The effect of natural zeolite as microbial immobilization media in anaerobic digestion at

various concentrations of palm oil mill effluent (POME)

Erika Dyah Ayu, Lenny Halim, Melly Mellyanawaty, Hanifrahmawan Sudibyo, and Wiratni Budhijanto

Citation: AIP Conference Proceedings 1840, 110005 (2017); doi: 10.1063/1.4982335

View online: http://dx.doi.org/10.1063/1.4982335
View Table of Contents: http://aip.scitation.org/toc/apc/1840/1
Published by the American Institute of Physics

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 The Effect of Natural Zeolite as Microbial Immobilization
Media in Anaerobic Digestion at Various Concentrations of
Palm Oil Mill Effluent (POME)
Erika Dyah Ayu1, Lenny Halim1, Melly Mellyanawaty2, Hanifrahmawan
Sudibyo1,3, Wiratni Budhijanto1, 3, a)
1
Department of Chemical Engineering, Universitas Gadjah Mada, Yogyakarta 55281 Indonesia
2
Department of Environmental Engineering, Faculty of Engineering, Universitas Muhammadiyah Tasikmalaya,
Tasikmalaya Indonesia
3
Center for Energy Studies, Universitas Gadjah Mada, Yogyakarta 55281 Indonesia
a)
Corresponding author: wiratni@ugm.ac.id

Abstract. Anaerobic digestion is one of the solutions in POME treatment because it generates energy in the form of
biogas. Nevertheless, high concentration of POME fed into the digester will cause high acidification level and eventually
cause process failure. The failure can also be affected by high inhibitor concentration contained in POME, one of which
is long chain fatty acid. The addition of immobilization media is commonly used to increase the bacteria resistance to
inhibitor. Natural zeolite is considered as appropriate immobilization media for waste treatment purpose since it is cheap,
has high mechanical strength, high immobilization capacity, and its ability as cation exchanger. The digested biodiesel
waste was used as starter inoculum for its good capability in digesting oil-containing feed such as POME. This research
was conducted to evaluate critical concentration of POME fed to digester where the natural zeolite could not reduce the
inhibitory effect. The concentrations of POME evaluated were 10,000 mg sCOD/L and 17,000 mg sCOD/L, which were
higher than previous studies(5,000 to 8,000 mg sCOD/L). The research showed that at such high sCOD concentrations,
the addition of zeolite did not significantly increase COD reduction nor biogas production rate, for both POME
concentrations to be compared to control. The biogas produced by digester fed by 10,000 mg/L POME and 17,000 mg/L
POME was 751 and 100 mL/g sCOD, respectively, indicating higher inhibitor effect in the digester with 17,000 mg
SCOD/L initial concentration.

Keywords: Palm Oil Mill Effluent (POME), anaerobic digestion, natural zeolite, immobilization

INTRODUCTION
In Indonesia, oil palm plantation cover a total area of 11.44 million hectares (Statistics Indonesia, 2014). The
main product of this oil palm plantation is Crude Palm Oil (CPO). In CPO production in the mills, 3 tons of POME
were produced for every ton of CPO produced. In 2020, Indonesia is expected to produce 30 million tonnes of CPO
with the potential of producing 90 million tonnes of POME/year as the waste (World Growth, 2011). Unfortunately,
POME was characterized as liquid waste with high VFA concentration and high Chemical Oxygen Demand (COD).
Usually, POME contributed to as many as 55-67% of total liquid waste of a CPO plant (MCA-Indonesia, 2014).
Thus, POME emerged as the main concern in Indonesia due to its huge accumulation as the waste of CPO
production.
POME is a colloidal suspension in the form of black liquor as the output of the industry with a fairly acidic
condition. Most of the POME treatment processes used open pond system (Rahayu et al., 2015). In this process,
POME was passed through a series of ponds with several stages of processing. As the consequence, land
requirement was very spacious with long residence times of each. However, the worst disadvantage from applying

International Seminar on Fundamental and Application of Chemical Engineering 2016 (ISFAChE 2016)
AIP Conf. Proc. 1840, 110005-1110005-8; doi: 10.1063/1.4982335
Published by AIP Publishing. 978-0-7354-1510-2/$30.00

