Bornhoft (2013) Steady-State Analysis of The Anaerobic Digestion Model No 1

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Nonlinear Dyn (2013) 73:535–549

DOI 10.1007/s11071-013-0807-x

O R I G I N A L PA P E R

Steady-state analysis of the Anaerobic Digestion Model


No. 1 (ADM1)
Astrid Bornhöft · Richard Hanke-Rauschenbach ·
Kai Sundmacher

Received: 11 July 2012 / Accepted: 30 January 2013 / Published online: 12 February 2013
© Springer Science+Business Media Dordrecht 2013

Abstract The steady-state behavior of the Anaerobic Keywords ADM1 · Anaerobic digestion ·
Digestion Model No. 1 (ADM1) with respect to di- Steady-state multiplicity · Bifurcation · Biogas
lution rate and substrate concentration is analyzed in production
this study. Thereby, up to ten coexisting steady-state
solutions are observed under the same operating con-
ditions. The parameter region of a methane produc- 1 Introduction
ing operation is limited regarding high dilution rates
as well as low or high substrate concentrations. The
Anaerobic digestion of organic matter for biogas pro-
underlying mechanisms causing those limits are inves- duction is a promising future direction for renewable
tigated in detail, and the common core is identified, energy supply, since the biogas can be used in power
namely a positive feedback loop between growth of plants or fuel cells and can substitute fossil fuels. The
acetate degraders and acetate itself. The difference lies anaerobic conversion of organic waste or energy crops
in the activation mechanisms of this feedback loop, is a complex degradation process, which is performed
which differs in the three investigated cases. by numerous microbial species. Klocke et al. [10] for
The comparison of the present results with lit- instance found at least 60 different species in a biogas
erature studies of simpler two-step models reveals reactor fed with fodder beet silage. The different mi-
qualitative differences regarding the substrate concen- croorganisms interact as a community, which makes
tration. Therefore, an alternative simplified model is the process complex and hard to predict.
suggested, which shows qualitatively the same bifur- An important step toward understanding the pro-
cation behavior as the ADM1 considering variation of cess and the operational behavior of a biogas plant
the substrate concentration. is a reliable model. Several models describing this
process can be found in literature [17]. In 2002, the
Anaerobic Digestion Model No. 1 (ADM1) was devel-
A. Bornhöft · K. Sundmacher oped by the IWA task group for mathematical mod-
Process Systems Engineering, Otto-von-Guericke
University Magdeburg, Universitätsplatz 2, 39106 elling of anaerobic digestion processes to harmonize
Magdeburg, Germany the large number of slightly different models describ-
ing anaerobic digestion [2]. ADM1 has been success-
R. Hanke-Rauschenbach () · K. Sundmacher
fully used in several studies (see, e.g., review of Bat-
Max Planck Institute for Dynamics of Complex Technical
Systems, Sandtorstr. 1, 39106 Magdeburg, Germany stone et al. [3]), and has been applied to different reac-
e-mail: hanke-rauschenbach@mpi-magdeburg.mpg.de tor configurations, e.g., [5]. Furthermore, it has been
536 A. Bornhöft et al.

extended to include inorganic phosphorus [9] or sul- anisms. The summary, Sect. 4, contains the findings
phur [8]. The applicability not only to waste water pro- and conclusions of the whole presented study.
cessing but also to agricultural waste processing and
energy crop processing has been demonstrated, e.g.,
by Koch et al. [11]. 2 Model structure of ADM1
It is well known that bioreactors in general show a
strongly nonlinear operating behavior, such as steady- A detailed description of ADM1 can be found in the
state multiplicity, e.g., [1, 16, 19, 20]. For feed flow original work of Batstone et al. [2]. The model equa-
rates below a certain value at least two qualitative dif- tions are not repeated here. Instead, the main structure
ferent steady-states exist for the same operating con- of the model and the essential equations are introduced
dition, namely on the one hand the desired operating in this section as the basis for the present study.
state and on the other hand a washout state without any The anaerobic digestion process is usually per-
microbial biomass present. This washout state is un- formed in bioreactors of different variety. Figure 1
desired, since without any microbes in the reactor the shows a typical sketch of a simple biogas plant. In the
product is not formed anymore. It is common knowl- reactor, the substrate (i.e., organic waste) is biochem-
edge that by increasing the feed flow rate above a cer- ically degraded into biogas and digestate as a byprod-
tain point only the washout solution exists. Also, in a uct. Two different phases are present in the reactor,
biogas production system, such behavior is expected namely a liquid and a gas phase. Both phases are sepa-
and observed in technical applications. rately described in ADM1. In the liquid phase, the bio-
ADM1 is primarily formulated to describe the de- chemical degradation process takes place; in the gas
sired operating state. Nevertheless, it is based on the phase the biogas accumulates without any further re-
essential biochemical processes of the degradation, action.
which means that it probably shows steady-state mul-
tiplicity, also. The knowledge about the nonlinear dy- 2.1 General structure
namics of the model is important in two aspects. First,
for the numerical use of the model, it is important to
In ADM1, spatially lumped material balances were
know which one of the possible solutions is result-
formulated for the liquid as well as for the gas phase.
ing from the current set of input variables and initial
The liquid phase contains: (a) the particulate compo-
conditions. This information also helps the user to as-
nents, (b) the soluble components, and (c) the micro-
sess the results of simulations. A second aspect is to
bial species. The gas phase contains all gaseous com-
gain insight into the details of the degradation process,
ponents. The structure of the different material bal-
like interactions of some metabolites. That can be sub-
ances is similar; it is illustrated here using the balance
sequently applied to operation and control of biogas
equation of a soluble component in the liquid phase.
plants. However, to our knowledge, the nonlinear be-
havior of ADM1 has not been analyzed so far. Only dSi
the analysis of simpler two-step models describing the Vliq = q(Si,in − Si ) + Vliq σi + Vliq σT,i (1)
dt
essential parts of the process can be found in the lit-
erature [14–16, 18]. These findings are discussed in
Sect. 3.3 in more detail.
The overall goal of the article is the detailed anal-
ysis of ADM1 with respect to the steady-state mul-
tiplicity. In the following section, the model ADM1
is briefly summarized. In Sect. 3, the results of the
steady-state analysis are presented and discussed in
detail. Based on the findings from the bifurcation anal-
ysis the interactions leading to a washout state are
explained. A comparison with the obtained literature
analysis is presented and in the last part a new simpli-
fied model is proposed including the discussed mech- Fig. 1 Process sketch of a biogas reactor
Steady-state analysis of the Anaerobic Digestion Model No. 1 (ADM1) 537

