b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 3 4 5 e1 3 5 1

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The effect of waste paper on the kinetics of biogas yield from

the co-digestion of cow dung and water hyacinth

Momoh O.L. Yusuf*, Nwaogazie L. Ify

University Of Port Harcourt, Dept. of Civil & Environmental Engineering, PMB 5323, Choba, Rivers State, Nigeria

article info abstract

Article history: The effect of waste paper on biogas yield produced by co-digesting fixed amount of cow
Received 26 August 2009 dung and water hyacinth in five digesters AeE was studied at room temperature. Waste
Received in revised form paper was observed to improve biogas yield in digesters BeE with digester A acting as the
6 December 2010 control. However, as the amount of waste paper increased the biogas yield was observed to
Accepted 21 December 2010 decrease. Kinetic model based on first order kinetic was derived to estimate the maximum,
Available online 12 January 2011 ultimate, biogas yield and also the ultimate methane yield from these biomass mixtures.
The maximum biogas yield estimated using this model for digesters BeE were 0.282, 0.262,
Keywords: 0.233, and 0.217 lg
1 VS fed with goodness of fit (R2) of 0.995, 0.99, 0.889, and 0.925
Anaerobic respectively, which were obtained by fitting the experimental biogas yield ( yt) against (exp
Biogas yield (kt)
1)/exp(kt). The ultimate biogas and methane yield at very low batch solid load were
Ultimate methane yield extrapolated to be 0.34 and 0.204 lg
1 VS fed respectively. In essence, the addition of waste
First order kinetics paper in the co-digestion of cow dung and water hyacinth can be a feasible means of
Waste paper improving biogas yield and also alternative means of recycling waste paper. Furthermore,
the kinetic model developed can compliment other models used in anaerobic digestion of
agricultural and solid waste.
ª 2010 Elsevier Ltd. All rights reserved.

1. Introduction particulate nature, lignin, cellulose and hemicelluloses

The anaerobic digestion of solid waste has the potential of not
only treating solid waste, but also generating useful bio-fuel
which can be used for diverse purposes like cooking, powering
internal combustion engines, etc. The process of biogas
generation has been established to comprise four major pha-
ses that include hydrolysis, acidogenesis, acetogenesis and
methanogenesis. The hydrolysis phase involves the conver-
sion of complex organics into sugars; acideogenesis involves
the conversion of these sugars into organic acids; acetogenesis
involves the conversion of these organic acids into acetic acid.
Finally, the conversion of acetic acid into methane and carbon
dioxide consists the methanogenic phase [1].
A number of factors can affect the reaction process leading
to the ultimate formation of methane and carbon dioxide. The
content of biomass may affect the overall reaction kinetics
leading to biogas formation. Other factors that may affect the
biogas yield include, low pH due to accumulation of by-prod-
ucts formed during biodegradation, temperature and loading
rate. Knowledge about the biodegradability of biomass
employed in anaerobic digestion can be useful in selecting
suitable biomass for anaerobic process.
Many authors have developed kinetic models to describe
the biodegradability of organic material in order to charac-
terize the biodegradability process. Authors [2e6] have
employed models to study biodegradability of organic mate-
rials in anaerobic digestion. However, these models were based
on maximum specific growth rate of bacteria and required
short retention time which may not be applicable to energy
biomass [7]. Hence, models that describe the process of biogas

* Corresponding author. Tel.: þ234 8035386779.

