Process Biochemistry 37 (2002) 965– 971

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A kinetic study of the anaerobic digestion of ice-cream wastewater

W.C. Hu a, K. Thayanithy a, C.F. Forster b,*
a
School of Chemical Engineering, Uni6ersity of Birmingham, Edgbaston, Birmingham B15 2TT, UK
b
School of Ci6il Engineering, Uni6ersity of Birmingham, Edgbaston, Birmingham B15 2TT, UK

Received 29 May 2001; received in revised form 21 August 2001; accepted 9 October 2001

Abstract

The process kinetics of the mesophilic (35 °C) anaerobic digestion of ice-cream wastewater was investigated. The Monod
equation and the Contois equation were used to develop two basic steady-state models. The kinetic parameters required for the
application for the steady-state models were determined using a laboratory-scale continuously stirred tank reactor (5 l) fed with
a synthetic ice-cream wastewater at a range of hydraulic retention times (2.99– 7.45 days). Both models were evaluated with a set
of routine analytical data obtained from a pilot-scale (5 m3) anaerobic contact digester treating the ice-cream wastewater at a
commercial site. The steady-state model obtained with the Contois equation was more suitable than that obtained with the Monod
equation for describing the process kinetics of the pilot-scale anaerobic contact process. The main reason for this is that the kinetic
model based on the Contois equation considers the effect of any changes in influent substrate concentration in its prediction.
© 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Anaerobic digestion; Process kinetics; Ice-cream wastewater; Monod equation; Contois equation

1. Introduction son that the contact reactor is capable of providing an

The process of anaerobic digestion has been greatly
developed during the last two decades for the treatment
of wastewater from food industries; for example, from
the sugar manufacturing wastewater [1], starch wastew-
ater [2] and brewery wastewater [3]. However, for some
wastewaters which contain a high amount of fats and
proteins, such as ice-cream wastewater, anaerobic diges-
tion was found to be troublesome, due to the potential
of sludge flotation [4], the formation of fat/lipids scum
layers at the surface of the reactor, which did not digest
[5] and the inhibition/toxicity effects of the intermediate
compounds (long chain fatty acid) generated during the
anaerobic digestion of the wastewater [6]. The anaero-
bic contact reactor is one of the more widely used in
Europe and its designs and operational characteristics
are well defined [7,8]. This process has been reported to
give a better performance than other reactor types,
when treating ice-cream wastewater [9] due to the rea-
* Corresponding author. Tel.: + 44-121-414-5069; fax: + 44-121-
414-3675.
E-mail address: c.f.forster@bham.ac.uk (C.F. Forster).
adequate mixing of the digester contents.
Process modelling is a useful tool for describing and
predicting the performance of anaerobic digestion sys-
tems. Monod type kinetic models have been widely
used to describe the process kinetics of anaerobic di-
gesters [10,11]. Although there has been some success in
applying Monod type kinetics to the anaerobic process,
some research workers found it difficult to apply them
for their systems [12,13]. For instance, Grady et al. [12]
have shown that the effluent substrate concentration,
expressed as COD, was not independent of the sub-
strate concentration entering the reactor when pure or
heterogeneous cultures were used.
In the equation proposed by Contois [14], the specific
growth rate was considered as a function of the growth-
limiting nutrient in both input and effluent substrate
concentration by using an empirical constant, which
was related to microbial concentration. On this basis,
Chen and Hashimoto [15] developed kinetic models for
substrate utilisation and methane production and sug-
gested that the Contois type kinetic models would be
more suitable than the Monod type kinetic models to
predict digester performance. However, there is not