The first term represents the accumulation of the kinetics under inclusion of inhibition factors. All bio-
balanced component Si and the second term describes chemical reaction rates ρj have the following general
the inflows and outflow. The last two terms are sink structure:
and source terms of the biochemical reactions and the
Ssub
liquid-gas mass transfer, respectively. They are com- ρj = km,j Xdeg Ij (6)
KS,j + Ssub
puted from stoichiometric factors νi,j using kinetic
equations for the reaction rates ρj of the correspond- where Ssub represents the concentration of the de-
ing processes. graded substrate of the process j , Xdeg the concentra-
 tion of the corresponding degrading microbial species
σi = νi,j ρj (2) and km,j and KS,j are kinetic parameters. Ij is repre-
senting an inhibition factor. In ADM1 several inhibi-
The microbial species, mentioned above, are group-
tion mechanisms were considered, namely pH, ammo-
ed with respect to their substrate. For example all ac-
nium and hydrogen inhibition and furthermore nitro-
etate degraders are described by one state variable and gen limitation. For example, the empirical term of the
were computed from one material balance. The corre- pH inhibition has the following structure:
sponding stoichiometric coefficients νi,j are averaged
over the different microbial species and set constant. 1 + 2 · 100.5(pHLL,j −pHUL,j )
This means that the metabolism of the microbial com- IpH,j = (7)
1 + 10(pH−pHLL,j ) + 10(pHLL,j −pH)
munity is assumed not to change during the simula-
tion. where pH is the actual pH value and pHUL,j and
The material balances for the acids and bases were pHLL,j are the limits of the inhibition of process j .
not solved dynamically since the acid base reactions Above the upper limit the process is not inhibited, be-
are fast in comparison to the biochemical reactions. low the lower limit the process is completely inhibited.
For the involved components a stoichiometric equa- For the transfer between the liquid and the gas
tion for acids Si,acid , bases/acid residues Si,base , and phase, a first-order kinetics with respect to Henry’s law
total concentration of a component Si is formulated. is considered.

0 = Si − Si,acid − Si,base (3) 2.3 Parameters and input variables

The equilibrium between acids and bases is as- ADM1 contains a large number of parameters. In this
sumed to be established instantaneously. It is de- study, the original parameter values for the mesophilic
scribed by the following mass action law: case suggested by Batstone et al. [2] were used.
Various values can be chosen as input variables of
Si,base · SH+
0 = Kacid − (4) ADM1. In the presented analysis the dilution rate D
Si,acid
(in 1/d) was considered first. It is defined by the vol-
where Kacid is the equilibrium constant and SH+ is the umetric flow rate q (in m3 /d) scaled by the volume of
concentration of protons. This is computed from an the liquid phase Vliq (cf. Eq. (1)).
overall charge balance (Eq. (5)) and used to determine q
the pH value. D= (8)
Vliq
 
0= Si+ − Si− (5) The inlet substrate concentration was selected as
the second input variable. In real applications, the re-
2.2 Kinetics actor inlet contains the substrate in different degraded
states, e.g., acetic acid. But the composition of the inlet
The reaction rates ρj in Eq. (2) are defined by kinetic cannot be chosen arbitrarily. Therefore, in this whole
equations. For the disintegration, hydrolysis, and de- study, it was assumed that the fermentation does not
cay of microbial biomass, one assumes a first-order ki- start before the material enters the reactor and the inlet
netics in ADM1. The microbial degradation processes consists only of a fixed substrate mixture, called com-
of the soluble components were modeled with Monod posite with the concentration, XC,in . The composition
538 A. Bornhöft et al.

is fixed by the stoichiometric factors of the first degra-


dation step and is selected due to the suggested param-
eters in Batstone et al. [2] as follows: 20 % carbohy-
drates, 20 % proteins, 25 % lipids, and 35 % inerts.
The nitrogen content is 0.002 kmole/kgCOD (chemi-
cal oxygen demand). All other components of the feed,
like inorganic nitrogen and carbon as well as cations
and anions, are assumed to be zero, also.
In summary, the ADM1 system is a differential-
algebraic equation system with 44 state variables. 29
variables are of dynamic nature, and 15 variables are
algebraic states.