110005-1
this method was the easy release of greenhouse gases in the form of methane and carbon dioxide to the atmosphere.
On the other hand, methane was combustible gas which could be used as renewable energy resource.
POME had organic load range between 15,000 65,000 mg/L in term of COD. This high organic load represents
the potential of POME as energy sources. POME could be converted into energy in the form of biogas (Rahmi,
2015). To convert POME into biogas (bio-methane), anaerobic digestion was an economical method. Anaerobic
digestion was identical with free oxygen environment so that no energy consumed for aeration. POME conversion
into energy using anaerobic digestion passed through four phases (Shuler et al., 2002). The first phase was
hydrolysis in which the long-chain polymers were broken down into short-chain polymers by enzyme produced by
microorganism. The second phase was acidogenesis in which the product of hydrolysis process was used as
substrate and converted into carboxylic acid group chemicals which were known as volatile fatty acid. Volatile acid
would be the substrate for the methanogenesis phase to be converted into biogas such as methane, carbon dioxide,
H2S, etc (Rahayu et al., 2015). Reaction mechanism in anaerobic digestion of organic compound was shown in Eq.
(1).
Anaerobic
Organic matter VFA CH4 + CO2 (1)
Microorganism

However, anaerobic digestion required large volume of digester (bioreactor) due to the slow growth of
microorganism so that the wastewater digestion usually asked for high Hydraulic Retention Time (HRT) operation
to achieve its greatest performance (Shabrina, 2015). Another problem with the anaerobic digestion was the land
requirement increases with increasing volume of waste and ultimately affecting economic factors of the wastewater
treatment (Kristanty, 2015).
The characteristic of anaerobic digester mentioned above occurred because most anaerobic digestion process was
still running conventionally by the aid of only bacteria. To overcome problems associated with the HRT of the
bioreactor, immobilization media could be added to maximize the growth rate of microorganisms and to minimize
the effects of inhibition of the pollutant. Immobilization media could also minimize the effect of inhibition through
supplying the micro nutrients or through adsorbing specific pollutants from POME which were toxic for
microorganism. Specifically in POME, its components in the form of fat and protein potentially possess high free
ammonia and fatty acids content (Solli et al., 2014).
Better growth rate of microorganism would lead to better pollutant removal (in term of COD removal) and better
rate of biogas production. At the end, HRT of the bioreactor could be reduced and the bioreactor volume could be as
low as possible. Natural zeolite were considered as appropriate immobilization media for waste treatment purpose
since it was cheap, had high mechanical strength to accommodate shear stress during fluidization, and had cation
and anion content which were useful as both macronutrient and micronutrient for microorganism (Halim, 2015).
Media immobilizations which have been studied are zeolite and activated carbon. Media immobilization of zeolites
can produce 150% more biogas than the activated carbon. However activated carbon has advantages in terms of the
adsorption capability, which is able to achieve 70.62% COD removal compared with zeolite (50%) and 84.9%
ammonia removal compared with zeolite (74.15%) (Wondah, 2016). However, since natural zeolite had maximum
adsorption capacity and cation exchange capacity, POME concentration was essential to be taken into account. The
higher the concentration of POME meant the higher concentration of specific pollutants which could easily turn
natural zeolite saturated with inhibitors. This research aimed to evaluate critical concentration of POME fed into
digester where the natural zeolite could still function well in minimizing the inhibitory effect of the inhibitors carried
by POME.

MATERIALS AND METHODS

POME was taken from PT. Perkebunan Nusantara VII, Lampung with measured soluble COD (sCOD) of
17,000-20,000 mg/L. The digested biodiesel waste used as starter inoculum was obtained from the biodiesel industry
operating in East Java with the sCOD value of 1,140 mg/L, VFA of 66.1350 mg/L and pH of 7.43. The natural
zeolite was supplied by CV. Minamata, Lampung. High purity chemicals were used in this work for analytical
routines, which included H2SO4 98% (Merck), HCl 37% (Merck), NaOH (Merck), C8H5KO4 p.a (EMSURE),
HgSO4 p.a (EMSURE), AgSO4 p.a (Merck), K2Cr2O7 p.a (EMSURE), Na2B4O7.10H2O 99.55% (Merck), and
CH3COOH 96% p.a. (Merck).