E-mail addresses: yusuf_mom@yahoo.com (M.O.L. Yusuf), ifynwaogazie@yahoo.com (N.L. Ify).
0961-9534/$ e see front matter ª 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2010.12.033
1346 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 3 4 5 e1 3 5 1
production from biomass are essentially absent. Recently,
works of authors [8,9] showed that a simple model can be
developed based on the first order kinetics to relate biogas yield
and loading rate for completely mixed stirred reactors.
In this work, a similar approach was used to develop
simple kinetic model based on first order kinetics for deter-
mining biogas yield and the maximum biogas yield attainable
for co-digested substrates at room temperature in batch
reactors. Some specific feature of the batch process such as its
simple design and process control, robustness toward coarse
and heavy contaminants and lower investment cost can make
them particularly attractive for developing countries [10].
2. Materials and method
The materials used for this experiment were cow dung, waste
paper, and water hyacinth. Pre-treatment operations involved
weighing about 500 g of freshly harvested water hyacinth and
allowing it to sun-dry for a period of 30 days, after which they
were oven-dried. This oven-dried water hyacinth was then
ground to fine particles using a grinding mill. Similar operation
was applied to the waste paper. Standard methods were used
for waste paper and water hyacinth measurements [11] with
respect to the total and volatile solids. The cow dung was sun
dried for a period of 20 days to preserve its microbial population
and then crushed mechanically using a mortar and pestle.
2.1. Preparation of digesters
A set of five batch reactors were used as digesters. Each digester
contained fixed amount of cow dung and water hyacinth, but
an increasing amount of waste paper. These digesters were
labeled A, B, C, D, and E, respectively. The digester labeled, had
no waste paper, 5 g of cow dung and 5 g of water hyacinth. This
digester acted as the control. Waste paper is biodegradable and
readily available in the environment. Compositions of other
batch reactor digesters BeE contain waste paper in increasing
order as described below. The digester material was made of
glass material of 500 mL capacity,
(i) Digester-B consisted of 4 g of waste paper, 5 g of cow dung
and 5 g of water hyacinth.
(ii) Digester-C consisted of 8 g of waste paper, 5 g of cow dung
and 5 g of water hyacinth.
(iii) Digester-D consisted of 12 g of waste paper, 5 g of cow
dung and 5 g of water hyacinth.
(iv) Digester-E consisted of 20 g of waste paper, 5 g of cow
dung and 5 g of water hyacinth.
The volatile solids of the biomasses were determined
before digestion commenced according to APHA [11] using
a muffle furnace-Carbolite model LMF 4 manufactured in
England. These biomasses were weighed using a weighing
balance Mettler model PN163, manufactured in Switzerland
with specification range between 0.1 mg and 160 g. The
biomasses were mixed with 250 mL of water respectively and
then corked to exclude air. Subsequent connections were as
depicted in Fig. 1. The digesters content were allowed to
ferment for a period of 62 days and agitated twice daily, the
Fig. 1 e Experimental set-up.
morning and evening hours, respectively. After digestion, the
volatile solid content of the digested slurry was determined
according to APHA [11]. Ambient temperature measurements
were determined using a thermometer. The pH of the digester
mixture was determined before and after experiment using
pH meter PN 209. Biogas measurement was carried out using
water displacement method [12].
3. Results and discussion
The data collected for pH values determined before and after
experiment, total solids composition and corresponding
biogas produced in each digester are presented in Table 1. It
was observed that the pH before experiment commenced lie
within the optimum range for biogas production that is
6.6e7.6 [13]. After the experiment, pH values were observed to
increase slightly which is consistent with work of Shoeb et al.
[14]. The average temperature for the period of study was
observed to be 26  C.
The plots of the biogas yield with time for the digesters AeE
are presented in Fig. 2. Digester A with no waste paper had the
lowest biogas yield. The reduced biogas yield obtained here
could be attributed to the composition of biomass undergoing
degradation. Cow dung and water hyacinth are known to
contain cellulose and hemicelluloses which are not easily
susceptible to biodegradation. However, the addition of water
paper to this biomass led to improvement in biogas yield. In
Digester B, biogas yield progressed almost in a linear manner
indicative of and efficient conversion process at work. This
digester composition seemed just suitable for co-digestion
purposes because beyond this amount of waste paper allocated
to Digester B, the biogas yield was observed to generally decline
as shown in digesters C, D and E. The improved biogas yield in
the digesters containing waste paper can be attributed to the
pre-treated nature of waster paper (physical and chemically)
during its manufacture that makes cellulose present in waste
paper easily susceptible to biodegradation [15].
3.1. Kinetic model development
The first order rate equation can provide an empirical
approach in studying the biodegradability of organic material
by observing changes in the volatile solids influent and
effluent concentration. Table 1 showed the first order kinetic
constants and the corresponding biogas production for the
five digesters. There exists some degree of closeness in the
first order kinetic constant obtained in digesters B, C, D and E
which contained certain amount of waste paper as opposed to
what was obtained in digester A. Despite the high kinetic
constant of Digester A, the biogas yield was small in relation to
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 3 4 5 e1 3 5 1 1347

Table 1 e Digester characteristics.

