Bioresource Technology 106 (2012) 1–9

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Mathematical modeling of process liquid flow and acetoclastic methanogenesis

under mesophilic conditions in a two-phase biogas reactor
Ivo Muha a, Alfio Grillo a, Michael Heisig a, Mandy Schönberg b, Bernd Linke b, Gabriel Wittum a,⇑
a
Goethe-University, Goethe-Center for Scientific Computing, Kettenhofweg 139, 60325 Frankfurt a.M., Germany
b
Potsdam-Bornim e.V. (ATB), Leibniz-Institut für Agrartechnik, Max-Eyth-Allee 100, 14469 Potsdam, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Acetoclastic methanogenesis in the second stage of a two-phase biogas reactor is investigated. A math-
Received 15 July 2011 ematical model coupling chemical reactions with transport of process liquid and with the variation of
Received in revised form 22 November 2011 population of the microorganisms living on the plastic tower packing of the reactor is proposed. The evo-
Accepted 24 November 2011
lution of the liquid is described by an advection–diffusion–reaction equation, while a monod-type kinetic
Available online 1 December 2011
is used for the reactions. Moreover, a new inhibition factor MOmax is introduced, which hinders the
growth of microorganisms when the plastic tower packing is overpopulated. After estimating the reaction
Keywords:
parameters, the acetate outflow measured experimentally is in good agreement with that predicted by
Mathematical modeling
Methanogenesis
simulations. For coupling liquid transport with reaction processes, a spatial discretization of the reactor
Two-phase biogas reactor is performed. This yields essential information about the distribution of acetate and the production of
Anaerobic methane in the reactor. This information allows for defining a measure of the effectiveness of the reactor.
ADM1 Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction
In order to provide long-term energy supply, a worldwide sus-
tainable energy production needs to be established. In this context,
research and extension of renewable energies are essential. Biogas
produced by anaerobic digestion fermenters plays an important
role (Chynoweth et al., 2001). Methane production is the result
of several chemical and physical processes that occur in a biogas
reactor. This is a reactor in which a duly chosen biomass leads to
generation of methane through fermentation. The gas has to be
conveyed to other parts of the plant and has to be finally delivered
to a users network. As any other industrial plant, the efficiency of
the production cycle has to be optimized. The scope of research
is thus to optimize methane production. Several factors concur to
achieve this goal. These concern the technical aspects related to
the design of the biogas plant, the composition of the biomass,
and the processes taking place in the reactor. The influence of
the composition of the biomass on the methane yield was investi-
gated, for example, by Amon et al. (2006b). Additionally, the influ-
ence of energy crops on the methane yield was investigated in
order to achieve a sustainable crop rotation with maximal methane
yield (Amon et al., 2006a). The crucial process occurring in a biogas
reactor is the anaerobic digestion performed by microorganisms. In
order to be able to understand this process and quantify the meth-
ane yield, Batstone et al. (2002) formalized an anaerobic digestion
⇑ Corresponding author. Tel.: +49 69 798 25223; fax: +49 69 798 25258.
E-mail address: wittum@gcsc.uni-frankfurt.de (G. Wittum).
model (ADM1). The ADM1 model covers all four phases of the
anaerobic digestion process (hydrolysis, acidogenesis, acetogenesis
and methanogenesis). Since then, the ADM1 model was used to
further investigate and optimize anaerobic digestion in biogas
plants (Blumensaat and Keller, 2005). Wett et al. (2007) optimized
the design of a biogas plant according to results obtained through
mathematical modeling. Anaerobic co-digestion of olive mill
wastewater with olive mill solid waste was studied by Boubaker
and Ridha (2008), Wichern et al. (2009) examined monofermenta-
tion of grass silage under mesophilic conditions by using the ADM1
model, and Thamsiriroj and Murphy (2011) investigated the mono-
digestion of grass silage in a 2-stage CSTR anaerobic digester. The
research in this field has considered neither the coupling between
process liquid flow and models for anaerobic digestion nor the spa-
tial dependence of microorganisms and chemical substances. How-
ever, this is an important issue to determine relevant parameters of
a biogas plant, e.g., its effectiveness (ratio of local to maximal
methane production). A further understanding should thus be
achieved by formulating a mathematical model, which couples
process liquid flow with the chemical reactions carried out by
microorganisms. Such a mathematical involves quantities that
are spatially resolved. Investigating a mathematical model which
addresses the above described problems is the main purpose of
this contribution. For modeling process liquid flow, the second
stage of the biogas reactor is considered to be filled with a porous
medium, where the matrix consists of the plastic tower packing
with microorganisms growing on it, the latter being assumed to
be immobile. The concept of porous media is used in various fields,

0960-8524/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2011.11.087
2 I. Muha et al. / Bioresource Technology 106 (2012) 1–9