0032-9592/02/$ - see front matter © 2002 Elsevier Science Ltd. All rights reserved.
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966 W.C. Hu et al. / Process Biochemistry 37 (2002) 965–971

much published information available for the process Five different HRTs (7.45, 5.99, 4.60, 3.76 and 2.99
kinetics of anaerobic digestion treating ice-cream days) were used to investigate the anaerobic digestion
wastewater using Contois type kinetics. The aim of this of ice-cream wastewater. In order to establish a normal
paper was, therefore, to compare these two types of steady-state condition, the digester was fed with the
kinetic models for describing the process kinetics of ice-cream wastewater for at least five residence times at
anaerobic contact reactor treating an ice-cream each HRT values. The effluent from the digester was
wastewater. collected and analysed for pH, soluble chemical oxygen
demand (SCOD), volatile fatty acids (VFA), alkalinity
and total suspended solids/volatile suspended solids
2. Materials and methods (TSS/VSS). The biogas produced from the digester was
analysed for methane (CH4) and carbon dioxide (CO2).
2.1. Digesters
2.2. Chemical analysis
The laboratory-scale continuously stirred tank reac-
tor (CSTR) which was used in this study has been
The following measurements were carried out ac-
described previously [16]. Essentially, it was a purpose-
cording to standard methods for the examination of
built glass tank fitted with a side U-pipe, with a work-
water and wastewater [18]: alkalinity and TSS/VSS. The
ing volume of 5 l. The feed was pumped (Watson
SCOD was measured by the sealed tube method (sam-
Marlow, Model 502S) at a rate defined by the hydraulic
ple size, 2 ml) (Hach, 1500 mg l − 1 range). All analyses
retention times (HRTs) required. The stirrer speed was
were duplicated and the results quoted as mean values.
arbitrarily set at 60 rpm (Electrolab, Bredon, Glos) as
The amounts of CH4 and CO2 in the biogas produced
this gave adequate mixing of the reactor contents. The
was measured by gas chromatography (Pye Unicam,
temperature was maintained at 3591 °C by a thermo-
Model 104). The system had a 16.3 m glass column (3
statically controlled heating pad (Electrolab, Bredon,
mm i.d.) with a Porapack Q (mesh size 80–100) sup-
Glos). Gas was collected by the downward displace-
port and was maintained at 90 °C. The carrier gas was
ment of acidified (0.05 M H2SO4) water and measured
helium (40 ml min − 1) and the sample size was 1.0 ml.
at STP.
The variation of the actual results from the mean values
The inoculum used in this work had a total solids
was B5%. VFA were determined by gas chromatogra-
concentration of 10% and was obtained from a 14 l
phy (Cambridge model Ai) using a megabore column
anaerobic digester, which was used to digest molasses
(D-BFFAP, 30 m × 0.536 mm i.d.). Helium served as
wastewater in the Environmental Biotechnology Labo-
the carrier gas (3.2 ml min − 1).
ratory at the University of Birmingham.
A synthetic ice-cream wastewater was prepared by
diluting white vanilla flavour soft ice-cream (Sains-
3. Results and discussion
bury’s Economy) with distilled water. A 1.5% (w/v) was
selected for this study as this concentration gave a
3.1. Performance
similar level of COD (5500 mg l − 1) as the real effluent
from the industry [9,17]. The synthetic ice-cream
Steady-state results obtained during the reactor oper-
wastewater was supplemented with sources of nitrogen
ation at five different HRTs are summarised in Table 2.
and phosphorus by adding NH4Cl and KH2PO4. The
They show that the pH and alkalinity remained within
composition of the ice-cream wastewater is summarized
the optimal working range for anaerobic digesters (6.8–
in Table 1. The sludge was allowed to acclimatize for 4
7.2 and above 1500 CaCO3 mg l − 1, respectively). A
weeks before the trials were commenced.
soluble COD removal in excess of 90% was obtained at
Table 1
all HRTs used in this work. The specific methane yield
Composition of the synthetic ice-cream wastewater varied from 0.341 to 0.308 l g CODrem − 1 as the HRT
was decreased and the maximum methane yield of
Parameter Mean concentration Standard deviation 0.341 l g CODrem − 1 was obtained at HRT of 7.45 days.
(mg l−1) (mg l−1)
This was close to the theoretical methane yield of 0.35
pH 7.70 l g CODrem − 1 and is comparable with results reported
CODtotal 5500 159 previously [9]. Fig. 1 shows data for the VFAs pro-
CODfiltered 3700 104 duced by the digesters. The total VFA concentration
Alkalinity 1500 (as CaCO3) 7 remained below 200 mg l − 1 at all the HRTs and con-
VFA 175 9.6 sisted mainly of the higher acids (higher than acetic and
NF4–N 165 11.3
TSS 635 36
propionic acids), especially valeric, isocaproic and
VSS 585 35 caproic acids. The concentrations of these acids made
up approximately 61–80% of the total VFA produced.
 W.C. Hu et al. / Process Biochemistry 37 (2002) 965–971 967