Digester Total Volatile solids (g) in pHb pHa Cumulative k (day
1)
solids (%) 250 mL water biogas (L)

A 3.846 7.49 7.18 7.96 0.320 0.00795

B 5.303 10.91 6.81 7.57 0.720 0.00434
C 6.716 14.53 6.71 7.35 0.842 0.00401
D 8.088 17.79 6.69 7.40 1.052 0.00390
E 10.70 24.67 6.41 7.35 1.110 0.00336

a After experiment.
b Before experiment.

other digester with waste paper. It does mean therefore, that dC

VR ¼ VR rC (2)
the addition of waste paper can improve biogas yield by dt
modifying composition of the biomass mixtures. Pavan and where rC is the substrate removal rate as a function of (C ). At
Mata-Alvarez [16] reported that the composition of waste can any time (t) the first order rate model can be written as (3) with
affect biogas yield. Thus, the biomass composition of digesters first order kinetic constant (k) i.e,
B, C, D, and E could be considered similar due to the presence
of certain amount of waste paper. dC
¼
kC (3)
Because it has been established that waste paper increased dt
biogas yield in digesters B, C, D and E, subsequent kinetic This equation can be written in the analytical form as,
studies were limited to these four digesters. The estimation of Co
the maximum biogas yield and the ultimate biogas yield ln ¼ kt: (4)
Ct
attainable using these biomass types was established in this
This equation generally relates to substrate (biomass) biode-
study. The maximum biogas yield ( ym) is the biogas yield
gradability with no information about the biogas yield. However,
obtainable if biomass is allowed to undergo biodegradation for
a correlation between substrate biodegradability and biogas
very long period of time in batch reactors (Fig. 3), while the
yield at any time ( yt) can be developed assuming all substrate
ultimate biogas yield ( yL) is the maximum biogas yield
(biomass) are converted into biogas as shown in Fig. 3 [8],
equivalent to the ultimate anaerobic biodegradability that
although, in reality all substrate may not be converted to biogas.
results at total solid loading or organic loading rate very close
From the correlation it can be deduced that,
to zero [8]. Though, it’s possible to determine these values
experimental through long period of anaerobic digestion, it Co
Ct yt
¼ (5)
may also be possible to estimate these values through curve Co ym
fitting as developed here.
and
The development of the model describing biogas produc-
tion process in batch reactors with volume (VR) by co-digesting Co ym
¼ (6)
cow dung and water hyacinth with waste paper was based on Ct ym
yt
mass balance approach by observing changes in the volatile Substituting Co/Ct in equation (4) with ym/( ym
yt) we
solids concentration (C ) i.e., obtained,
 
dC ym
VR ¼ Qo Co
Qo C þ VR rC (1) ln ¼ kt (7)
dt ym
yt
However for a batch system flow of input (Qo) ¼ 0, (where Co This can be rearranged to obtain,
and C are the influent and effluent volatile solids) so that the

equation can be written as yt ¼ ym 1
e
kt (8)

Fig. 2 e Plot biogas yield against time.

1348 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 3 4 5 e1 3 5 1

Co
ym - yt ym

Biogas yield
C o - Ct
Substrate

yt

C(t)

t time (t)

Fig. 3 e Substrate transformation into biogas during

anaerobic degradation. Fig. 5 e Plot to estimate maximum biogas yield ( ym) in
Digester C.