Nomenclature
 
xsMO mass fraction of microorganisms in the solid phase (1) C lAc concentration of acetate kg
m3
xlAc mass fraction of acetate intheliquid phase (1)  
kg C gCH4 concentration of methane kg
qs density of the solid phase m 3
m3  
  C sMO concentration of microorganisms kg
ql density of the liquid phase m kg   m3
PgCH4 kg
3
  accumulated local methane production m 3
kg 1
qlAc density of acetate m 3 km;Ac uptake rate of microorganisms (h )
  Y Ac fraction of uptaken acetate used for growth (1)
l kg
q H2 O density of water m 3
MOmax plastic tower packing dependent parameter (kg)
 
qsMO density of microorganisms m kg
3
kdec decay rate of microorganisms (h1)
  fac;MO fraction of decayed microorganisms converted to ace-
kg
qsPTP density of plastic tower packing m 3 tate (1)  
kg
/ volume fraction of the solid phase (1) K sAc Michaelis–Menten constant for acetate m 3

ql Darcy velocity of the liquid ms td doubling time of microorganisms under optimal condi-
pl pressure within the liquid phase tions (h)
  (Pa)
g gravity acceleration vector m lmax growth rate of microorganisms under optimal condi-
  s2
tions (h1)
kg
l viscosity ms
 2
K permeability tensor
ms  m
D diffusion tensor s

e.g., in geosciences where the flow of groundwater in geological
porous media (e.g., aquifers) is investigated (Grillo et al., 2010). An-
other example is drug penetration through the skin, which is a bio-
logical porous medium (Naegel et al., 2008).
In order to couple flow and reaction processes, the biogas reac-
tor needs to be spatially discretized. This means that the biogas
reactor is approximated by a computational grid consisting of tri-
angles or quadrangles in 2D or tetrahedra in 3D. Typically, in each
grid point all variables (concentrations, pressure, etc.) are com-
puted. This information can help to improve the effectivity of the
biogas plant as spatial dependencies can be considered, e.g., a spa-
tially varying concentration of acetate or pH. A measure for effec-
tivity of the biogas reactor can be defined by investigating local
methane production (in each grid point).
2. Methods
2.1. Experimental setup
This section describes briefly the laboratory scale plant used in
the experiments. The anaerobic filter (cf. Fig. 1 [3]) and the second
fluid circulation (cf. from Fig. 1 [5]) are described in detail as the
main focus of this work lies on these two parts.
2.1.1. Design of the laboratory scale plant
A laboratory-scale plant (Fig. 1) consists of a hydrolysis reactor
(Fig. 1 [1]), a reservoir (Fig. 1 [2]), a downstream fixed film anaer-
obic filter (Fig. 1 [3]), two circulation systems (Fig. 1 [4], [5]), a bio-
gas bag (Fig. 1 [6]), and an automated gas analysis system (Fig. 1
[7]).
The hydrolysis reactor is a square-box-fermenter made of poly-
vinyl chloride (PVC) and having a total usable volume of 100 l. The
reservoir and the anaerobic filter are double-walled bodies of
cylindrical shape made of transparent acrylic glass and having a to-
tal usable volume of 55.4 and 32.12 l, respectively. The anaerobic
filter is 0.71 m high, features a cross section with a diameter of
0.24 m, and is randomly packed with plastic tower packing ‘‘Bio-
flow 40’’ (Rauschert, Judenbach-Heinersdorf, Germany). Both the
reservoir and the anaerobic filter are equipped with a thermo-
stated water jacket ‘‘E 100’’ (Lauda, Lauda-Königshofen, Germany),
and are heated up to 55 and 38 °C, respectively. The hydrolysis
reactor is heated up by the leachate in the reservoir.
The first circulation system features a membrane pump W 100
(Wilden, Grand Terrace, USA) and connects the leachate reservoir
with the hydrolysis reactor. In the second circulation system, a
continuous volume flow is achieved by a peristaltic pump PD
5201 (HEIDOLPH, Schwabach, Germany). This system connects
the anaerobic filter with the hydrolysis reactor. The biogas bags
are TECOBAG having a volume of 100 l (Tasseraux, Bürstadt, Ger-
many). The automated gas analysis system consists of a Drum-type
Gasmeter TG 05/5 (RITTER, Bochum, Germany) and a gas analysis
device SSM 6000 (PRONOVA, Berlin, Germany).
2.1.2. Operation of the laboratory scale plant
The biomass (10 kg rye silage, 1 kg rye straw) is discontinuously
filled in the hydrolysis reactor during a 21 d period of experiments.
The circulation of process liquid operates in two different circula-
tion systems. Due to percolation, the dissolved organic compounds
are accumulated in the process liquid which is collected in the
hydrolyzate reservoir.
1
In the first circulation, the process water ð60 l h Þ is led back
into the hydrolysis reactor by the membrane pump W 100 for reg-
ulating the temperature regime and maintaining the optimal mois-
ture content in the organic solid matter. Furthermore, the
microorganisms, which are involved in the biomass degradation
process, are transported back.
1
In the second circulation, a continuous volume flow ð1 l h Þ is
achieved by the peristaltic pump PD 520. Here, the process liquid is
transferred from the reservoir of the process liquid into the fixed
film anaerobic filter. Before the process liquid flows in the anaero-
bic filter, the concentration of the following organic acids are
determined by a gas chromatography: acetic acid, propionic acid,
butyric acid, valeric acid and caproic acid. Furthermore, the acetic
acid equivalence and the pH are measured. The process liquid that
flows out of the anaerobic filter, is analyzed for acetic acid equiva-
lence and pH.
The generated biogas is collected in the separate 100 l gas bags
TECOBAG. Once a day an automated gas analysis is performed and
the volume is recorded. A magnet valve is activated by a control
unit. The gas is extracted through the Drum-type Gasmeter TG
05/5 and the gas analysis device SSM 6000 for gas composition
analysis. Depending on the amount of gas, the gasmeter sends im-
pulses to the control unit. At the same time the pressure sensor
examines the difference between system pressure and ambient
 I. Muha et al. / Bioresource Technology 106 (2012) 1–9
Fig. 1. Scheme of a two-phase laboratory scale anaerobic digestion system consisting of: [1] a hydrolysis reactor (100 l), [2] a reservoir for leachate from the hydrolysis
reactor (60 l), [3] a fixed film anaerobic filter (32.12 l), [4] a small leachate circulation system ð60 l h Þ, [5] a complete leachate circulation system ð1 l h Þ [6] two biogas
bags and [7] an automated gas analysis system.
pressure. With an empty gas tank the pressure difference drops,
resulting in a voltage drop. The pump is turned off and the magnet
valve closes. The incoming data is logged.
2.2. Mathematical model
In this section the mathematical model for process liquid flow
and acetoclastic methanogenesis is presented.
Degradation, which takes place in the anaerobic filter, consists
of the decomposition of acetate into methane and carbon dioxide
(cf. [3] in Fig. 1). Hereby, the degradation process is performed
by microorganisms. Table 1 shows the denotation of every mod-
eled process.
The model presented in this section is very general and only lit-
tle modification is needed to apply this model to similar multi-con-
stituent flow/reaction problems. Note that it is always necessary to
distinguish between the model for flow 2.2.1, and the model for
reactions 2.2.2, where the processes from Table 1 are modeled.
2.2.1. Modeling of flow
The study of the anaerobic filter requires considering processes
involving a solid, a fluid and a gaseous phase. Each phase com-
prises several constituents. The features and functions of these
constituents are very diverse. Indeed, the constituents of the liquid
and gaseous phases are mainly chemical species that take part in,
or are the products of, reactions, whereas the constituents of the
Table 1
Denotation of reaction terms included into the mathematical model.
Denotation Process
RAc!MO Consumption of acetate by microorganisms (proliferation)
RAc!CH4 Degradation of acetate to methane
RAc!CO2 Degradation of acetate to carbon dioxide
RMO!l Transfer of microorganisms to the liquid phase (death)
RMO!Ac Transfer of microorganisms to acetate (death)
Rl!s Phase transition (from liquid to solid phase)
Rs!l Phase transition (from solid to liquid phase)
Rl!g Phase transition (from liquid to gas phase)
3
1 1
solid phase confer an internal structure to the filter. Such a struc-
ture is determined by the arrangement of the plastic tower packing
inserted in the filter and may depend on the local population of the
microorganisms deposited on the packing because a change in
population alters the space available to the circulation of the liquid
and gases in the filter. In principle, a comprehensive analysis of the
processes occurring in the filter should take into account all phases
and all constituents. This could be accomplished by means of a
multi-constituent, multiphase-flow model with chemical reac-
tions. This is a mathematical description in which both the liquid
and the gases, which co-exist in the void space of the solid phase,
are subjected to flow and chemical reactions, and their constitu-
ents follow advection–diffusion–reaction equations. Such a model,
however, would have to face two major difficulties: the first one is
technical and due to the fact that a very large number of nonlinear,
coupled partial differential equations should be solved; the second
one arises from the fact that more experimental information would
be needed, which is neither currently available in the literature nor
easy to extract from the performed experiments. These reasons im-
pose some limitations to the modeler, who has to select the pro-
cesses which are essential for the production of methane, neglect
those whose contribution is believed to be marginal, and consider
only the equations describing the evolution of the constituents
which, under appropriate working hypotheses, play a major role
in the characterization of the phase in which they are present. In
this respect, the principal constituents of the solid, liquid and gas-
eous phase are, respectively, the plastic tower packing (PTP) and
the microorganisms (MO) deposited on it, water ðH2 OÞ and acetate
(Ac), and methane ðCH4 Þ and carbon dioxide ðCO2 Þ. Each of the
mentioned constituents should be studied by considering appro-
priate balance laws. However, a satisfactory agreement between
simulations and experiments can be achieved by considering even
a smaller number of constituents as explicitly present in the model.
Meaning that, even when a given constituent has to be accounted
for, nothing will be said about the balance laws associated with it
(cf. Section 3.6).
In summary, the equations of the reduced mathematical model
describe the flow of a multi-constituent single-phase liquid
through a porous medium (plastic tower packing and microorgan-
4 I. Muha et al. / Bioresource Technology 106 (2012) 1–9