Table 2
Experimental results obtained under steady-state conditions (mean values)

Parameter HRT (day) Standard deviation

7.45 5.99 4.60 3.76 2.99

pH 7.00 6.95 6.90 6.90 6.90 0.01–0.02

Alkalinity (CaCO3 mg l−1) 1836 1794 1745 1725 1680 7.55–10.58
Effluent conc. (SCOD mg l−1) 91 128 163 226 304 2.08–6.06
SCOD removal (%) 98 97 96 94 92 –
Total gas production (l l−1 d−1) 0.314 0.389 0.505 0.611 0.712 0.01–0.1
CH4 yield (l g CODadded−1) 0.332 0.322 0.317 0.305 0.283 –
Total VFA (mg l−1) 82 99 115 121 151 8.19–14.11
Effluent biomass conc. (VSS mg l−1) 1002 1089 1075 1062 1053 20.88–52.65

vmax × S
This might indicate that the population of acetogenic v= . (2)
(KS + S)
bacteria present in the digester was not enough to
convert these higher acids into acetic acid. Further- Eq. (1) reduces to
more, it has also been suggested that the acetogenic
vmax × S 1
bacteria could be inhibited by the presence of higher = +Kd. (3)
acids when their concentration exceeds 42% of the total KS + S HRT
VFA produced [19]. This equation can be rearranged to estimate the
In addition, it was found that a white scum-like effluent substrate concentration at the steady-state con-
material was present in the broth within the reactor at dition as follows:
the end of the investigation (HRT= 2.99 days). This
KS × (Kd + (1/HRT))
type of material has been reported previously and was S= . (4)
thought to be undigested lipid [4,5]. It was only ob- vmax − Kd − (1/HRT)
served at the shortest HRT and was in the form of a The rate of change in substrate concentration in the
fragmented, particulate scum. This phenomenon was system could be expressed as:
very different from that found by other research work-
ers who reported the scum as a layer floating at the
dS Q
= (S0 − S)−
v×X
,
  (5)
surface of the digester. This could be attributed to using dt V Y
a CSTR in this work. Contact reactors give better
mixing than other reactor configurations (i.e. UASB)
and, therefore, would decrease the potential of a scum-
layer of undigested lipids being formed. This could also
affect the treatment efficiency of the digester.

3.2. Kinetic model—based on Monod equation

For a CSTR without biomass recycle, the rate of

change of biomass in the system can be expressed as
dX Q Q
= X0 − X +vX −KdX, (1)
dt V V
where Q is the flow rate (l day − 1); V the volume of the
reactor (l); X0 and X are the concentrations of biomass
in the feed and the reactor/effluent (g VSS l − 1), respec-
tively; v and Kd are the specific growth rate (day − 1)
and death rate constant (day − 1), respectively
If it is assumed that the concentration of biomass in
the influent can be neglected, that at steady-state dX/
dt =0 and that the HRT is defined as the volume of the
reactor divided by the flow rate of the influent, and
since the relationship between the specific growth rate
and the rate limiting substrate concentration can be
expressed by the Monod equation: Fig. 1. Variation in the VFA concentrations.
968 W.C. Hu et al. / Process Biochemistry 37 (2002) 965–971

where, Y is the yield coefficient (g VSS g COD − 1); S0

the substrate concentration in the feed (g COD l − 1).
Under steady-state conditions, the rate of change in
substrate concentration is negligible and by a similar
technique to that used for the substrate concentration,