110005-2
 Anaerobic digestion was operated in batch system using a vertical-cylinder-formed digester made of acrylic
equipped with vertical tube gasometer. As much as 2 L POME was added into 2.8 L bioreactor (see Figure 1). Two
variations of POME concentration examined which were 10,000 mg sCOD/L (lower) and 17,000 mg sCOD/L
(higher) with and without zeolite addition each.

4
Annotations:
1. Anaerobic batch bioreactor
2. Bubbler
3. Gasometer
4. Gas sampling port
5. Liquid sampling port
6. Natural zeolite
7. Brine solution
1 3 8. Brine container

5
6
2

7 8

FIGURE 1. Experimental set-up

There were four parameters to be measured during the experiment which were sCOD, VFA concentration, pH
level, biogas volume and methne purity. The analysis method of soluble Chemical Oxygen Demand (sCOD) and
Volatile Fatty Acid (VFA) concentration were performed following Standard Methods for the Examination of Water
and Wastewater (APHA, 2005). The analysis method of pH measurements was performed directly by using a pH
meter Lutron PH-208 that has been calibrated using pH 7 buffer solution. The analysis method of the gas volume
was performed using the gasometer outlined by Walker et al (2009) while the methane content was analyzed by
using Gas Chromatography (GC).

RESULTS AND DISCUSSION

The actual initial sCOD values measured for bioreactors using 10,000 mg sCOD/L and 17,000 mg sCOD/L
POME concentration after mixing with inoculum were 6,750 mg/L and 13,050 mg/L respectively. According to
Figure 2, sCOD fluctuation happened in all four bioreactors. However, bioreactor with lower initial measured sCOD
of 6,750 mg/L tended to decrease until day 42 while bioreactor with higher POME concentration tended to be
constant even until day 42. In general, the addition of immobilization media had no effect to the sCOD decrease
because the curve formed between bioreactor added by natural zeolite and bioreactor without natural zeolite are
almost identical.

110005-3
 25000

20000
sCOD (mg/L)

15000

10000

5000

0
0 3 6 9 12 15 18 21 24 27 30 33 36 39 42
Time (days)

FIGURE 2. The measured sCOD versus time for initial POME concentration of 10,000 mg sCOD/L (lower) and 17,000 mg
sCOD/L (higher) (: lower POME concentration without zeolite; : lower POME concentration + zeolite; ': higher POME
concentration without zeolite; o: higher POME concentration + zeolite)

Figure 3 presents the second parameters which is pH as one of the environmental factors important for
microorganism growth. Most of methanogenic bacteria work on a range of pH 6.7 to 7.4 and the rate of
methanogenesis can be reduced if the pH is lower than 6.3 or higher than 7.8 (Arifiantari et al., 2012).
The pH values in bioreactors with high POME concentration tended to be constant before decreasing from day
36 to day 42 (see Figure 3). On the other hand, the pH values in low POME concentration will reach pH of 6.4-7.5
from day 28. Methanogenesis could be carried out at its optimum in the pH range of 6.6 to 7.6 while acidogenesis
process occured in a pH range of 5 to 6.5. This depicted that bioreactor with low POME concentration had started its
methanogenesis phase at day 18. In this case, bioreactor with high POME concentration would not be conducive for
methane production because until day 42, it was clearly seen that acidogenesis still dominated and there was no
indication that methanogenesis started (indicated by the increase of pH). However, this interpretation still needed to
be further clarified through VFA and biogas production data.