isms deposited on it). Despite the single-phase approach, the mod- @ð/qs xsMO Þ
¼ RAc!MO  RMO!l ð10Þ
el is able to simulate the transport processes and reactions in @t
which the constituents of the liquid phase take part, the variation
of the population of the microorganisms, the production of carbon @½ð1  /Þql 
¼ rðql ql Þ þ Rs!l  Rl!s  Rl!g ð11Þ
dioxide, and the production of methane (main goal of the plant and @t
necessary to evaluate the effectiveness of the reactor). Within the  
solid and the liquid phase, every quantity has an associated mass @ ð1  /Þql xlAc  
¼ r ql xlAc ql  ql Dð/ÞrxlAc þ RMO!Ac
fraction and density. The theory reported in the rest of this section @t
is widely documented in the publications by Bear and Bachmat  RAc!MO  RAc!CH4  RAc!CO2 : ð12Þ
(1990) and Hassanizadeh and Gray (1980).
Hereby, D is the diffusion tensor and ql is Darcy velocity of the li-
The solid phase, P s , is defined by
quid, which is given by
P s :¼ fMO; PTPg: ð1Þ Kð/Þ
ql ¼  ðrpl  ql gÞ; ð13Þ
The mass fraction of the microorganisms is denoted by xsMO and the
l
mass fraction of the plastic tower packing by xsPTP . The apparent where K is the permeability tensor, l is viscosity, pl is pressure, g is
density of the solid phase qs is the gravity acceleration vector.