2.4 Numerical solution

Due to its complexity, the present analysis of this


model was performed numerically using MATLAB
(MathWorks) and the parameter continuation tool
MatCont. MatCont uses a prediction-correction con-
tinuation algorithm based on the Moore–Penrose ma-
trix pseudoinverse. The mathematical background and
the full range of functions of MatCont can be found in
Dhooge et al. [6].
Since MatCont handles ordinary differential equa-
tion systems, the algebraic part of ADM1 was solved
simultaneously by the MATLAB function fsolve, us-
ing a Newton-method with a trust-region dogleg algo-
rithm.

3 Results and discussion

3.1 Results of bifurcation analyses

Here, the steady-state behavior of ADM1 is discussed,


beginning with two one-parameter bifurcation analy- Fig. 2 Bifurcation diagram with respect to dilution
rate and constant substrate inlet concentration XC,in =
ses. These are done with respect to both input vari- 50 kgCOD/m3 (LP = limit point; BP = branch point).
ables, namely the dilution rate and the substrate inlet (a) Specific methane flow rate GCH4 [mol/d/m3 ].
concentration. After that, they are set into a common (b) Total microbial biomass Xt [kgCOD/m3 ]. (c) Dif-
context by a parameter chart, which is important for ferent branches with marks which microbial species is
present (su = sugar degraders; aa = amino acid degraders;
the operation of a biogas plant. fa = fatty acid degraders; c4 = valerate and butyrate de-
graders; pro = propionate degraders; ac = acetate degraders;
3.1.1 Influence of dilution rate h2 = hydrogen degraders)

First, the influence of the dilution rate, D, is studied


in detail. Figure 2 shows the steady-state solutions of effects in one plot. Solid lines represent stable solu-
ADM1 depending on the dilution rate with fixed sub- tions and dashed lines unstable solutions. Those solu-
strate concentration at the inlet, XC,in . The abscissa tion branches that are not physically meaningful due
(i.e., dilution rate) has a logarithmic scale to show all to negative concentrations are not presented in the di-
Steady-state analysis of the Anaerobic Digestion Model No. 1 (ADM1) 539

agrams. In detail, Fig. 2(a) shows the influence of the In summary, the analysis reveals ten different solu-
dilution rate, D, on the gas flow rate of methane scaled tion branches. Out of these ten, only branch I is de-
by the volume of the liquid, GCH4 (in mol/d/m3 ). It is sired, since most methane is produced and it is stable.
defined as follows: It might come as a surprise that several neighboring
branches are unstable. But this is caused by skipping
qgas RT xCH4
GCH4 = (9) solution branches with negative concentrations and as
Vliq well by the specific projection that was selected here
for the presentation of the results.
where qgas is the biogas flow rate and xCH4 the molar
fraction of methane in the gas phase. 3.1.2 Influence of substrate concentration of the inlet
It can be seen from Fig. 2(a) that two solution
branches with a significant methane production rate In the second part of the analysis, the substrate concen-
exist. Branch I is stable and hence desired for the op- tration of the inlet is varied. In Fig. 3, the steady-state
eration of a biogas plant, while branch II is unstable. solutions are presented for a fixed dilution rate, D.
Several further branches were detected, but in these Figure 3(a) shows again the specific methane flow rate,
cases only a small amount of methane or even no GCH4 , and (b) the total microbial biomass concentra-
methane at all is produced (Fig. 2(a)). These branches tion, Xt . The labeling of the branches corresponds to
also differ in other state variables like the microbial the one used in Fig. 2.
species that are present (see Fig. 2(b)). This figure Many of the branches discussed before appear in
shows the concentration of the total microbial biomass Fig. 3 as well. In general, it can be seen that rising sub-
Xt (in kgCOD/m3 ). It is the sum of the concentrations strate inlet concentrations lead to higher biomass con-
of the different microbial species in the liquid phase centrations (branches III, IV, VI, and VII in Fig. 3(b)).
of the reactor. Additionally, the single branches are
shown in Fig. 2(c) with their range of validity and the
specific microbial species that are present at these so-
lutions.
Only at branches I and II all microbial species
are existing in the reactor (Fig. 2(c)), especially the
methane producing acetate degraders (ac) and hydro-
gen degraders (h2) are present. This can be concluded
from Fig. 2(a), also. Between branch I and II, the sys-
tem undergoes a stability change. This is marked as a
limit point (LP) and is typically called a saddle-node
bifurcation. Branch III is a further stable solution, as
only sugar degraders (su) and amino acid degraders
(aa) are present (Fig. 2(c)). The branch ends at a dilu-
tion rate point, where the sugar degraders are washed
out. There is a branch point (BP), also known as tran-
scritical bifurcation, with branch IV.
At branch IV, only the amino acid degraders ex-
ist and for lower dilution rates it is unstable. Four
further branches (VI–IX) intersect with branch IV.
They are characterized by individual sets of micro-
bial species and they are all unstable. For high dilution
rates, branch IV becomes stable and ends in a limit
point, where the unstable branch V arises. Addition- Fig. 3 Bifurcation diagram with respect to substrate in-
let concentration and constant dilution rate D = 0.15 1/d
ally, branch X exist for all dilution rates, and there are
(LP = limit point). (a) Specific methane flow rate GCH4
no microbial species present. The branch is stable, in [mol/d/m3 ]. (b) Total microbial biomass concentration Xt
contrast to other simpler models. [kgCOD/m3 ]
540 A. Bornhöft et al.

Again, branch I is desired, since it is stable and the


only one with methane production (Fig. 3(a)). The
branch ends at limit points for high and low substrate
inlet concentrations, which means it is only valid in a
limited range of operating conditions. If the substrate
concentration is chosen too low, the desired solution is
not existent and independent of the initial conditions
no methane can be produced. Also, for high substrate
concentrations, the reactor cannot be operated effec-
tively.

