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International Journal of Green Energy

ISSN: 1543-5075 (Print) 1543-5083 (Online) Journal homepage: http://www.tandfonline.com/loi/ljge20

Kinetic modelling of augmenting biomethane yield


from poultry litter by mitigating ammonia

Balaji Selvaraj, Senthilkumar Krishnasamy, Sakthivel Munirajan, Pasupathy


Sangareddy Alagirisamy, Mohanraj Dhanushkodi, Sukanya Gopalsamy &
Karthick Kumar Kuppusamy

To cite this article: Balaji Selvaraj, Senthilkumar Krishnasamy, Sakthivel Munirajan, Pasupathy
Sangareddy Alagirisamy, Mohanraj Dhanushkodi, Sukanya Gopalsamy & Karthick Kumar
Kuppusamy (2018): Kinetic modelling of augmenting biomethane yield from poultry litter by
mitigating ammonia, International Journal of Green Energy, DOI: 10.1080/15435075.2018.1529580

To link to this article: https://doi.org/10.1080/15435075.2018.1529580

Published online: 10 Oct 2018.

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INTERNATIONAL JOURNAL OF GREEN ENERGY
https://doi.org/10.1080/15435075.2018.1529580

Kinetic modelling of augmenting biomethane yield from poultry litter by mitigating


ammonia
Balaji Selvaraj a, Senthilkumar Krishnasamyb, Sakthivel Munirajanc, Pasupathy Sangareddy Alagirisamyd,
Mohanraj Dhanushkodie, Sukanya Gopalsamyf, and Karthick Kumar Kuppusamya
a
Department of Mechanical Engineering, Kumaraguru College of Technology, Coimbatore, India; bDepartment of Mechanical Engineering, Adhitya
Institute of Technology, Coimbatore, India; cDepartment of Mechanical Engineering, Koneru Lakshmaiah Education Foundation, Guntur, India;
d
Department of Electronics and Communication Engineering, Kumaraguru College of Technology, Coimbatore, India; eDepartment of Mechanical
Engineering, Sasurie College of Engineering, Coimbatore, India; fDepartment of Electrical and Electronics Engineering, Sri Krishna College of
Technology, Coimbatore, India

ABSTRACT ARTICLE HISTORY


In this study, the kinetics of biogas production was studied by performing a series of the laboratory Received 10 November 2017
experiment with air stripped poultry litter. Four kilograms of Raw Poultry Litter is mixed with water in Accepted 25 September 2018
the ratio 1:3, respectively, and loaded inside the digesters and the samples are compared with Air KEYWORDS
stripped Poultry Litter for a retention time of 21 days. The modified Gompertz equation suitably Air stripped Poultry litter;
construes the cumulative biogas produced as a function of time. From the kinetics of the system, it is ammonia mitigation; biogas
inferred that the biogas production potential (A), maximum biogas production rate ðrm Þ, and lag phase production rate; kinetics of
period (λ) of Raw Poultry litter is 18.77 (l/kg of VS); 1.08 (l/kg of VS/day); 1.5 days, respectively, comparing biogas production; modified
with Air stripped Poultry Litter of 22.05 (l/kg of VS); 1.30 (l/kg of VS/day); 1 day, respectively. These gompertz equation
results show that biogas production can be enhanced efficiently by means of ammonia removal pre-
treatment process.