qs ¼ xsMO qsMO þ ð1  xsMO ÞqsPTP ; ð2Þ

Remark 2.1. As the sum of all reactions used in the equations for
s s the gas phase (5), the solid phase (9) and the liquid phase (11)
where q is the density of the microorganisms and q
MO the den- PTP
cancel out, the local mass is preserved.
sity of the plastic tower packing. Note that the sum of all mass frac-
tions within a single phase equals one. Therefore, the equation
ð1  xsMO Þ ¼ xsPTP holds.
The liquid phase, P l , is defined by
P l :¼ fH2 O; Acg: ð3Þ 2.2.2. Modeling of reactions
This section covers all reactions used in this model. In acetoclas-
Let xlH2 O denote the mass fraction of water and xlAc the mass frac- tic methanogenesis methane is produced by degradation of
tion of acetate. The apparent density of the liquid phase reads acetate. Hereby, the degradation process is carried out by microor-
ganisms. The model includes growth, uptake and decay of acetate
ql ¼ xlAc qlAc þ ð1  xlAc ÞqlH2 O ; ð4Þ
degrading microorganisms. Solubility of methane in the liquid
l
where q is the density of acetate and q
Ac the density of water. l
H2 O
phase is not included due to the very low solubility of methane.
The accumulated local gas production is computed by the Furthermore, a new inhibition factor is introduced to account for
formula the size, shape and number of the plastic tower packing in the
Z t
reactor. Note that in this section local concentrations are used. Lo-
Pg ðt; xÞ :¼ Rl!g ðT; xÞdT cal concentrations are computed depending on the substance’s
0 phase:
Z t
¼ ðRAc!CO2 ðT; xÞ þ RAc!CH4 ðT; xÞÞdT: ð5Þ C sMO :¼ /qs xsMO microorganisms concentration ð14Þ
0
C lAc :¼ ð1  /Þql xlAc acetate concentration: ð15Þ
The accumulated local methane production is then given by
Z t As suggested, e.g., by Batstone et al. (2002) and Wichern et al.
4
PCH4 ðt; xÞ ¼ Pg ðt; xÞ ¼ RAc!CH4 ðT; xÞdT: ð6Þ (2009) a Michaelis–Menten term for uptake is used, with growth
15 0 and methane production being implicit (cf. Table 1):
Hereby, the fraction 4/15 is needed to account for the molecular
C lAc
weight of CH4 and CO2 (cf. Section 2.2.2). RAc!MO :¼ km;Ac Y Ac C sMO IðC sMO ; C lAc Þ ð16Þ
In order to study the effectiveness of the reactor, the maximal K sAc þ C lAc
local methane production is defined: 4 C lAc
RAc!CH4 :¼ km;Ac ð1  Y Ac Þ C sMO IðC sMO ; C lAc Þ ð17Þ
Pmax ðtÞ :¼ max PCH4 ðt; xÞ: ð7Þ 15 K sAc þ C lAc
x
11
The effectiveness of the reactor can then be defined by RAc!CO2 :¼ RAc!CH4 ; ð18Þ
4
Z
1 PCH4 ðt; xÞ where km;Ac is the uptake rate, Y Ac is the fraction used for growth,
EffðtÞ :¼ dx; ð8Þ K sAc is the Michaelis–Menten constant and IðC sMO ; C lAc Þ the inhibition
V Reactor V Reactor Pmax ðtÞ
factor. Although carbon dioxide is not considered in the gas phase,
where V Reactor is the total usable volume of the reactor. the reaction term RAc!CO2 is still needed for the phase transition
The volume fraction of the solid phase is denoted by /. Depend- reactions and for the reaction terms regarding acetate. The fractions
ing on whether the population of microorganisms increases or not, 11/4 and 4/15 in RAc!CO2 and RAc!CH4 are needed to account for the
the volume fraction of the solid phase can either increase or different molecular weights of carbon dioxide (44 g/mol) and meth-
decrease. ane (16 g/mol).
The volume fraction of the pore space is ð1  /Þ. It is assumed to First order decay for microorganisms is used:
be completely filled with liquid. By applying the mass balance laws
RMO!l :¼ kdec C sMO ð19Þ
for microorganisms, acetate, the solid and the liquid phase, the fol-
lowing closed set of partial differential equations is obtained: RMO!Ac :¼ kdec fac;MO C sMO ; ð20Þ
where kdec is the decay rate and fac;MO is the fraction, which is con-
@ð/qs Þ
¼ Rl!s  Rs!l ð9Þ verted back into acetate. These reaction terms are used in Eqs. (5),
@t
(10) and (12).
 I. Muha et al. / Bioresource Technology 106 (2012) 1–9
Remark 2.2. If the condition C lAc  K sAc holds true and no inhibi-
tion occurs, the following can be written
C lAc
1 ð21Þ
K sAc þ C lAc
IðC sMO ; C lAc Þ  1: ð22Þ
In this case, the doubling time td and the maximal specific growth
rate lmax of the microorganisms read:
lmax ¼ km;Ac Y Ac  kdec ð23Þ
lnð2Þ
td ¼ :
lmax
Finally, the phase transition reactions have to be defined. Although
an equation for carbon dioxide is not included, the phase reaction
term RAc!CO2 needs to be considered here in order to maintain the
correct mass of the liquid phase.
Rl!s :¼ RAc!MO ð24Þ
Rs!l :¼ RMO!l ð25Þ
Rl!g :¼ RAc!CH4 þ RAc!CO2 : ð26Þ
Phase transition terms are used in Eqs. (5), (9) and (11). According
to experimental data the variation of pH around 7.9 is very small
and hence pH inhibition can be neglected in this case. Although,
pH inhibition can be included for example by using inhibition fac-
tors according to Batstone et al. (2002).
The microorganisms grow on the plastic tower packing, and the
maximal mass of microorganisms depends on the size, shape and
the number of the plastic tower packing. Therefore, the inhibition