110005-4
 8.00
7.60
7.20
6.80
6.40
pH

6.00
5.60
5.20
4.80
4.40
4.00
0 6 12 18 24 30 36 42
Time (days)

FIGURE 3. The pH values versus time for POME concentration of 10,000 mg sCOD/L (lower) and 17,000 mg sCOD/L (higher)
(: lower POME concentration without zeolite; : lower POME concentration + zeolite; ': higher POME concentration without
zeolite; o: higher POME concentration + zeolite)

Another concern in this work was the VFA concentrations. At bioreactor with lower POME concentrations, the
value of VFA concentration which initially rose to a peak value and then started decreasing indicated that
methanogenic microorganism activity started after enough VFA concentration was provided. On the other hand, at
bioreactor with higher POME concentration, there was indication that the methanogenic microorganism activity
inside the bioreactor was very low due to the inhibition by high VFA concentration from day 7 to day 35 (Figure 4).
For the higher POME, the seemingly constant sCOD in Figure 2 actually also measured the VFA as the sCOD
component. In other words, although sCOD in Figure 2 seems constant, actually the chemical species has changed
from complex organic matter into organic acids (read as VFA). In normal anaerobic process, the VFA is readily
consumed by methanogenic microbes to form organic gases (biogas) released to leave the reaction liquid, so that
both the sCOD and the VFA values is decreasing. In the case of higher POME, the biogas production fail so that no
reduction of the chemical species (as both sCOD and VFA) in the reaction liquid.

110005-5
 12000

10000
VFA (mg acetic acid/L)

8000

6000

4000

2000

0
0 3 6 9 12 15 18 21 24 27 30 33 36 39 42
Time (days)

FIGURE 4. The values of VFA concentration versus time for POME concentration of 10,000 mg sCOD/L (lower) and 17,000
mg sCOD/L (higher) (: lower POME concentration without zeolite; : lower POME concentration + zeolite; ': higher POME
concentration without zeolite; o: higher POME concentration + zeolite)

Figure 5 and Figure 6 present biogas production data. At bioreactor with lower POME concentration, the rate of
methane production could achieve 751 mL/g sCODo without zeolite addition while zeolite addition made the rate of
methane produced lower which was 365 mL/g sCODo. Although biogas production was still possible in the lower
POME concentration, addition of zeolite did not increase the productivity of biogas producing microbes. At higher
POME, biogas production was negligible. This fact indicated that methanogenic activity failed at the higher
concentration tested in this study, which was POME with 17,000 mg sCOD/L initial concentration. This is in good
accordance to the consistently high VFA concentrations displayed by the higher POME in Figure 4, which is
inhibitory to the biogas producing microbes.
The aforementioned comparison between lower and higher POME implied that at higher POME, acid formation
was dominating the anaerobic process. The acidogenic microbes were quite strong to keep high capacity in acid
production even at very high VFA concentration (in the range of 8,000-10,000 mg VFA/L in Figure 4). Zeolite
addition did not help to lower the VFA concentration. An interesting phenomena happened at day 36 when VFA
suddenly decreased and biogas formation was observed in the case of higher POME without zeolite. This might lead
to further study to explore what triggers the methane production at this point after more than 30 days with no biogas
production at all. Once the delayed methanogenic activity understood, more efficient reactor for POME treatment
could be designed and optimized.

110005-6
 800

Cumulative volume of biogas (mL/g

700
600
initial SCOD)
500
400
300
200
100
0
0 3 6 9 12 15 18 21 24 27 30 33 36 39 42
Time (days)

FIGURE 5. The values of cummulative volume of biogas versus time for POME concentration of 10,000 mg/L (lower) and
17,000 mg/L (higher) (: lower POME concentration without zeolite; : lower POME concentration + zeolite; ': higher POME
concentration without zeolite; o: higher POME concentration + zeolite)

800
Cumulative volume of methane

700
600
(mL/g initial SCOD)

500
400
300
200
100
0
0 5 10 15 20 25 30 35 40
Time (days)

FIGURE 6. The values of cummulative volume of methane versus time for POME concentration of 10,000 mg/L (lower) and
17,000 mg/L (higher) (: lower POME concentration without zeolite; : lower POME concentration + zeolite; ': higher POME
concentration without zeolite; o: higher POME concentration + zeolite)

CONCLUSIONS
Anaerobic bioreactor to treat POME using digested biodiesel waste as starter innoculum had critical POME
concentration to keep functioning well (reduce sCOD and produce biogas). The addition of natural zeolite as the
immobilization media would not significantly influence the bioreactor performance when the POME concentration
fed was greater than the critical POME concentration. According to this work, the critical POME concentration was
estimated about 17,000 mg/L, which was labeled as high POME in the study.

110005-7
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