Introduction only provides valuable business, in turn at tail end it accumu-


lates a huge volume of wastes which is a serious matter of
Energy is required for human beings to sustain at every stage of life
discussion in recent times (Kirubakaran et al. 2007). Improper
for their shelter, food, transportation, and industrial activities
managed poultry wastes can cause severe harm to the envir-
(Herbert and Krishnan 2016). In the recent past, the global energy
onment by polluting water and air, which eventually reduce
consumption has been increased progressively in too many folds.
the quality of life (Abouelenien et al., 2010). Considering all
The rural energy demand is growing rapidly which is supplied by
advantages in converting poultry waste into energy, anaerobic
the fossil fuels predominantly such as coal, oil, gas. The use of fossil
digestion (AD) is found to be an economically viable, fruitful
fuel accompanies the emission of carbon compounds and other
technique which manages the wastes effectively resulting in
inorganic substances into the atmosphere which results in climate
the production of gaseous fuel and nutrient-rich manure
change, global warming and various health hazards (Panwar,
compared to any other technique used for waste treatment
Kaushik, and Kothari 2011). For independent and stable future
(Panwar, Kaushik, and Kothari 2011). The working and mon-
in energy production, exploration of new renewable energy
itoring the anaerobic systems are typical whose stability is
resources are the way to meet the energy demand (Demirbas and
always uncertain. The instability is observed as a reduction
Balat 2009). The biomass plays an important role among all other
in methane production rate, increase in Volatile Fatty Acid
renewable energy resources because it is the primary source for
(VFA) content causing failure of the digester. The high level
rural households. Biomass is used to produce heat by means of
of ammonia is identified as a major cause of digester failure
combustion directly or it can be converted into several forms of
since it inhibits the microbial activity directly by exterminat-
bio-fuel indirectly (Munda et al. 2012). Usage of biomass for
ing the microbial ambiance (Rajagopal, Massé, and Singh
energy production aids to uphold ecological balance by reducing
2013).
harmful emissions and purifying the environment, apart from the
Poultry litter comprises a huge amount of organic nitrogen
economic and social aspects (Saha, Biswas, and Pal 2014).
which mainly constitutes proteins and amino acids (60–80%)
While considering biomass sources, the wastes resulting
(Krylova et al. 1997 Kelleher et al. 2002). For the growth of
from livestock breeding has a significant role to play in energy
anaerobic organisms, the presence of nitrogen is inevitable
production (Okuo, Waheed, and Bolaji 2016). Poultry breed-
when the concentrations are within the limits (Strik,
ing plays a vital role in the rural economy, poultry farms are
Domnanovich, and Holubar 2006). While biological anaerobic
better organized, and it is progressing towards modernization
degradation of nitrogen, ammonia is evolved. As discussed,
than the rest of the livestock sector. The poultry breeding not

CONTACT Balaji Selvaraj balajimechanical05@gmail.com Department of Mechanical Engineering, Kumaraguru College of Technology, Coimbatore, India
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/ljge.
© 2018 Taylor & Francis Group, LLC
2 B. S ET AL.