factor is introduced:
C sMO
IðC sMO ; C lAc Þ :¼ 1  ; ð27Þ
MOmax
where MOmax is a parameter depending on size, shape and total
number of the plastic tower packing. This inhibition factor will de-
crease growth and uptake for C sMO ! MOmax , which is the case when
the plastic tower packing is being overpopulated. In (27) MOmax cor-
responds to the maximal possible concentration of microorganisms
C sMO , hence, 0 6 C sMO < MOmax holds.
2.3. Computational methods
2.3.1. Model geometry, boundary and initial conditions
The inflow and outflow of the anaerobic filter are assumed to be
equally distributed along the top and bottom plate, respectively. A
two dimensional model with radius and height as coordinates was
used for all computations. As expected, the solution was actually
one dimensional. The usage of a 2D or 3D geometry is motivated
by the possibility to incorporate a non-equally distributed inflow
at the top plate and also to include information about the position
of the plastic tower packing, if available, in the computation. The
size of the model geometry was determined from experimental
data (cf. Section 2.1).
In order to cope with the fluid circulation, the velocity
1l
ql  n ¼ ð28Þ
1 hð0:12 mÞ2 p
1
is used in order to achieve a total influx of 1 l h at the top plate.
Hereby, n is the normal vector at the top plate of the reactor. Addi-
tionally, Dirichlet boundary conditions for acetate concentration
according to measured data from experiments are chosen at the
top plate. The pressure was set to a constant value while acetate
concentration was set to zero on the bottom plate. With these
boundary conditions it is possible to measure the outflow of the li-
5
quid and its acetate concentration in the model and compare these
values to experimental data (cf. Section 3.2). Normal flux was set to
zero for acetate and the liquid-phase on the lateral surface.
Linear initial conditions were used for xsMO ; / and xlAc . Addi-
tionally, a linear function was chosen for p to account for hydro-
static pressure.
2.3.2. Discretization and solver
In summa, the equations to be solved are (9)–(12) in conjunc-
tion with (5). All computations were performed using the software
tool UG (Lang and Wittum, 2005; Bastian et al., 2000). The discret-
ization in time was performed using a backward Euler method. For
the discretization in space, a finite volume scheme with linear ele-
ments was employed (Bank and Rose, 1987; Michev, 1996). Since
the system is nonlinear, Newton’s method was applied. Within
Newton’s method an algebraic multigrid solver was used to invert
the Jacobian. In total up to 331,000 degrees of freedom (DOF) were
used. Further information on solving nonlinear problems with a
high amount of DOF can be found in Ortega and Rheinboldt
(1987), Hackbusch (1985, 1992) and Deuflhard (2006).
2.3.3. Parameter estimation techniques
The fitness function f, which is defined below, can be split into
two parts. The first part, ~f , is a measure for the relative deviation of
experimental data compared to data derived by the model
~f ðkm;Ac ; Y Ac ; k ; K s ; MOmax ; fac;MO Þ
dec Ac
43  2
1 X
¼ AcExp Mod
out; i  Acout; i : ð29Þ
44 i¼0
Hereby, AcExp Mod
out is the total measured outflow of acetate and Acout is
the outflow of acetate computed by the model. The reaction param-
eters were estimated with respect to experiment a–d from Fig. 2 at
the same time, meaning that the first four experiments were com-
bined to one larger experiment with a total of 44 measurement
points and 84 d (each experiment had 11 measurement points
and lasted 21 d).
We remark that minimizing ~f leads to a very good fitting of
experimental data. Nevertheless, this is not a sufficient criterion
for correct parameter estimation; all considered variables need
to be observed very carefully in order to detect incorrect behav-
ior. Indeed, by minimizing ~f , one would observe a monotonically
increasing number of microorganisms from day 1 to day 84. How-
ever, this is not realistic because, if the reactor has already been
used for a large number of experiments (all experiments are sim-
ilar and last 21 d), an almost periodic behavior of the total mass
of microorganisms (with a periodicity of 21 d) should be ob-
served. In order to deal with this issue, the second part of
f ; D2MO , is defined:
Z
MOðtÞ ¼ C sMO ðt; xÞdx ð30Þ
1
MO ¼ ðMOð0Þ þ MOð42Þ þ MOð63ÞÞ ð31Þ
3
" 2  2  2 #
1 MOð0Þ MOð42Þ MOð63Þ
D2MO ¼ 1 þ 1 þ 1 ;
3 MO MO MO
ð32Þ
where MO(t) is the total mass of microorganisms at time t. The total
number of microorganisms is proportional to the total mass. In or-
der to account for the expected periodicity, the average number of
microorganisms, MO, is evaluated at three critical points of the
combined experiment (day 0, day 42, day 63). The computations
showed that a minimum of at least three critical points is needed
6 I. Muha et al. / Bioresource Technology 106 (2012) 1–9

a 10 b 10
outflow experiment outflow experiment
flow of acetate [kg/m³/h]

flow of acetate [kg/m³/h]