3.1.3 Influence of both input parameters

From the one-parameter bifurcation analyses, shown


above, it was deduced that branch I is the desired solu-
tion with regard to operating issues. In Fig. 2, it can be
seen that branch I ends at a critical dilution rate. The
value of this dilution rate depends also on the substrate
concentration, which can be seen in Fig. 3. This inter-
dependency between the washout limit of the dilution
rate and the substrate concentration was further ana-
lyzed. Figure 4(a) shows this critical dilution rate as
a function of the substrate inlet concentration (solid Fig. 4 Critical dilution rate as a function of the substrate inlet
black line). concentration. (a) For two different parameter sets. Black: [2]
The horizontal cut in the diagram (red dashed line) and grey: [5]. Red lines indicate the correspondence to one-pa-
represents the correspondence to the bifurcation anal- rameter diagrams Figs. 2 and 3. (b) Black: Critical dilution rate
computed with ADM1. Grey: Organic load rate isolines. The
ysis with respect to the substrate inlet concentration differences are indicated by hatched areas
in Fig. 3; at the two intersection points of the black
and the red lines the set of input variables of the limit
points in Fig. 3 can be seen. Furthermore, in the mid- lower one, a desired operation of the plant is possi-
dle part of the figure, the desired solution is present, ble and methane can be produced. In the upper region,
meanwhile left and right of the black limit curve no no methanogenic biomass can be present in a steady-
methane can be produced. Correspondingly, the ver- state. This aspect can be followed best by comparing
tical red line shows the connection of the diagram to the cuts in Fig. 4(a) with the one-parameter bifurcation
the one-parameter bifurcation analysis with respect to diagrams in Figs. 2 and 3 as discussed before.
the dilution rate shown in Fig. 2. In Fig. 4(a), the in- This result can be compared with the commonly
tersection point of the vertical red line and the shown used measure for an operating state, the organic load-
black boundary corresponds to the critical dilution rate ing rate (OLR) (e.g. [12]). Figure 4(b) shows, addi-
shown in Fig. 2. tionally to the discussed results, curves of constant
The grey curve in Fig. 4(a) shows the dependency OLR in grey. In general, a maximal value for the OLR
of the critical dilution rate on the substrate inlet con- is determined experimentally, such that the reactor can
centration computed with another parameter set for be operated safely. Depending on the operation point,
ADM1, given by Blumensaat and Keller [5] for the where this maximal OLR is determined, this rule leads
mesophilic case. For both sets of parameter, the shape to other results than the simulations of ADM1 shows.
of the curves is qualitatively the same. That means the That is illustrated in Fig. 4(b) exemplary for the or-
shape is worthwhile to analyze since it is not a special ganic loading rate of 30 kgCOD/m3 /d. It can be seen
case of the first parameter set. that the rule of a maximal OLR is invalid for small
The curve shown in Fig. 4(a) divides the space of inlet substrate concentrations and for larger substrate
possible operating conditions into two areas. In the inlet concentrations it is too conservative.
Steady-state analysis of the Anaerobic Digestion Model No. 1 (ADM1) 541

3.2 Discussion of limiting mechanisms degraders. This results in a positive feedback on the
acetate (Fig. 5(a)) and even more acetic acid is present
In the first part of the present analysis, the stationary in the system. Therefore, the inhibition of the acetate
behavior with respect to the operating parameter were degraders is strengthened by itself, and leads to the
shown. It was found that branch I in the one-parameter washout of the acetate degraders.
analyses is the most important solution branch for the To support the described argumentation of the
operation of a biogas plant. This valid solution ends in washout mechanism 1, the bifurcation analysis of the
three qualitatively different limit points in Fig. 2 and desired operating branch I is performed for a modified
Fig. 3. The resulting question is about the mechanisms formulation of ADM1, where the pH is artificially set
which cause these limits in ADM1. For each limit to a constant value, so that the interaction chain is cut
point, a hypothesis regarding the underlying mecha- off (Fig. 5(a)) and the feedback loop does not exist
nisms is formulated and validated by simulations. anymore. Figures 5(b) and (c) shows the steady-states
of the acetate and acetate degrader concentration of the
Mechanism 1: Washout due to increase of dilution rate original and modified formulation. Due to clarity only
In this first case, the washout by exceeding a critical the desired branches I and II are displayed in the fig-
dilution rate, as seen in Fig. 2, is analyzed. The un- ure. The results of the original formulation are shown
derlying mechanism is a well-known interaction chain, in black and the results of the modified formulation
which is illustrated in Fig. 5(a). An increased dilution in red (branch I ). It can be seen that the acetate ac-
rate leads to a higher acetic acid concentration in the cumulates for increasing dilution rates in both cases.
liquid phase of the reactor due to a lower residence Branch I (original formulation) ends abruptly in a limit
time of the substrate. The accumulation of acetic acid point, if the acetate concentration rises. In contrast to
is directly connected to a lower pH, which causes in that, at branch I (modified formulation) the acetate
ADM1 an inhibition of the growth rate of the acetate concentration increases with increasing dilution rates,
until the acetate degraders are washed out naturally
(see Fig. 5(c)). That means that without the feedback
loop no limit point would occur and the shown interac-
tion chain for this case is confirmed by the simulation
results.
The discussed mechanism is commonly known as
substrate inhibition and often modeled with a special
kinetic equation, e.g., a Haldane kinetics. However, in
ADM1, it is taken into account through the pH inhibi-
tion factor of the acetate uptake rate.

