental impact caused by the fossil fuel use encourages society to look for new sources
of renewable energy, such as biodiesel. During the last years, palm oil production has dramatically
increased in Colombia, since it is the main raw material for biodiesel production. As consequence
of the process, palm oil mill effluents with high content of pollutants are released to the environment. Since
these effluents have physicochemical characteristics that make them suitable for the production of biogas by
anaerobic digestion of residual water, this research evaluates the production of methane using wastewater as
substrate from a Colombian palm oil mill. Anaerobic digestion experiments were conducted in batch mode to
evaluate the influence of pH and inoculum to substrate ratio, by using two differents inoculums. It was found
that the most suitable inoculum was a mixture of 1:1 v/v urban Wastewater Treatment Plant (WWTP) anaerobic
sludge/pig manure at a ratio 2 g Volatile Solids (VS) inoculum/g VS substrate, which presented the highest
accumulated methane production, reaching 2740 mL methane (0.343 m3 CH4/kg VS) without neutralizing pH.
How to cite: Nabarlatz, D. A., Arenas-Beltrn, L. P., Herrera-Sorac, D. M. & Nio-Bonilla, D. A. (2013). Biogas production
by anaerobic digestion of wastewater from palm oil mill industry. CT&F - Ciencia, Tecnologa y Futuro, 5(2), 73-84.
+
V Congreso Internacional de Ciencia y Tecnologa de los Biocombustibles, CIBSCOL 2012, Universidad Industrial de Santander, Bucaramanga,
Santander, Colombia. 5 - 8 de junio de 2012.
RESUMEN
E
l impacto ambiental generado por el uso de combustibles fsiles, incentiva a la sociedad a buscar
nuevas fuentes de energa renovables tales como el biodiesel. En Colombia, la materia prima ms
utilizada para producir biodiesel es el aceite de palma, con lo que su produccin ha aumentado
drsticamente en los ltimos aos, generando efluentes con alta carga contaminante para el medio am-
biente como consecuencia del proceso. Dado que las caractersticas fisicoqumicas de estos efluentes son
propicias para la produccin de biogas mediante digestin anaerobia, este trabajo evala la produccin de
metano a partir de agua residual de una empresa extractora de aceite de palma colombiana. Se realizaron
experimentos de digestin anaerobia en modo batch para evaluar la influencia del pH y la relacin inculo/
sustrato utilizando dos inculos diferentes. Se encontr que la mezcla 1:1 v/v lodo anaerobio de planta de
tratamiento de aguas residuales urbanas y estircol de cerdo usada como inculo, gener la mayor produc-
cin de metano acumulado, alcanzando 2740 mL de metano (0.343 m3 CH4/kg SV), usando una relacin de
2 g SV de inculo/g SV de sustrato, sin necesidad de neutralizar el pH del sistema.
RESUMO
O
impacto ambiental gerado pelo uso de combustveis fsseis, incentiva sociedade a procurar
novas fontes de energia renovveis, tais como o biodiesel. Na Colmbia, a matria-prima mais
utilizada para produzir biodiesel o leo de palma, devido a isso a sua produo tem aumentado
drasticamente nos ltimos anos, gerando efluentes com alta carga contaminante para o meio ambiente como
consequncia do processo. Dado que as caractersticas fsico-qumicas destes efluentes so propcias para
a produo de biogs mediante digesto anaerbia, este trabalho avalia a produo de metano a partir
de gua residual de uma empresa extratora de leo de palma colombiana. Foram realizados experimentos
de digesto anaerbia em modo batch para avaliar a influncia do pH e a relao inoculo/substrato utili-
zando dois inculos diferentes. Encontrou-se que a mistura 1:1 v/v lodo anaerobio de tratamento de guas
residuais urbanas e esterco de porco usada como inculo, gerou a maior produo de metano acumulado,
atingindo 2740 mL de metano (0,343 m3 CH4/kg SV), usando uma relao de 2 g SV de inculo/g SV de
substrato, sem necessidade de neutralizar o pH do sistema.
The application of the AD technology depends on the substrate included pH, Total and Volatile Solids (TS,
the design, use and development of anaerobic reactors, VS), Total and Volatile Suspended Solids (TSS, VSS),
and is determined by operational parameters that have Volatile Fatty Acids (VFA), COD, BOD5, Phenols, Fat
direct influence on the metabolism of the microorga- and Oils content measurements. These analytics were
nism, the kinetic of the reactions involved in the AD carried out under American Public Health Association
and the reactor design (Sharma, Unni & Singh, 1999). (APHA) standards (APHA, 1995).