8 outflow model 8 outflow model
6 inflow inflow
6
4
4
2
2
0
0
-2
-4 -2
-6 -4
-8 -6
0 5 10 15 20 0 5 10 15 20
time [d] time [d]

c 10
outflow experiment
d 10
outflow experiment
flow of acetate [kg/m³/h]

flow of acetate [kg/m³/h]

8 outflow model 8 outflow model
inflow inflow
6 6
4 4
2 2
0 0
-2 -2
-4 -4
-6 -6
0 5 10 15 20 0 5 10 15 20
time [d] time [d]

e 12
outflow experiment
flow of acetate [kg/m³/h]

10 outflow model
8 inflow
6
4
2
0
-2
-4
-6
0 5 10 15 20
time [d]

Fig. 2. Comparison of model outflow of acetate with experimental data for the five considered model cases.

in order to obtain the periodic behavior. It was not necessary to use
all five possible critical points (day 0, day 21, day 42, day 63, day
84). The quantity D2MO is a measure of the relative change in the
mass of microorganisms at these three critical points. The fitness
function f is then chosen as a combination of ~f and D2MO :
f ðkm;Ac ; Y Ac ; kdec ; K sAc ; MOmax ; fac;MO Þ ¼ ~f þ D2MO ~f  103
¼ ð1 þ 103  D2MO Þ~f :
As ~f measures an absolute error and D2MO is a relative measure,
D2MO is rescaled in Eq. (33). This choice of f yields the expected peri-
odicity for the total mass of microorganisms (cf. Fig. 3b).
The function f is minimized by applying a gradient descent
method with upper and lower bounds for all reaction parameters
(cf. Nocedal and Wright, 2006).
3. Results and discussion
In this section, results are presented. In Section 3.1, the esti-
mated reaction parameters are reported. Additionally, a sensitivity
analysis with respect to these parameters is performed. Section 3.2
compares the model with experimental data. In Section 3.3, the
effectiveness of the reactor is discussed. In Section 3.4, the reaction
parameters are studied in detail while Section 3.5 investigates the
total amount of methane, which could be generated from the mea-
sured quantity of acids, and compares this amount with experi-
mental data.
Table 2 shows the model parameters which are known from the
outset. The density of the plastic tower packing, qsPTP , is chosen
ð33Þ according to the technical data sheet provided by the manufac-
turer. The density of microorganisms, qsMO , is computed by assum-
ing that a microorganism is of cylindrical shape with a length of
0:764  106 m, a diameter of 1  106 m and an average weight of
6:55  1016 kg. These values are taken from Garrity et al. (2001)
and experiments. The value for D is chosen as the diffusion coeffi-
cient from acetate in water multiplied with the unit tensor (Cuss-
ler, 1997).
For l the viscosity of water is used. Due to the chosen boundary
conditions the choice of K does not influence the computation. For
other boundary conditions, e.g., nonuniformly distributed inflow,
this would not be the case and K should be included in the param-
eter estimation. Furthermore, simplification to the mathematical
model are discussed in Section 3.6 and an outlook is presented in
Section 3.7.
 I. Muha et al. / Bioresource Technology 106 (2012) 1–9 7

3.1. Parameter estimation and sensitivity analysis

a 0.7

0.6 The fitness function f (cf. Eq. (33)) was minimized and the esti-
mated values for the reaction parameters are reported in Table 2.
0.5 The results of the sensitivity analysis are shown in Fig. 4. Appar-
Reactor height [m]

ently, the parameters fkm;Ac ; Y Ac ; kdec ; MOmax ; K SAc g have a strong

0.4 influence on the fitness function, since small changes of these
parameters cause a strong change in f. The parameter MOmax has
0.3 the highest sensitivity, fac;MO the lowest. Nevertheless, it is essential
that all reaction parameters are included in the model. On the
0.2 other hand the relative change in the fitness function caused by
> 80 % Pmax a change of fac;MO is very low. The reason for this behavior is that
0.1 > 50 % Pmax fac;MO is at its upper bound. A further increase of fac;MO would de-
> 30 % Pmax stroy mass conservation.
0.0
t = 2d t = 12d t = 20d 3.2. Comparison of model and experiment

1.26 This section investigates five experiments, each of which lasted

b 1.920
21 d. The inflow of acetate at the top plate of the reactor was mea-
15

1.25 1.910
number of MO in 10

sured and implemented in the model. The outflow was then com-
mass of MO [kg]

1.900 puted and compared to experimental data. The results are shown
1.24 in Fig. 2. The reaction parameters fkm;Ac ; Y Ac ; K sAc ; kdec ; fac;MO ;
1.890
1.880 MOmax g were estimated with respect to four experiments
1.23
(Fig. 2a–d) simultaneously. The model predicts accurately the out-
1.870
flow of acetate in these four experiments.
1.22 1.860 Although the reaction parameters were not estimated with re-
1.850 spect to experiment e shown in Fig. 2, the model is capable of pre-
1.21
0 5 10 15 20 dicting very accurately the outflow of acetate with the same set of
time [d] parameters. This test proves that the parameters used are frame
independent and that the model is sound in this respect, i.e., the
Fig. 3. (a) Local methane production P CH4 compared to P max for different times; (b) same set of parameters can be used for simulations of similar
evolution of microorganisms mass according to experiment 4 (cf. Fig. 2d). experiments.