 
the above equation can be reduced to
1 X 1
(S0 −S) = +Kd . (6)
HRT Y HRT
The above equation can then be rearranged to esti-
mate the effluent biomass concentration under steady-
state condition as follows.
Y ×(S0 − S)
X= . (7)
(1+ Kd × HRT)
Fig. 2. Determination of growth and decay rates.
3.3. Kinetic model—based on Contois equation
By plotting Eq. (11), the values of Y and Kd can be
A similar technique was used to develop a kinetic calculated from the slope and intercept of the line.
model based on the Contois equation. The relationship The value of vmax and KS could be determined by
between the specific growth rate and the rate limiting plotting Eq. (12), which was derived by rearranging Eq.
substrate concentration can be expressed by the Con- (3). The value of vmax can then be calculated from the
tois equation as follows: intercept of the straight line while Ks can be obtained
from the slope of the line.
vmax × S
v= , (8) HRT K 1 1
BX + S = S × + . (12)
1+ HRT × Kd vmax S vmax
where, B is the kinetic parameter
(g COD g biomass − 1). Similarly, the values of vmax and B can be obtained
By substituting Eq. (8) instead of the Monod equa- by plotting Eq. (13), which is obtained by rearranging
tion into Eq. (1) gives Eq. (9). The value of vmax can be calculated from the
intercept of the straight line while B could be obtained
vmax ×S 1 from the slope of the line.
= + K d. (9)
BX +S HRT
HRT B X 1
Substituting Eq. (7) into Eq. (9) and then rearranging = × + . (13)
1+ HRT ×Kd vmax S vmax
it, the effluent substrate concentration at steady-state
Five steady-state sets of data were used to determine

 
conditions can be expressed as
the kinetic parameters required for applying these two
B ×Y kinetic models. Fig. 2 was plotted for determining the
S= ×S0. (10)
(vmax − Kd)× HRT + B × Y −1 values of Y and Kd while the values of vmax and Ks
In this model, the equation for the effluent biomass (Monod model) were determined from Fig. 3. For the
concentration has the same expression as Eq. (7) due to Contois type model, the values of vmax and B were
a similar technique being used.
Eq. (4) and Eq. (7) form the basis of the Monod type
model while Eq. (10) and Eq. (7) form the basis of the
Contois type model. If the kinetic parameters are
known, Eq. (4), Eq. (10) and Eq. (7) can be used to
predict the effluent substrate concentration and micro-
bial biomass concentration under steady-state
conditions.

3.4. Determination of the kinetic parameters

The kinetic parameters Y, Kd can be obtained by

  
rearranging (Eq. (6)) as shown below:
(S0 −S) 1 1 1 Fig. 3. Determination of maximum specific growth rate and half
=× + ×Kd. (11)
HRT ×X Y HRT Y saturation constant (Monod type model).
 W.C. Hu et al. / Process Biochemistry 37 (2002) 965–971
Fig. 4. Determination of maximum specific growth rate and kinetic
constant (Contois type model).
determined from Fig. 4 and the kinetic parameters are
given in Table 3.
3.5. E6aluation of the kinetic model
The Monod type model and Contois type model were
evaluated by comparing the predicted COD values with
a set of routine analysis from a pilot-scale (5 m3)
anaerobic contact digester treating ice-cream wastewa-
ter at a commercial site (Fig. 5). Both models gave
correlations, which were significant at the 95% level.
However, both models predicted effluent COD values,
which were lower than the actual measured values. The
most likely reason for this is that the factory wastewa-
ter and the simulated wastewater had different chemical
and biodegradation characteristics. An examination of
the kinetic parameters of a range of food-related
wastewaters has shown that Y does not vary very
widely and that Kd had values such that the variations,
which were found did not have any appreciable effect
on the effluent COD predicted by the Contois type
model [20]. The sensitivity of the model was, therefore,
assessed by examining the effect of a 10% change to the
values of B and vmax. The results (Table 4) show that
variations in vmax had the greater influence on the
effluent COD. A similar analysis of the Monod based
model showed that, again, vmax had the greatest influ-
ence (data not shown). No kinetic data were available
from the pilot-scale study. However, an examination of
the analytical data, which were available, showed that
Table 3
Kinetic parameters
vmax (day−1) KS (g COD l−1)
Monod Contois
0.7844 0.9297 0.4028
969
Fig. 5. Comparison between the predicted and the actual effluent data
from the full-scale anaerobic contact process (Contois type model
(); Monod type model (")).
the main difference between the factory and the simu-
lated wastewaters was that the former contained a
higher concentration of suspended solids, 95% of which
were volatile. These particles would contribute to the
COD but would degrade more slowly than the soluble
fraction. This would imply that the biomass in the pilot
plant would have a lower vmax than that in the labora-
tory reactor. The model based on the Contois equation
was, therefore, re-applied using vmax values lower than
the one determined in the laboratory. This showed that
the simple, albeit arbitrary, change in the vmax value
from the measured value of 0.93 to one of 0.697
produced predicted COD values, which were very simi-
lar to those which had been measured (Fig. 6). Chang-
ing the value of vmax in the model based on the Monod
equation by the same amount did not produce as good
a comparison (Fig. 6) This suggests that the Contois
type model would be more suitable than the Monod
type to express the performance of the pilot-scale
anaerobic contact process. It also demonstrates that the
results derived from laboratory-scale studies can be
used successfully on full-scale plant as long as the
kinetic constants are applied with a degree of common
sense. The major difference between the Monod type
model and the Contois type model is that in the latter,
the prediction of the effluent substrate concentration is
related to the influent substrate concentration (Eq. (10))
whilst in the Monod type model, it is totally indepen-
B (COD g VSS−1) Y (g VSS g COD−1) Kd (day−1)
0.4818 0.2116 0.0131
970 W.C. Hu et al. / Process Biochemistry 37 (2002) 965–971