Mechanism 2: Washout due to increase of substrate


inlet concentration The second mechanism corre-
sponds to an increase of the substrate concentration
of the inlet over a critical limit. It is connected to the
upper limit point in Fig. 3. The analysis and argumen-
tation is done in analogy to mechanism 1. The corre-
sponding interaction chain for this case is illustrated in
Fig. 6(a).
In simple models with Monod type kinetics, the
Fig. 5 (a) Interaction chain of dilution rate on washout of substrate concentration within the reactor is not de-
acetate degraders. (b) (c) Bifurcation diagram with respect pending on the inlet concentration; this is shown in the
to dilution rate and constant substrate inlet concentration Appendix. In contrast to that, in the case of ADM1, an
XC,in = 50 kgCOD/m3 for the original formulation (black) and
increased substrate concentration leads to accumula-
the modified formulation with constant pH (red). (b) Acetate
concentration Sac [kgCOD/m3 ]. (c) Concentration of acetate de- tion of ammonia, because this is a byproduct of the
graders Xdac [kgCOD/m3 ] degradation of amino acids, and it is not defined as
542 A. Bornhöft et al.

Fig. 6 (a) Interaction chain of increase of substrate concentra- Fig. 7 (a) Interaction chain of decrease of substrate concen-
tion on washout of acetate degraders. (b) (c) Bifurcation dia- tration on washout of acetate degraders. (b) (c) Bifurcation di-
gram with respect to substrate inlet concentration and constant agram with respect to substrate inlet concentration and con-
dilution rate D = 0.15 1/d for the original formulation (black) stant dilution rate D = 0.15 1/d for the original formulation
and the modified formulation without ammonia inhibition (red). (black) and the modified formulation with constant inorganic
(b) Acetate concentration Sac [kgCOD/m3 ]. (c) Concentration nitrogen and carbon concentration (red). (b) Acetate concentra-
of acetate degraders Xdac [kgCOD/m3 ] tion Sac [kgCOD/m3 ]. (c) Concentration of acetate degraders
Xdac [kgCOD/m3 ]

a substrate in a subsequential degradation step. Other


intermediate products, like acetate, are directly con- Branch I for the modified formulation shows no de-
nected to the Monod type kinetics, thus they are only pendency on increasing substrate concentrations and,
indirectly influenced by the substrate inlet concentra- therefore, the branch does not lead to washout of the
tion. The increase of ammonia leads to the inhibi- acetate degraders. It can be seen in Fig. 6(c), too,
tion of the growth of acetate degraders, and conse- that the increased substrate concentration has no in-
quently, the positive feedback loop, as discussed be- fluence and the microbial biomass is further increas-
fore in mechanism 1, is activated (Fig. 6(a)). Reduced ing.
acetate degradation and a drop of the pH is the result. Another aspect of Fig. 6 is the behavior for low sub-
That reduces the growth rate of the acetate degraders strate inlet concentrations. Both models, the original
even more by the pH inhibition, and finally leads to the and the modified one, have no desired solution branch
washout of the acetate degraders. for low substrate concentrations. This means that an-
To validate the stated hypothesis for mechanism 2, other mechanism comes into play in this case. This is
the model is modified by disabling the ammonia inhi- discussed in the next paragraph.
bition of the acetate degraders. In this modified formu-
lation, the increase of substrate concentration should Mechanism 3: Washout due to decrease of substrate
not have any influence on the acetate degrader, if the inlet concentration The last mechanism, discussed
suggested interaction chain is right. Again, Fig. 6(b) here, is a case where the washout is caused by a de-
shows the acetate concentration and (c) the concen- creased substrate concentration below a critical limit.
tration of acetate degraders for the original and mod- This mechanism 3 corresponds to the lower limit point
ified formulation. It can be seen that for the origi- in Fig. 3. The relevant interaction chain of mechanism
nal formulation the acetate concentration is increasing 3 is shown in Fig. 7(a). Here, a lower substrate con-
with increasing substrate concentrations (branch I). centration results in the depletion of the intermediates
Steady-state analysis of the Anaerobic Digestion Model No. 1 (ADM1) 543