3.3. Effectiveness of the reactor

Table 2 Fig. 3 shows the local methane production P CH4 ðt; xÞ. In an effec-
Fixed model parameters and reaction parameters estimated by minimizing the fitness tive reactor, the local CH4 production should everywhere be equal
function according to Section 2.3.3. to its maximum leading to a constant PCH4 ðt; xÞ in space. Fig. 3a
Fixed paramter Value Unit Est. parameter Value Unit shows that in the beginning (t < 2 d) most of the methane is pro-
qsMO 1090 kg km;Ac 1 duced in the upper part of the reactor and, therefore, the lower part
m3
1:54  102 h
qsPTP 950 kg Y Ac 1
of the reactor is not used effectively. At day 12 (Fig. 3a, t ¼ 12 d)
1:88  101
m3
PCH4 ðt; xÞ is almost constant. The whole reactor is used for methane
q l
Ac
1050 kg K sAc 2:00  100 kg
m3 m3
1
production and is thus working effectively. At the end of the exper-
q l 1000 kg kdec 4:16  104
H2 O m3 h
iment (Fig. 3a, t ¼ 20 d) the lower part of the reactor is again not
D 1:210  109  1 m2 fac;MO 1:00  100 1
m
s working effectively. Fig. 2 shows that the inflow of acetate is very
g ð0; 9:806Þ MOmax 5:47  101 kg
s2 m3 small at the beginning and at the end of each experiment. In this
case most of the acetate is consumed in the upper part of the reac-
tor leading to a shortfall of acetate in the lower part of the reactor.
Such a shortfall leads to a noneffective reactor. On the other hand,
if acetate inflow is large enough ð> 4 kg=m3 =hÞ, acetate will reach
100 the lower part of the reactor and will be consumed there. In this
case methane production is equally distributed within the reactor,
rel. change in f [%]

80
and the reactor is working effectively.
60 As it can be seen in Fig. 3 the lower part of the reactor is not
used very effectively most of the time. In order to optimize meth-
40 ane production the lower part of the reactor needs to increase its
methane production. This can be achieved by improving environ-
20 mental conditions for microorganisms, e.g., by using better filling
material in the lower part.
0
-30 -20 -10 0 10 20 30
rel. variation of parameter [%] 3.4. Reaction parameters
k m,Ac k dec MOMAX
YAc Ks f ac,MO
The reaction parameters can be divided into two different
Ac
groups. The first group consists of fkm;Ac ; Y Ac ; kdec g. These parame-
Fig. 4. Relative change in the fitness function f depending on the relative variation ters influence the outflow of acetate during the whole experiment.
of reaction parameters. This means that changing any of these parameters will change ace-
8 I. Muha et al. / Bioresource Technology 106 (2012) 1–9

tate outflow in all time intervals. On the other hand, the parame-
ters fK sAc ; MOmax g influence acetate outflow only under certain
circumstances.
Remark 3.1. For small concentrations of acetate ðC lAc  K sAc Þ the
following holds:
order to study methane formation in detail, further experimental
data about organic substances in the inflowing and outflowing li-
quid of the anaerobic filter need to be measured and included into
the mathematical model.
3.6. Remarks about simplifications of the model

C lAc This section deals with simplification to the mathematical mod-

 1: ð34Þ
K sAc þ C lAc el concerning local concentrations of carbon dioxide and methane.
The determination of the amount of carbon dioxide present in
the filter should be studied in conjunction with the variation of
Remark 3.2. For a large population of microorganisms pH, which, in turn, necessitates solving a set of algebraic equations
ðC sMO  MOmax Þ the following holds: coupled with the partial differential equations describing balance
laws. On the other hand, it can be observed that the pH in the
C sMO experiments fluctuates slightly about the mean value of 7.9. This
1  1: ð35Þ
MOmax observation can be used in order to drop the algebraic equations
Fig. 3b shows the total mass of microorganisms within the determining the value of pH, and disregard the balance laws asso-
anaerobic filter. For time t 2 [10 d, 15 d] the mass reaches a maxi- ciated with carbon dioxide. Notwithstanding, the reaction terms by
mum. Within this time interval, the influence of MOmax on acetate which carbon dioxide is produced are retained so that the global
outflow is maximal. If MOmax is decreased the population maxi- balance of mass of the filter is not violated.
mum will be lower and the consumption of acetate will decrease. Furthermore, it is more interesting to determine the net pro-
Hence, the outflow of acetate will increase within this time duction of methane rather than studying its motion through the fil-
interval. ter. The desired information can be gained entirely through the
definition of the reaction terms that describe the production of
Fig. 2d shows that the total inflow of acetate is very low for
gas at the expenses of the liquid phase, provided these terms are
t > 18 d. In this case, the parameter K sAc influences acetate outflow.
made independent of the methane concentration in the filter. In
Increasing K sAc will inhibit uptake of acetate and, therefore, in-
this respect, considering an equation for the flow of methane
crease the outflow of acetate.
would not add any useful knowledge to the mathematical model.
By considering Eq. (23), the doubling time td and the maximal
This, in general, does not authorize to eliminate such an equation,
specific growth rate of the microorganisms, lmax , can be computed
because high concentrations of methane (which forms bubbles in
as follows:
the filter) may influence the flow of the liquid phase and the trans-
lmax ¼ km;Ac Y Ac  kdec ¼ 2:48  103 h1 ¼ 5:95  102 d1 ð36Þ port of acetate, which, in turn, affect the production of methane it-
self. A considerable simplification can be achieved by assuming
lnð2Þ that the total volume of the gas bubbles is small enough as com-
td ¼ ¼ 11:649 d: ð37Þ pared to the volume of liquid and solid, and the motion of the
lmax
1 1
gas does not have appreciable influence on liquid flow. These
Additionally, kdec ¼ 4:16  104 h ¼ 0:009984 d was found to be hypotheses, although being quite strong in general, seem to have
the optimal value to minimize the fitness function f. These values no dramatic consequences on the final results, which are in good
are according to literature Stams et al. (2003) and Conklin et al. agreement with experimental observations (cf. Fig. 2).
(2005).