In order to improve the reaction velocity per unit of
reactor volume, different reactor configurations have
Two different inoculums were used for the ex-
been tested, differing mainly in the immobilization and
periments. The first one (called PP inoculum) co-
retention way for the microorganisms. The immobiliza-
rresponded to a mixture composed by an anaerobic
tion of biomass increases the system stability and the
sludge coming from the municipal Wastewater Treat-
resistance to toxics action.
ment Plant (WWTP) (Floridablanca, Colombia), and
pig manure obtained from a pig processing plant (Los
Depending on the fat, carbohydrate and protein Santos, Colombia), in a proportion 1:1 (v/v) (Castillo,
content of the different substrates used for AD, the Cristancho & Arellano, 2006). The second one (called
methane fraction contained in the biogas obtained LP inoculum) corresponded to the anaerobic sludge
varied between 50 to 75%. The composition of the coming from the oxidation ponds from the same palm
biomass or substrate used determines the amount and oil mill industry that provided the substrate.
final composition of the biogas produced. In general,
fats and oils have a higher biogas yield (measured as
The physicochemical characterization of the inocu-
m/ton VS), with an average methane content. Pro-
lums included pH, TS and VS content, TSS and VSS
teins have a comparative lower biogas yield, but with
content, VFA and alkalinity (Alk). These analytics
higher methane content. In the case of carbohydrates,
were carried out under APHA standards (APHA, 1995).
they have an average yield and productivity of biogas,
but with lower methane content. The concentration of
solids is of importance for the biological process, for The different inoculums were also evaluated in
mixing effects and handling inside the reactor, as well order to determine the Specific Metanogenic Activity
as for the feeding system in the plant. (SMA) which is the own capacity of the inoculums to
produce methane (Daz, Espitia & Molina, 2002). The
experiments were carried out in 500 mL reactors. To
The different technologies and commercial systems
each reactor, an inoculum volume equivalent to a con-
for AD existent and emergent at industrial scale used
centration of 1.5 g/L VSS, and a mineral balch medium
in several countries like Japan, Switzerland, Spain,
were added until reaching 300 mL operation volume.
Austria, Germany, France, China, Italy and Belgium,
The experiments were carried out by triplicates during
present a biogas production between 0.10 to 0.15 m3/
kg of wet residue, while containing 50 to 70% methane 15 days at 372C incubation temperature. The biogas
in volume (Nichols, 2004). volume produced was quantified by alkaline displace-
ment method using a Mariottes bottle filled with NaOH
0.1 N solution for CO2 retention (Daz et al., 2002).
The SMA was expressed in g COD/g VSS* day.
tion of the reactor content by adding NaOH 5 N every 4. RESULTS AND DISCUSSION
two days in anaerobic conditions. Two blank samples
were prepared by adding the same inoculum quantity
used in the experiment and completing the volume with Physicochemical Characterization of the Substrate
distilled water. The experiments were carried out using (POME)
500 mL batch reactors with 300 mL operation volume Table 1 presents the physicochemical characteriza-
by triplicate. Methane production was evaluated during tion of POME wastewater. As it can be observed, it
30 days at 372C, measuring the volume of methane presents a high solids content and COD that makes it
produced by the alkaline displacement method (Daz an appropriate substrate for biogas production. This
et al., 2002). The final volume of methane produced wastewater presents acid pH (4.8), and for this reason,
by the substrate was determined by subtracting the it is convenient to evaluate if AD at this pH is possible,
methane produced by the blank sample. The methane due to previous research that indicated optimal pH
accumulated yield (Yp/s) during the retention time is values between 6.8-7.2 (Daz et al., 2002). The other
expressed in m3 CH4/ kg VS of substrate. parameter values are in the range reported by previous
authors (Chan, Chong & Law, 2010; Mustapha, Ashhuby,
Rashid & Azni 2003; Poh & Chong, 2009).
Inoculum to Substrate Ratio (ISR) Influence on
Biogas Production
Table 1. Physicochemical characterization of POME substrate.