This equation can be used to estimate maximum biogas

yield if experimental data on the daily biogas yield and first
order kinetic constant are available. In essence a plot yt against
(1
e
kt) would produce a linear curve fit with slope ym.
Sometimes, studies on anaerobic degradation may require
that certain percentage or proportion ( p) of the maximum
biogas yield at any time (t) be determined, especially when the
time for maximum biogas yield (tmax) requires long period of
biodegradation. In such cases, the time to attain certain
percentage or proportion of the biogas yield for example 80%
(0.8) or 90% (0.9) of maximum biogas yield can be of great
importance for design purposes.
In order to obtain a model that can predict the time for
certain percentage or proportion ( p) of the maximum biogas Fig. 6 e Plot to estimate maximum biogas yield ( ym) in
yield, Equation (7) was employed. Digester D.
By letting yt ¼ pym we obtain,
 
ym
ln ¼ kt (9) 3.2. Application of kinetic model in the estimation of
ym
pym
maximum biogas yield
This reduced to,
  The estimation of the maximum biogas yield in digesters B, C,
1 D and E employing Equation (8) are presented in Figs. 4e7. The
ln ¼ kt (10)
1
p
model seemed to follow a linear curve fit as expected. The
So that maximum biogas yield of 0.282, 0.262, 0.233, and 0.217 lg
1 VS
fed were obtained for digesters B, C, D, and E with goodness of
p ¼ 1
e
kt (11) fit 0.995, 0.99, 0.889 and 0.925 respectively. Thus, it can be
Thus, by plotting ( p) against different time (t) for known inferred that as waste paper increased in the mixture, the
value of k, would provide charts which can be employed for maximum biogas yield decreased. Linke [8] obtained similar
estimating the time at which certain percentage or proportion decrease in the maximum biogas yield as organic loading rate
of the maximum biogas yield can be obtained in batch reactors.

Fig. 4 e Plot to estimate maximum biogas yield ( ym) in Fig. 7 e Plot to estimate maximum biogas yield ( ym) in
Digester B. Digester E.
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 3 4 5 e1 3 5 1 1349

Fig. 8 e Plot of proportion of ym against time.

increased from anaerobic digestion of solid waste from potato
processing, though for a continuous stirred tank reactor.
The kinetic model is also significant in determining the
time required to obtain certain proportion or percentage of the
maximum biogas yield. The application of Equation (11) was
used to obtain Fig. 8. It was observed that to obtain 50% or 0.5
of the maximum biogas yield for the digesters B, C, D and E
required160, 175, 180 and 205 days retention time respectively,
under room temperature condition. Hence performance of
digester can be assessed through this approach.
3.3. Application of kinetic model in the estimation of
ultimate biogas ( yL) yield
C, D and E could be described by Equation (12) with a goodness
of fit 0.973.
y ¼
76:50x þ 26:71 (12)
where y represents percent total solids fed in the digesters and
x represent the corresponding maximum biogas yield. The
ultimate biogas yield was estimated by assuming total solids
of 0.5% which is close to zero. Substituting into Equation (12)
yields a value of x that is 0.3426 lg
1 VS.
Similarly, the relationship between the waste paper as
percent of total solid fed into the digester and the maximum
biogas yield for digester B, C, D and E can be described by the
Equation (13) with goodness of fit 0.936.

y ¼
547:2x þ 184:5 (13)

The ultimate biogas yield which is the maximum biogas yield
obtainable at solid loading very close to zero was determined
by plotting the total solids (%) and/or waste paper addition
(% of total solids) against their corresponding maximum
biogas yield observed in the various digesters (Fig. 9).
The relationship between the percent of total solids fed
into the reactor and the maximum biogas yield for reactor B,
where y represents waste paper as percent of total solids fed
and x represents maximum biogas yield. Again, by assuming
0.5% waste paper (% total solids), the ultimate biogas yield was
estimated to be 0.336 lg
1 VS. In essence, the ultimate biogas
yield attainable from these biomass mixture comprising
cow dung, water hyacinth and waste paper in the manner

Fig. 9 e Plot to determine the ultimate biogas yield attainable.