inorganic nitrogen and carbon in the reactor. Thereby, 3.3 Comparison with literature
the influence of ammonia comes into account first (not
shown here). Consequently, the pH decreases and this To assess the results of the shown analysis, they are
activates again the positive feedback loop, already dis- compared with bifurcation analyses from the litera-
cussed in mechanisms 1 and 2. The growth of the ture. So far, only a few authors focused on the non-
acetate degraders is inhibited and the acetic acid ac- linear behavior of anaerobic digestion systems. All
cumulates, which decreases the pH even more. The of them studied simpler two-step models of the pro-
whole scenario ends again in the washout of the ac- cess, which consist of mass balances for two micro-
etate degraders. bial species, the substrate and the intermediate, i.e., ac-
To verify the interaction chain of this mechanism, etate. Two reactions were considered, the acidogene-
the inorganic nitrogen concentration is set to a con- sis, where acetate is formed from the substrate, and the
stant value in a modified formulation. Since the inor- methanogenesis, converting acetate to methane. They
ganic carbon is decreasing with decreased inlet con- were modeled by Monod kinetics and Haldane kinet-
centration, it influences the pH as well. Because of ics, respectively.
that the inorganic carbon concentration is set constant, Before the results of nonlinear dynamic analyses
also. Figures 7(b) and (c) shows the acetate and ac- are compared to the present findings, the articles are
etate degrader concentration against the substrate in- summarized in Table 1 and briefly explained in the
let concentration. In the original formulation, it can order of increasing complexity in the following. Rin-
be seen that for low substrate concentrations the ac- con et al. [14] analyzed the bifurcation behavior of the
etate concentration is rising again and leads to the limit model of Bernard et al. [4] with respect to the dilu-
point. In the modified formulation, the acetate concen- tion rate. The results were used for control purposes.
tration is not changing by varying substrate concentra- Sbarciog et al. [15] took the same model, but for-
tions (see branch I ), which means that the feedback mulated the kinetics in a more general fashion. They
loop is not activated. As a consequence, the acetate showed analytically and parameter independent under
degraders are still present for low substrate concentra- which operating conditions multiple steady-states are
tions (Fig. 7(c)). possible. The input variables were again the dilution
It should be mentioned that if inorganic nitrogen is rate, and additionally the inlet concentrations of the
directly fed to the reactor with the inlet, the described substrate and the intermediate. Volcke et al. [18] an-
mechanism is reduced or even disabled, since the ni- alyzed a general two-step model, which includes dif-
trogen will not deplete. ferent kind of inhibition mechanisms and is not lim-
It can be concluded that the core of the three mech- ited to anaerobic digestion. They chose the dilution
anisms is the positive feedback loop associated with rate and the inlet substrate concentration as input vari-
the interplay between the growth inhibition of the ac- ables, as well. Another important work in this area
etate degraders and the accumulation of acetic acid. was performed by Shen et al. [16]. They discussed
The difference in each case originates from the vary- a more detailed two-step model originally introduced
ing initial activations. Whereas the dilution rate influ- by Marsili–Libelli [13]. It includes the pH as well as
ences directly the acetate concentration, the substrate material transfer to the gas phase. Shen et al. [16] re-
inlet concentration has only influence on the washout duced the model and analyzed it with respect to the
boundary through inorganic nitrogen accumulation or input variables, namely the dilution rate and the in-
depletion. let substrate concentration. Additionally, they varied
Regarding a control scheme, the following conclu- the cations concentration in the inlet, introduced by
sions can be drawn from these findings. A control unit sodium bicarbonate.
should be designed taking into account the volatile All analyzed literature models showed qualitatively
fatty acid concentration such as acetic acid, to deac- the same results (c.f. Table 1). They all observed
tivate the discussed positive feedback loop. Another washout due to dilution rate changes in form of a limit
option is to control the inorganic nitrogen content, if point (mechanism 1). But the other washout mecha-
disturbances in the substrate inlet concentration may nisms due to changes in the substrate inlet concentra-
occur, so that mechanisms 2 and 3 have no effect on tion cannot be observed (mechanisms 2 and 3). To il-
the microbial biomass. lustrate these differences, Fig. 8 shows the bifurcation
544 A. Bornhöft et al.

Table 1 Survey of related analyses in the literature

Study Model Analyzed input Comments Washout due to


variables increase of increase of decrease of
dilution rate substrate substrate
concentration concentration

[16] [13] Dilution rate, Influence of three × – –


substrate inlet parameters, conclusions
concentration, for operation regarding
sodium bicarbonate robustness and
inlet concentration productivity
[14] [4] Dilution rate Control purposes × – –

[15] General Dilution rate, inlet Parameter independent × – –


two-step concentration of analysis with
model and [4] substrate and conclusions for
intermediate operation
[18] General Dilution rate, Different applications × – –
two-step substrate inlet possible, analytic
models concentration solutions
This analysis ADM1, [2] Dilution rate, × × ×
substrate inlet
concentration

analyses for the model of Bernard et al. [4] (Figs. 8(a), The presented findings can be found in the parame-
(c), and (e)) in comparison with the current results of ter charts shown in Figs. 8(e) and (f), also. In the two-
ADM1 (Figs. 8(b), (d), and (f)). The comparison can step model, the continuation of the limit point shown
only be done qualitatively since the parameter sets are in Fig. 8(a) is a vertical line. That means it does not
not calibrated for the same situation and different units depend on the substrate concentration. For low sub-
are used. strate concentrations the computed limit points are not
Figures 8(a) and (b) presents the concentration of feasible, since they correspond to negative concentra-
the acetate degraders as a function of the dilution rate. tions (grey part in Fig. 8(e)). For those cases, the in-
In both results, there is a desired branch I, which ends tersection point with solution III is shown as the limit
at a limit point. The operating range with respect to the for a feasible operation. In contrast to that, the desired
dilution rate is therefore limited in both cases. The un- operating area in ADM1 is defined by the continua-
stable branch II is of qualitatively different shape due tion of the limit point (discussed above). The result-
to the very strong pH inhibition in ADM1 in compari-
ing curve (Fig. 8(f)) shows a decreasing tendency for
son to the substrate inhibition in the two-step model.
high substrate concentrations. This is the most impor-
Figures 8(c) and (d) reveals the main difference be-
tant difference to the two-step models, also observed
tween ADM1 and the other models, they show the one-
in Figs. 8(c) and (d).
parameter bifurcation diagram with respect to the sub-
In summary, the simpler models show the limit
strate inlet concentration or density. In the model of
point in the bifurcation with respect to the dilution
Bernard et al. [4], the desired branch I is not limited
for high substrate inlet concentrations. Furthermore, rate, but not the limit points regarding the substrate
the lower limit is not at a limit point, but at a branch concentration. The two-step models do not show qual-
point, where the concentration of the acetate degraders itatively the same behavior like ADM1; that becomes
reaches zero. This means that this is a qualitatively very important, especially if the substrate concentra-
different phenomenon. In contrast to that, branch I tion may change during the operation. If a simpli-
in ADM1 is limited by two limit points. The mecha- fied two-step model should show the limitation with
nisms, causing those limit points, were discussed ear- respect of the substrate concentration, the identified
lier. mechanisms have to be incorporated into the smaller
Steady-state analysis of the Anaerobic Digestion Model No. 1 (ADM1) 545