To evaluate the ISR influence on biogas production
three different ISR levels were evaluated: 1, 1.5 and
2 g VS inoculum/g VS substrate. 500 mL bioreactors Parameter Value
with a 300 mL operation volume were used for the pH 4.8
experiments. The inoculum and substrate concentra-
TS (mg/L) 48000492.5
tions were varied in order to maintain the operation
volume constant. The blank samples were prepared VS (mg/L) 1010092.5
by adding the amount of inoculum corresponding to
TSS (mg/L) 34000175
each ISR experiment, and completing the volume by
adding distilled water to the reactor. Both biorreactors VSS (mg/L) 620025
(test and blank) were incubated at 372C during 20
VFA (mg/L) 67009.34
days. The experiments were carried out by triplicate.
In order to obtain the final methane volume produced COD (mg/L) 728002.57
by the substrate, the methane volume produced by the
BOD5 (mg/L) 2400010%
blank was subtracted. Several operational parameters
were measured during the experiments, like VFA, VS, Fats and oils (mg/L) 9010%
COD content and pH by destructive sample every 4
Phenols (mg/L) 410%
days. The methane volume obtained in the experiments
was measured by the alkaline displacement method
(Daz et al., 2002).
Physicochemical Characterization of the Inoculums
Table 2 shows the physicochemical characterization
The maximal methane accumulated yield (Yp/s) of both inoculums used in the experiments. The inoculum
during the retention time is expressed in m3 CH4 / kg composed by WWTP anaerobic sludge and pig manure
VS substrate, and it was calculated dividing the metha- (PP) (1:1 v/v) presents a pH higher than 7 giving to the
ne accumulated during the whole AD time at standard reactor an increment in this value, which probably will
pressure and temperature conditions, by the amount favour the AD process. In contrast, sludge from palm
of substrate added (g VS) (Raposo, Banks, Siegert & oil mill oxidation pond (LP) has a more acidic pH and a
Borja, 2006). The accumulated methane productivity semisolid appearance; therefore, the VFA and Alkaline
(Qp) was also determined in mL CH4 /day. content could not be measured.
PP sludge presents a higher content of Methanogenic Table 3. Evaluation of SMA for both inoculums.
Acetoclastic Bacteria, which are the main microorga-
nisms capable of generating 2/3 of methane produced, Inoculum SMA (g COD/g VSS*day)
being the main responsible of the anaerobic degradation PP 0.113
of organic matter (Castro, 2012; Quintero, 2011). LP 0.086
800
Evaluation of Specific Methanogenic Activity (SMA)
The parameters used in the calculation of SMA are 700
Accumulated CH4 Volume (mL)
0
180 0 5 10 15 20 25 30
Time (days)
160
PP - pH 7 LP - pH 7 PP - pH 4.8 LP - pH 4.8
Accumulated CH4 Volume (mL)
140
80
Previous studies have demonstrated that AD at
60
neutral pH increases the methane production because it
40
favours the microorganisms growth, as well as avoids
20
VFA accumulation which negatively affects the system
0 stability (Poh & Chong, 2009; Chen, Cheng & Creamer,
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
2008). However, at the end of the AD process, for the
Time (days)
experiments using PP inoculums,the difference in the
PP LP
final accumulated methane volume (at pH 4.8 and pH
Figure 1. Kinetics of accumulated CH4 production (mL) for each inocu-
7) is lower than the final accumulated methane volume
lum used. Initial solids concentration 1.5 g VSS/L pH= 7 T= 372C. obtained when using LP inoculum. That indicates that
after the starting up, the AD process progresses at the From the data obtained,the percentage of VS removal
same velocity in both cases. This can be attributed to was calculated, and it was related to the maximal accu-
the fact that PP inoculum has neutral pH (7.6), which mulated methane volume obtained. As it can be expected
contributes to the own microorganisms adaptability to for a typical AD process, while the VS concentration
the medium. decreases, the accumulated methane volume production
increases. This can be attributed to the operation time
On the other side, when using LP as inoculum, it in which the organic matter degrades, which is used by
presents a higher difference in methane production at the microorganisms for producing methane. As it can be
the two different pH used in the experiments. This is observed, the % VS removal was in the range between
because LP inoculum is acidic (pH 6.3) in comparison 13.42 - 55.52% corresponding to LP at ISR 1 and PP
to PP inoculum, which is not enough to neutralize the at ISR 2, respectively. These data are concordant with
pH of the system, and consequently the AD system is the methane production results. The percentage of VS
unstable, producing lower amount of methane. Due to removal for PP at ISR 2 was higher than the reported
the difficulties in controlling the pH during the deve- by Forster, Prez and Romero (2008), who studied the
lopment of the AD process (in which the neutralization influence of solids in the AD process using urban solid
is necessary every two days) it was decided to continue residues as substrate, finding a value of 49.7% VS
working with both inoculums at the original pH of removal.
residual wastewater (pH 4.8), avoiding the continuous
neutralization of the system inside the reactors.