the ammonia concentration while exceeding the limits of stripping in biomethanation of poultry litter. In addition, model-
0.7 g/l to 2.6 g/l will impede the microbial activity resulting ing the kinetics of cumulative biogas production was simulated
in low yield (Koster and Lettinga 1988). The ammonia pro- using the modified Gompertz model.
duced inside the digester is basically in two forms, namely
Ammonium ions (NH4 +) and free ammonia (NH3). The high
concentrations of free ammonia can pass through the cell Materials and methods
membrane and into cell resulting in proton imbalance and Sample collection and preparation
potassium deficiency, which ultimately reduce the microbial
population inside the digester and this makes the FA as an Poultry litter was collected from a brooder house in Erode
utmost toxic element for the AD (Appels et al. 2008). On district, Tamil Nadu, India. To increase the ammonia nitrogen
another hand when the ammonium ion concentration exceeds level by converting the proteins and uric acids, the collected
the limits, the degradation of organic compounds are hin- poultry litter was kept under anaerobic for 60 days maintained
dered and at the tail end, the ammonium ions are highly at room temperature. After anaerobiosis, the treated poultry
corrosive in nature which leads to high maintenance and litter was heated in an oven at 80°C and aerated for 24 hr for
handling costs. This drags the attention of the researchers to ammonia removal which is known as air stripping.
lower the nitrogen content in the feedstock, in order to
mitigate the ammonia production inside the digester. It Analytical methods
finds it essential to have low ammonia levels for any treatment
and handling of poultry litter (Kelleher et al. 2002). The organic carbon, ash content, Total Kjeldahl Nitrogen,
The common methods to reduce the ammonia inhibition volatile solids (VS) and total solids (TS) present in the sample
are dilution (Rajagopal, Massé, and Singh 2013), acclimation was estimated by the standard methods and procedures. The
(Abouelenien, Nakashimada, and Nishio 2009), addition of total solids were determined by drying the feedstock in the
phosphorite ore (Krylova et al. 1997), removing ammonia by hot air oven for 1 hr at 105°C. Volatile solids were determined
biogas recycle (Abouelenien et al. 2010), nitrification/denitri- by heating the dried sample at 550°C for 2 hr in a muffle
fication process, Anaerobic ammonia oxidization (Anammox) furnace. pH was measured using a digital pH meter. The gas
(Dong and Tollner 2003), ammonia stripping (Gangagni Rao generated was passed through the scrubbing apparatus and
et al., 2008) and co-digestion (Abouelenien et al., 2014). then through the positive displacement wet-type gas flow
Among these methods, stripping is used to get rid of ammo- meters for measuring the daily biomethane production. The
nia from the sample to be digested, and higher removal of temperature of the generated gas measured by using a
ammonia could be possible using this stripping method (Liao, thermometer.
Chen, and Lo 1995). The chemicals are not needed for strip-
ping process due to that it was found to be economical and Digester design
efficient physical method. Removal of ammonia by stripping
is based on forcing the dissociation equilibrium of NH4 The anaerobic digestion was conducted in a fixed dome type
+/NH3 to favor the formation of free ammonia. It is a gaseous digester in a batch mode operation. The digester is made up
molecule which is easily stripped out from aqueous solution. of Poly Ethylene Terephthalate (PET) and it is designed to
The pH of the sample should be greater than 10 or/and have a volume of 22 l with a height–diameter ratio of 1.9. The
temperature should be raised to enhance the free ammonia slurry inside the digester is mixed manually twice a day to
species. The addition of enormous alkalis (NaOH, CaO, KOH, avoid scum formation during the period of the digestion. If
and Ca (OH) 2) needed to raise the pH. Thus, raising the not, the scum formed will act as a membrane and hinder the
temperature is the primary choice to enhance the ammonia gas released out of the slurry to occupy the gas storage region
disassociation (Markou 2015). in the digester. The working volume of the digester was 16 l.
Many mathematical models have been developed, to describe Two different fermentation slurry samples, sample 1 (4 kg of
the bacterial growth curve in a batch culture of the anaerobic RPL+ 12 l of water) and sample 2 (4 kg of APL + 12 l of
system (Gibson, Bratchell, and Gibson 1987). Among them, water) were prepared in 1:3 ratio. After loading the digester
Modified Gompertz equation was the most suitable model for the valves are shut airtight in order to ensure anaerobic
defining bacterial growth. In this study, to remove nitrogen from conditions in the headspace of anaerobic digesters. The gen-
Poultry Litter (PL) by stripping, proteins or uric acid should be erated biogas from the digester was collected on a daily basis
first degraded down to ammonia. For this reason, PL could be using a gas flowmeter. The gas scrubbing arrangement is
stored under dry anaerobic conditions for protein and uric acid shown in Figure 1. The experiments were carried out at
degradation to convert organic nitrogen to ammonia mesophilic conditions for a hydraulic retention time of
(Abouelenien, Nakashimada, and Nishio 2009), followed by 21 days.
ammonia stripping to reduce the nitrogen content. Laboratory
experiments performed in batch mode using 20-l biodigester. The
Model development for biogas production kinetic in
biogas production from Air Stripped Poultry Litter (APL) is com-
batch mode
pared with Raw Poultry Litter (RPL). The results obtained from
these experiments were used to fit and check the fitness of the The working and biomethane production from anaerobic diges-
Modified Gompertz equation (MGE) (Budiyono et al., 2010). The tion can be enhanced by validated mathematical models developed
objective of this study is to investigate the effect of ammonia from mechanistic studies which give the better understanding of
INTERNATIONAL JOURNAL OF GREEN ENERGY 3

Figure 1. Gas scrubbing arrangement.