1350 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 3 4 5 e1 3 5 1

Fig. 10 e Plot of digester sizes against retention time.

 kt 
described here would approximately be 0.34 lg
1 VS fed into e
1
yt ¼ ym (17)
the digester. e kt

Though the methane composition of biogas was not deter-

mined in this research, a basic assumption is that biogas
comprises 60% methane and 40% carbon dioxide [17]. Based on
this assumption the ultimate methane yield attainable by these
biomass mixtures is 0.204 lg
1 VS fed. This value is so close to
the biochemical methane potential of related biomass reported
in literature [15,18]. The biochemical methane potential assay
relies on very low substrate loading to ensure that the batch
digester does not suffer imbalance through products inhibition
[15]. An average ultimate methane yield of 0.22 lg
1 VS fed for
fresh water aquatics and 0.24 lg
1 VS fed for forage/grasses have
been reported [18], while [15] estimated the ultimate methane
yield for waste paper to range between 0.28 and 0.37 lg
1 VS fed.
Thus, the ultimate methane yield at low total solids concen-
tration extrapolated here through this approach may as well
correspond to the ultimate methane yield obtained through the
typical biochemical methane potential assay approach
employed by researchers in biogas studies.
3.4. Application of kinetic model in batch reactor design
Most models for reactor design are based on bacteria growth
e.g. Monod, Contois etc. However, design approaches based on
the yield of product are few with works of authors [8]
contributing to the list of available works in this area. A sim-
ilar approach based on yield of products has been employed in
the design and sizing of batch reactors for anaerobic digestion.
A ratio of 1:3 was used by [19] to establish a relationship
between the volume of the gas chamber (which is proportional
to the volume of biogas produced) and the volume of the
anaerobic digester. Hence for a given mass of volatile solids (m)
fed into the digester, the following deductions can be obtained.
1 biogas yield which can be determined from very long periods
Vgc ¼ Vdigester
3 of anaerobic batch reaction was alternatively estimated
Rearranging,
3Vgc ¼ Vdigester
But
Vgc ¼ yt $m
and
Substituting Equation (17) into (16)
 kt 
e
1
Vgc ¼ kt
ym $m (18)
e
rThus,
 kt 
e
1
Vdigester ¼ 3 kt
ym $m (19)
e
Hence, for a given value for k and ym, the volume of the
batch reactor can be estimated for any retention time
required. For example the plot of Vdigester against various
retention times for digesters B, C, D and E (Fig. 10) showed that
2.2, 2.4, 2.7 and 3 L reactors would be required to contain the
reaction process and biogas produced for retention period of
62 days respectively. Similar, capacity in cubic meter is
possible depending on the solid loading.
This means, that 0.73, 0.8, 0.9 and 1.0 L of biogas was
produced by digester B, C, D and E respectively. These estimated
values approximate reasonably with the volume of biogas
obtained experimentally (Table 1). A safety factor between 1.05
and 1.2 may be used for final correction when designing batch
reactor for these biomass types at room temperature.
4. Conclusion
The anaerobic biodegradation of biomasses comprising cow
dung, water hyacinth and waste paper is feasible at room
temperature. The addition of waste paper to fixed amount of
cow dung and water hyacinth was observed to improve biogas
production. However, biogas yield was observed to decrease
with increase in waste paper concentration. The ultimate
(14)
through curve fitting. The maximum biogas yield for digesters
B, C, D and E was estimated to be 0.282, 0.262, 0.233 and
(15) 0.2176 lg
1 VS fed respectively, while the ultimate biogas and
methane yield attainable from these mixtures were estimated
to be 0.34 and 0.204 lg
1 VS fed respectively, at 0.5% total solids
(16)
concentration in which waste paper comprised 0.5% of the
total solids. This would correspond to 5 g each of cow dung
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 3 4 5 e1 3 5 1
and water hyacinth co-digested with 0.05 g of waste paper in
2 L of water or inoculums solution. The result obtained
through these methods of curve fitting could help compliment
biochemical methane potential assay.
In addition, the kinetic model was employed in batch
reactor design for given value of k and ym. The batch reactor
volume required was estimated to be 2.2, 2.4, 2.7 and 3 L for
digesters B, C, D and E respectively for retention period of 62
days. Again, the use of first order kinetics and maximum
biogas yield in reactor design may compliment other design
approach available in literature.
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