3.5. Distribution of anaerobic digestion phases to reactor stages 3.7. Outlook

In Section 2.1 the biogas reactor was described as a two-phase
anaerobic-digester. The first stage is the hydrolysis reactor and
the second stage is the anaerobic filter. The anaerobic digestion
consists of five different phases. The first phase (hydrolysis) takes
place in the hydrolysis reactor. The third and forth phase (aceto-
genesis and methanogenesis) mainly take place in the anaerobic
filter. In order to find out where the acidogenesis takes place, the
total potential of methane formation from the measured organic
acids has to be considered and compared to the methane formation
from the experiments. In Table 3 the total methane formation po-
tential from organic acids within the anaerobic filter is in average
only about 61% of the measured methane. This means that a large
fraction of acidogenesis has to take place in the anaerobic filter. In
Table 3
Comparison of methane formation potential from inflowing organic acids and
measured methane at 0  C and 1:0133  105 Pa.
Experiment number Methane potential Measured methane
1 481 L 746 L qgCH4 is the density of methane and qgCO2 is the density of CO2. The
2 372 L 770 L densities qgCH4 and qgCO2 depend on the ambient pressure pg , the tem-
3 487 L 757 L
4 512 L 745 L
In the mathematical model the solid and liquid phase are con-
sidered as separate phases leading to information about local con-
centration of solids (plastic tower packing and microorganisms)
and liquids (water and acetate). Gases are only considered by
means of production rates. Therefore, no information about local
concentration of gases can be extracted from the model. To include
local concentration of gases into the model, a third phase needs to
be introduced. This is typically performed by dividing the pore
space into a liquid part with a volume fraction Sl and a gas part
with a volume fraction Sg :¼ 1  Sl . The gas phase then has a sepa-
rate pressure pg . Let the gas phase P g be defined as
P g :¼ fCH4 ; CO2 g: ð38Þ
g
The mass fraction of methane is denoted by x and the mass frac-
CH4
tion of carbon dioxide within the gas phase by xgCO2 . The apparent
mass of the gas phase qg is then given by
qg ¼ qgCH4 xgCH4 þ ð1  xgCH4 ÞqgCO2 : ð39Þ
perature and the volume fraction Sg . The new set of equations then
includes the mass fraction of methane.
 I. Muha et al. / Bioresource Technology 106 (2012) 1–9 9

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¼ RAc!MO  RMO!l ð41Þ composition on the methane yield. Agriculture, Ecosystems and Environment
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@t Bastian, P., Birken, K., Johannsen, K., Lang, S., Reichenberger, V., Wieners, C., Wittum,
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 RAc!MO  RAc!CH4  RAc!CO2 ð43Þ Batstone, D., Keller, J., Angelidaki, I., Kalyuzhnyi, S., Pavlostathis, S., Rozzi, A.,
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size, shape and number of plastic tower packing. The sensitivity Journal of Pharmaceutics and Biopharmaceutics 68 (2), 368–379.
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The computed acetate outflow was compared with experimental Several Variables (Classics in Applied Mathematics). Society for Industrial
data and it was shown that the model is frame independent and, Mathematics.
Stams, A.J.M., Elferink, S.J.W.H., Westermann, P., 2003. Metabolic interactions
therefore, can be applied with the same set of parameters to sim-
between methanogenic consortia and anaerobic respiring Bacteria. Advances in
ilar problems. By using information about the local production of Biochemical Engineering/Biotechnology 81, 31–56.
methane, the effectivity of the reactor EffðtÞ is obtained. The Thamsiriroj, T., Murphy, J., 2011. Modelling mono-digestion of grass silage in a 2-
knowledge of EffðtÞ can be used to improve the biogas reactor. stage CSTR anaerobic digester using ADM1. Bioresource Technology 102 (2),
948–959.
Wett, B., Schoen, M., Phothilangka, P., Wackerle, F., Insam, H., 2007. Model-based
Acknowledgements design of an agricultural biogas plant: application of Anaerobic Digestion Model
No. 1 for an improved four chamber scheme. Water Science and Technology 55
(10), 21–28.
This research was supported by the German Ministry for Educa- Wichern, M., Gehring, T., Fischer, K., Andrade, D., Lübken, M., Koch, K., Gronauer, A.,
tion and Research (BMBF) under Contract No. 03SF0349D. Horn, H., 2009. Monofermentation of grass silage under mesophilic conditions:
measurements and mathematical modeling with ADM1. Bioresource
Technology 100, 1675–1681.
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