Fig. 9 (a) Reaction scheme of simplified model. (b) Reaction


scheme of the model of Bernard et al. [4]

covering qualitatively the same behavior as observed


in ADM1, should have a special form and has to fulfill
some conditions corresponding to the discussed mech-
anisms. These conditions are presented below. Fig-
ure 9(a) shows the reaction scheme of the simplified
model, and Fig. 9(b) the reaction scheme of the model
Fig. 8 Bifurcation analysis of the model of Bernard et al. [4] of Bernard et al. [4] as a reference. The illustrations are
in (a) (c) (e) and ADM1 in (b) (d) (f). (a) Acetate degrader con- designed with the software Omix according to Droste
centration with respect to the dilution rate and constant substrate
inlet density Sin = 50 g/l. (b) Acetate degrader concentration et al. [7].
with respect to the dilution rate and constant substrate inlet con- In Fig. 9(a), S1 is the organic substrate, which is
centration XC,in = 50 kgCOD/m3 . (c) Acetate degrader concen- degraded by the biomass X1 (step I). In this degra-
tration with respect to the substrate inlet density and constant
dation process, the intermediate volatile acids S2 , the
dilution rate D = 0.5 1/d. (d) Acetate degrader concentration
with respect to the substrate inlet concentration and constant di- byproduct ammonia S3 and the biomass X1 is pro-
lution rate D = 0.15 1/d. (e) Parameter chart of the limit point duced. Step II on Fig. 9(a) is the methanogenesis,
and feasible operating boundary with respect to substrate inlet which is catalyzed by the corresponding biomass X2 .
density and dilution rate. (f) Parameter chart of the limit point
This reaction is inhibited by a low pH, which is influ-
with respect to substrate inlet concentration and dilution rate
enced through the acids S2 and the ammonia S3 . Fur-
thermore, the ammonia S3 inhibits the reaction, too,
models. One suggestion how this can be done is pre- like in ADM1. This structure can be modeled with the
sented in the last part of this section. help of the following balance equations.
3.4 Alternative simplified model S˙1 = (S1,in − S1 )D − y1 · μI X1 (10)
For control and analysis applications, a simpler model Ṡ2 = −S2 D + y2,I · μI X1 − y2,II · μII X2 (11)
with less state variables than ADM1 is helpful, since
faster simulations or analytical solutions are possi- Ṡ3 = −S3 D + y3 · μI X1 (12)
ble. If the substrate concentration may change during Ẋ1 = −X1 D + μI X1 − kdec X1 (13)
the operation, it is important to include the identified
mechanisms into a simplified model. A simpler model Ẋ2 = −X2 D + μII X2 − kdec X2 (14)
546 A. Bornhöft et al.

S1 , S2 , S3 , P , X1 , and X2 stand for the concentra-


tions of the different components defined before, S1,in
the substrate concentration of the inlet and D the dilu-
tion rate. Factors with y are defined by the stoichiom-
etry and kdec is the rate constant for the decay of the
biomasses. The specific growth rates μI and μII are of
Monod type with inhibition factors:
μm,I S1
μI = (15)
kS,I + S1
μm,II S2
μII = · I1 (S2 , S3 ) · I2 (S3 ) (16)
kS,II + S2
μm and kS represent the kinetic constants. The in-
hibition terms I1 represent the pH inhibition of re-
action II, which is influenced by the ammonia and
the acetic intermediate. The second inhibition term
I2 stands for the ammonia inhibition. If the resulting
model should show qualitatively the same behavior
like ADM1, the inhibition factors have to fulfill the
following conditions.
∂I1
<0 (17)
∂S2
∂I1
>0 (18)
∂S3
∂I2
<0 (19)
∂S3 Fig. 10 Bifurcation analysis of the model of the alternative sim-
plified model in (a) (c) (e) and ADM1 in (b) (d) (f). (a) Acetate
That means that the inhibition factor I1 has to be degrader concentration with respect to the dilution rate and con-
decreasing with S2 and that reaction II is mostly in- stant substrate inlet density S1,in = 50 g/l. (b) Acetate degrader
concentration with respect to the dilution rate and constant sub-
hibited at high concentrations of S2 (condition (17)).
strate inlet concentration XC,in = 50 kgCOD/m3 . (c) Acetate
For S3 , it is the other way around and the reaction is degrader concentration with respect to the substrate inlet den-
inhibited for low concentrations, according to condi- sity and constant dilution rate D = 0.3 1/d. (d) Acetate degrader
tion (18). Condition (19) defines the second inhibition concentration with respect to the substrate inlet concentration
factor, which decreases the reaction rate at high con- and constant dilution rate D = 0.15 1/d. (e) Parameter chart of
the limit point with respect to substrate inlet density and dilu-
centrations of S3 . tion rate. (f) Parameter chart of the limit point with respect to
To exclude the trivial case, where the inhibition substrate inlet concentration and dilution rate
mechanisms are cancelled down, a fourth condition is
added.
where ki are kinetic constants, which defines the de-
∂I1 I2 gree of inhibition. The inhibition factors fulfill condi-
= 0 (20)
∂S3 tions (17)–(20) for positive values of ki .
If the chosen inhibition kinetics fulfill these condi- The results of the bifurcation analyses of this alter-
tions, the resulting model shows qualitatively the same native simplified model in comparison to ADM1 are
bifurcation behavior like ADM1. To support this state- shown in Fig. 10. For the simulations, the parameters
ment, a bifurcation analysis was done with the follow- given in Table 2 were used. They were chosen accord-
ing exemplary inhibition terms: ing to Bernard et al. [4] and modified for the alterna-
tive model when necessary. Figure 10 has the same
1 1
I1 = I2 = (21) structure and diagrams like Fig. 8 for literature com-
1+ S2 1 + S3 ki,2
S3 ki,1 parison.
Steady-state analysis of the Anaerobic Digestion Model No. 1 (ADM1) 547