Figure 3 shows the kinetics of methane production
at each ISR studied for both inoculums (PP and LP).
ISR Influence on Biogas Production
The highest yield (Yp/s) was obtained at ISR 2 using
The influence of ISR was evaluated on AD of POME PP as inoculum, obtaining 0.343 m3 CH4/kg VS. This
in batch experiments. The different parameters affecting value was lower in comparison with that obtained with
the AD process such as pH and VFA accumulation were
the same ISR but using fique pulp as substrate and a
measured. Due to this, they indicated acidification inside
mixture between rumen fluid and pig manure as inocu-
the reactor. The amount of inoculum and substrate to be
lum, reaching a maximal yield of 0.446 m3 CH4/kg VS
added in each reactor were also evaluated.
(Quintero, 2011).
Table 4 presents the accumulated methane volume and
Qp for both inoculums at the different ISR studied. The In the literature it was found that there is a linear
results showed that the higher methane production was relationship between methane yield and the ISR (Chen
obtained at ISR 2 using PP as inoculum, obtaining 2740 et al., 2008; Chaiprapat & Laklam, 2011). Recent studies
mL of accumulated methane volume. This demonstrates on the effect of ISR on AD of algae have demonstrated
that at higher organic load of inoculum added to the reac- that methane yield decreased from 0.140 m3 CH4/kg VS
tor, the methane production increases, and consequently to 0.094 m3 CH4/kg VS when the ISR was decreased
the volumetric productivity of methane per day. from 2 to 0.5 (Dinsdale, Premier & Hawkes, 2000).
Table 4. Qp, accumulated methane volume and % VS removal for the different ISR studied.
ISR PP LP PP LP PP LP
1 136030 89040 681.5 44.52 35.81 13.42
1.5 192228 94717.5 96.11.4 47.40.88 51.82 31.70
2 274040 14119 1372 70.50.45 55.52 44.60
7.5
3000
Accumulated CH4 Volume (mL)
2500 7
2000 6.5
1500 6
pH
1000 5.5
500 5
0
4.5
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Time (days) 4
0 4 8 12 16 20
PP ISR:1 PP ISR:1.5 PP ISR:2
LP ISR:1 LP ISR:1.5 LP ISR:2 Time (days)
Time (days)
When the values of VFA/Alk ratio are lower than 0.4, 100
% COD Removal
70
1000
was evidenced by the lower methane production for 800
60
50
those reactors inoculated with LP, because the VFA/Alk 600 40
ratio was between 0.8 - 1.4. 400
30
20
200
10
Figure 6 shows the evolution of the accumulated 0 0
COD removal reported by (Chan et al., 2010). It can be % COD ISR:1 % COD ISR:1.5 % COD ISR:2
2500
90
80
Investigaciones Ambientales (CEIAM) for finan-
cial resources and equipment used during this
% COD Removal
2000 70
60 research, and to Dr. Liliana Castro for her kind
1500 50
40
collaboration during the project.
1000
30
500 20
10
0 0
0 5 10 15 20
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AUTHORS
Debora-Alcida Nabarlatz
Affiliation: Universidad Industrial de Santander.
Ing. Qumica, Universidad Nacional de Mar del Plata, Argentina.
Ph. D. Ing. Qumica y de Procesos, Universitat Rovira i Virgili,
Espaa.
e-mail: dnabarla@uis.edu.co
Ligia-Patricia Arenas-Beltrn
Affiliation: Universidad Industrial de Santander.
Ing. Qumica, Universidad Industrial de Santander.
M. Sc. Ing. Qumica, Universidad Industrial de Santander.
e-mail: lparenas@gmail.com
Diana-Milena Herrera-Sorac
Affiliation: Universidad Industrial de Santander.
Ing. Qumica, Universidad Industrial de Santander.
e-mail: chanah123@hotmail.com
Diana-Andrea Nio-Bonilla
Affiliation: Universidad Industrial de Santander.
Ing. Qumica, Universidad Industrial de Santander.
e-mail: dianis1411@hotmail.com