Table 4 are responsible for producing sufficient quantities of

The effect on the predicted effluent COD of varying B and vmax by
9 10% for a range of operating conditions
Predicted COD (mg l−1)
HRT= 2.4 day HRT= 2.78
day
S0 =6.48 g l−1 S0 = 5.6 g l−1
extracellular enzymes for the hydrolysis of lipids. This
hypothesis is similar to that reported by Noike et al.
[21] who studied the anaerobic digestion of cellulose,
soluble starch and glucose, and suggested that the
HRT =3.8 day cellulose degradation data was best fitted to the Contois
equation, while the degradation data for soluble starch
S0 = 4.94 g l−1 and glucose fitted best to the Monod equation.

As modelled 507.5 346.0 194.8

B−10% 460.3 (−9%) 313.3 (−9%) 176.0 (−10%)
4. Conclusions
B+10% 553.9 (+9%) 378.3 (+9%) 213.5 (+10%)
vmax−10% 612.5 (+21%) 410.2 (+19%) 225.7 (+16%)
vmax+10% 433.2 (−15%) 299.1 (−14%) 171.4 (−12%) In this study, the kinetics of anaerobic contact pro-
B−10% and 556.4 (10%) 371.9 (7%) 204.0 (5%) cess treating ice-cream wastewater was investigated us-
vmax−10% ing models based on the Monod equation and the
B+10% and 473.4 (−7%) 327.3 (−5%) 187.9 (−4%)
vmax+10%
Contois equation and the following conclusions were
drawn:
“ The Contois type model was found to be more
suitable than that based on the Monod equation for
dent of the influent substrate concentration (Eq. (4)). predicting the performance of the anaerobic contact
The discharge of effluent from food industries are vari- process at pilot-scale due to the effect of the varia-
able and the amounts of substrate concentration tion of wastewater concentration being considered in
present in the effluent can change considerately during the Contois equation.
operation. In the case of ice-cream wastewater from the “ The Contois type model was found to be more
pilot-scale plant, the routine analytical data collected suitable than the Monod type model for expressing
during 1988–1990 showed that the wastewater concen- the microbial kinetics of anaerobic digestion treating
tration could vary from 2.6 to 6.4 g COD l − 1 within a fat-rich wastewater.
week.
Another reason is that the ice-cream wastewater con-
tained considerable amounts of fats and proteins, which Acknowledgements
require a longer time of hydrolysis than the simple
sugars. The model based on the Contois equation in- The data from the full-scale digester were obtained
corporates the effect of microbial concentration to pre- during work funded be the SERC Grant No. GR/E
dict the reactor performance and the micro-organisms 2873.4.

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