Table 2 Simulation parameter for alternative simplified model Among those ten solutions, only one solution
Stoichiometric Kinetic branch is of technical relevance, since it is stable and
methane is produced. This solution branch is limited
y1 = 42.14 μm,I = 1.2 1/d with respect to the studied input parameters in three
y2,I = 116.5 mmol/g μm,II = 1.64 1/d qualitative different cases. That are (1) high dilution
y2,II = 268 mmol/g KS,I = 7.1 g/l rates as well as (2) high substrate inlet concentra-
y3 = 1.165 mmol/g KS,II = 9.28 mmol/l tions and (3) low substrate inlet concentrations. These
ki,1 = 5 × 10−2 three limiting cases and the underlying mechanisms
ki,2 = 0.5 l/mmol were analyzed in the second part of this article. It
was found that in all three cases the same underly-
ing positive feedback loop is activated. Therein, an
Figures 10(a) and (b) shows again the one-parame- accumulation of acetic acid leads to a decrease of the
ter bifurcation with respect to the dilution rate. Like pH and to the inhibition of the growth of the acetate
the simple literature models and ADM1, this simpli- degraders, which in turn enforces the accumulation
fied model has a limit point for a critical dilution of the acetic acid. In the end, the relevant microbial
rate. The main improvement of the alternative model species are washed out. The initial reason for the acti-
becomes clear in Figs. 10(c) and (d). In the bifur- vation of this feedback loop are different in each case.
cation diagram with respect to the substrate density An increase of the dilution rate leads to an accumu-
(Fig. 10(c)), branch I exists only in a limited range lation of acetic acid and influences directly the feed-
like in ADM1. Furthermore, the parameter charts in back loop (mechanism 1). In contrast, an increase of
Figs. 10(e) and (f) are qualitatively the same for the the substrate inlet concentration reduces the growth of
alternative simplified model and ADM1. the acetate degrader by an accumulation of ammonia
In summary, it can be seen that the alternative (mechanism 2). Finally, mechanism 3 is caused by an
model can reproduce the bifurcation behavior of decrease of the substrate inlet concentration. There the
ADM1 qualitatively better than the simpler literature ammonia depletion leads to a decrease of the pH. The
models. Depending on the purpose of the application, knowledge of these mechanisms can be used for an im-
it can be helpful to use this model, if the dependency provement of control concepts. It has been discussed
of the operating boundary on the substrate inlet den- that the control should either focus on the volatile fatty
sity is important. For the application of this model, acids, like acetic acid, or on the ammonia content to
the inhibition factors have to be motivated physically. compensate disturbances in the substrate.
For example, the above presented conditions (17)–(20) In the third part, the results of the bifurcation anal-
should be fulfilled. Also, the parameters of the model ysis of ADM1 were compared to similar studies in the
have to be identified for the real case with measure- literature, which focused on simpler two-step models.
ments. The comparison showed that the simpler models do
not show qualitatively the same bifurcation behavior
with respect to the substrate inlet concentration. That
is because the influence of ammonia on the micro-
4 Conclusion
bial growth was not considered and, therefore, mecha-
nisms 2 and 3 are not included.
In the present contribution, the nonlinear dynamics of
For this reason, an alternative simplified model was
the anaerobic digestion model No. 1 (ADM1) is sys-
suggested in the last part of the article. There the in-
tematically analyzed with the help of the numerical
organic nitrogen was taken as a byproduct of one re-
tool MatCont. Up to ten coexisting steady-state solu-
action, which influences the methanogenesis, a second
tions were found depending on the input parameters,
reaction. Thereby, the results of ADM1 could be qual-
dilution rate, and substrate inlet concentration. The so-
itatively reproduced with the simple two-step model
lutions differ in the set of microbial species present in
and the dependency of the microbial state on substrate
the reactor as well as in the stability properties. Fur-
inlet concentration is incorporated better.
thermore, several bifurcation points, like limit points
(saddle-node bifurcation) and branch points (transcrit- Acknowledgements This work was funded by the Federal
ical bifurcation), were found. State of Saxony-Anhalt under the grant Green-FC (6003398800).
548 A. Bornhöft et al.

Appendix: Monod type model Furthermore, the dilution rate has to be chosen be-
neath a certain limit, such that Sss,1 is larger than zero.
A simple biochemical model for a one-step reaction in
a CSTR can be described as follows: D < μmax (28)

dS μ The second steady-state (Eq. (26)) is valid for the


= D(Sin − S) − X (22)
dt Y whole parameter region, but it is obviously not de-
dX sired.
= −DX + μX (23)
dt
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