the chemical kinetics of the microbial population involved in using poultry litter as feedstock. In addition, kinetics of biogas
anaerobic digestion (Yu et al., 2013). To interface the fundamental production was studied using an appropriate model. The
characteristics of the digestion processes, modeling can be used physicochemical parameters of the sample were determined,
(Yu and Wensel 2013). To predict the methane production, oper- and the results are shown in Table 1. The initial volatile solids
ating conditions, system stability, effluent quality, understanding (VS) of substrate ranged from 80% to 87%. This represents
of process mechanisms, and kinetics are required (Yu and Wensel that higher organic solids present in the sample which is
2013). From past studies, it is evident that the Modified Gompertz converted to biomethane.
equation is the most suitable model for describing bacterial growth It was observed that pH of the fermentation slurry was
(Budiyono et al. 2010). varying during the biogas production throughout the
retention time. The pH is an important factor that affects
Modified Gompertz model the digestion process. Low pH has been reported to inhibit
Modified Gompertz kinetic equation is a modified form of the methanogenic bacteria that are responsible for biogas pro-
Gompertz equation which is generally used to simulate the duction. pH value less than 5 or greater than 8 has been
cumulative biogas production. This model assumes that reported to rapidly inhibit methanogenesis. It has been
cumulative biogas production is a function of hydraulic reten- reported that anaerobic bacteria required a natural envir-
tion time. The biogas production in batch condition is related onment and thus a pH ranging from 6.4 to 7.2 is needed
and corresponding to the specific growth rate of methano- for optimum biogas production in accordance with the
genic bacteria in the digester and it will follow modified conclusions of (Kaur and Chauhan, 2017). From
Gompertz equation (Budiyono et al. 2010). Figure 2, it is observed that pH of the RPL and APL are
n hr  e io in a near neutral range which is desirable for an effective
m
P ¼ Aexp  exp ðλ  tÞ þ 1  ð1Þ AD. From Figure 2, it is inferred that the enhancement in
A
the biomethane yield is due to the increased metabolic
where P is cumulative of the specific biogas production (l/kg activity of the anaerobes inside the digester which is due
of VS), A is the biogas production potential (l/kg of VS), rm is to the consequence of the high concentration of hydrogen
the maximum biogas production rate (l/kg of VS/day), λ is the ions in the digesting slurry. This slight shift towards alka-
lag phase period or the minimum time required to produce linity will favor the microbial population to consume the
biogas (day), t is the hydraulic retention/cumulative time to organic load more effectively.
the feedstock for biogas production in days and e is mathe- Carbon to nitrogen ratio (C: N) is one of the important
matical constant with value 2.7182. The data obtained from factors that enhance biogas production from organic sam-
the experimental study was checked for the fitness of ples. The yield of biogas depends on the C/N ratio of the
Modified Gompertz equation. This will aid to evaluate kinetic various feedstocks. From the findings of Dalkilic et al. the
models and other parameters that can be used to design and C/N ratio for optimum yield of biogas is in the range of
scale-up of laboratory experiments into industrial size appli- 20–30 (Dalkılıc and Ugurlu 2015). The C: N ratio of RPL is
cations. The kinetics constant A, rm , and λ were determined
using a non-linear regression method for the best fittings with
Table 1. Physicochemical parameters.
the aid of POLYMATH software.
Constituent Raw poultry litter After air stripping
Organic Carbon % 47.07 47.17
Ash % 13.47 10.84
Results and discussion Total Kjeldahl Nitrogen (TKN) % 6.9 3.69
C/N 6.82 12.78
This research step was focused on investigating the influence Total Solids (TS) % 17 20
of ammonia stripping on cumulative biogas production while Volatile Solids (VS) % 87.5 84.78
4 B. S ET AL.

Figure 2. Effect of pH on biogas production.

found to be 6.82:1. Because of low C/N ratio of RPL, higher pre-treatment method, the C/N ratio is increased by about
nitrogen content to carbon present thus results in ammonia 87.3% compared to RPL.
accumulation. This leads to an increase in pH again leads The daily biogas production (l/kg of VS) was measured by
to low methane production. For APL, C/N ratio is 12.78:1. using gas flowmeter and the values are plotted as shown in
From the observation, it is clear that using air stripping as a Figure 3.

Figure 3. Daily biogas production.


INTERNATIONAL JOURNAL OF GREEN ENERGY 5

Figure 4. Cumulative biogas production.

From this, it is observed that the production of biogas was low system, with an assumption that biogas produced is a function of
in both starting and ending days of the digestion process. This bacterial growth. The modified Gompertz equation fit to equa-
indicates that the biogas generated in batch mode corresponds to tion (1) is shown in Figure 5 (RPL) and Figure 6 (APL). Kinetic
the specific growth rate of methanogenic bacteria. From Figure 3, constants of U, A, and λ is shown in equation 1 can be deter-
the peak biogas production was obtained on the 9th day in APL mined using nonlinear regression.
and 12th day in RPL and biogas production is high until peak Kinetic constants obtained are presented in Table 2. The raw
biogas production day. This is due to the activities of acclimatized poultry litter gave the kinetic parameters of biogas production,
methanogenic bacteria as they overcome the protective wall that i.e., biogas production potential (A), maximum biogas produc-
inhibits the cell destruction for conversion to biogas. On another tion rate ðrm Þ, and lag phase period or the minimum time
hand, it can also be interpreted as the degradation of lignin, required to produce biogas (λ) are 18.77 (l/kg of VS); 1.08 (l/kg
cellulose and hemicelluloses make accessible to the microorgan- of VS/day); 1.5 days, respectively. While stripped poultry litter
isms for conversion to biogas. gave the kinetic parameters A, rm and λ are 22.05 (l/kg of VS);
The cumulative biogas production observed for 21 days 1.30 (l/kg of VS/day); 1 day, respectively.
is shown in Figure 4. From Figure 4, it is observed that The biogas yield potential (P) which represents biogas
biogas production rate tends to follow sigmoid function accumulated inside the digester for 21 days. The P is
(S curve) as it normally occurs in the batch growth curve. maximum for APL of 21.42 l/kg of VS and minimum
The APL exhibit higher cumulative biogas production for RPL of 18.42 l/kg of VS. This shows that using air
than RPL. The cumulative production at day 21 was stripping as a pre-treatment method, biogas generation
18.42 l/kg of VS for RPL and 21.42 l/kg of VS for APL, increased. The maximum biogas generated per day is
respectively. The cumulative biogas production from APL is known as the maximum biogas production rate (rm ).
significantly higher than RPL. This study shows APL was to The rm for RPL is 1.08 l/kg of VS/day and 1.30 l/kg of
be capable of improving the yield of biogas production by VS/day for APL. The higher rm in APL indicates that
16.3% higher than digestion of RPL. The huge accumula- higher biogas generated during the digestion process. It
tion of ammonia and nitrogen content is undesirable for was observed that the stripping process will enhance the
the biogas production in RPL. Whereas in APL, ammonia biogas production rate considerably. The lag phase indi-
content is reduced considerably using air stripping method. cates the found to be 1.5 days for RPL and 1 day for APL
Thus, high biogas production was observed in APL. because, in APL, the organic brood in the digesting slurry
is consumed rapidly compared to the RPL.
From Figures 5 and 6, it is clear that the Modified
Kinetics of biogas production Gompertz equation fits well to the experimental data. The
The biogas production kinetics was studied by developing the Gompertz equation gives the best fit which is described
equation closest to fundamental for biogas production in a batch by higher R2 for APL (0.999) and RPL (0.998).
6 B. S ET AL.

Figure 5. Kinetic models of Modified Gompertz fitted to cumulative biogas production data from raw poultry litter.

Figure 6. Kinetic models of Modified Gompertz fitted to cumulative biogas production data of Stripped poultry litter.

Table 2. Summary of Kinetic data.


Modified Gompertz parameters (Model)
Digester Experimental Biogas yield (l/kg of VS) A (l/kg of VS) rm (l/kg of VS/day) λ(days) R2
Raw poultry litter 18.42 18.77 1.08 1.5 0.998
Stripped poultry litter 21.42 22.05 1.30 1 0.999

Conclusion RPL gave the kinetic parameters of biogas production, i.e.,


biogas production potential (A), maximum biogas production
The kinetics of biogas production was studied by performing
rate ðrm Þ, and lag phase of 18.77 (l/kg of VS); 1.08 (l/kg of VS/
a laboratory experiment using APL compared with RPL.
day); 1.5 days comparing with APL of 22.05 (l/kg of VS); 1.30
Modified Gompertz equation best describes cumulative gas
(l/kg of VS/day); 1 day, respectively. The best performance of
produced as a function of retention time. From this study, the
biogas generation was observed in APL. From this study, it is
INTERNATIONAL JOURNAL OF GREEN ENERGY 7

observed that optimizing biogas production from poultry Kelleher, B. P., J. J. Leahy, A. M. Henihan, T. F. O’Dwyer, D. Sutton, and
litter using air stripping as a pre-treatment method represents M. J. Leahy. 2002. Advances in poultry litter disposal technology–A
review. Bioresource Technology 83 (1):27–36. doi:10.1016/S0960-8524
a feasible and sustainable energy option. (01)00133-X.
Kirubakaran, V., V. Sivaramakrishnan, M. Premalatha, and P.
Subramanian. 2007. Kinetics of auto-gasification of poultry litter.
ORCID International Journal of Green Energy 4 (5):519–34. doi:10.1080/
Balaji Selvaraj http://orcid.org/0000-0003-4974-7490 15435070701583102.
Koster, I. W., and G. Lettinga. 1988. Anaerobic digestion at extreme
ammonia concentrations. Biological Wastes 25 (1):51–59. doi:10.1016/
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