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Bioresource Technology 211 (2016) 101–107

Contents lists available at ScienceDirect

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

Application of ADM1 for modeling of biogas production from anaerobic


digestion of Hydrilla verticillata
Xiaojuan Chen a, Zhihua Chen b, Xun Wang b, Chan Huo b, Zhiquan Hu b, Bo Xiao b,⇑, Mian Hu b
a
China-Eu Institute for Clean and Renewable Energy, Huazhong University of Science & Technology, Wuhan 430074, China
b
School of Environmental Science and Technology, Huazhong University of Science & Technology, Wuhan 430074, China

h i g h l i g h t s

 Batch anaerobic digestion experiments on Hydrilla verticillata were conducted.


 The ADM1 was used to model biogas production and composition.
 Sensitive parameters were optimized by parameter estimation.
 Optimized kinetic parameters indicated good fit with experimental results.
 Application of the modified ADM1 can well explain the reaction mechanisms.

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

Article history: The present study focused on the application of anaerobic digestion model no. 1 (ADM1) to simulate bio-
Received 27 December 2015 gas production from Hydrilla verticillata. Model simulation was carried out by implementing ADM1 in
Received in revised form 27 February 2016 AQUASIM 2.0 software. Sensitivity analysis was used to select the most sensitive parameters for estima-
Accepted 1 March 2016
tion using the absolute–relative sensitivity function. Among all the kinetic parameters, disintegration
Available online 8 March 2016
constant (kdis), hydrolysis constant of protein (khyd_pr), Monod maximum specific substrate uptake rate
(km_aa, km_ac, km_h2) and half-saturation constants (Ks_aa, Ks_ac) affect biogas production significantly,
Keywords:
which were optimized by fitting of the model equations to the data obtained from batch experiments.
Hydrilla verticillata
Anaerobic digestion
The ADM1 model after parameter estimation was able to well predict the experimental results of daily
ADM1 biogas production and biogas composition. The simulation results of evolution of organic acids, bacteria
Simulation concentrations and inhibition effects also helped to get insight into the reaction mechanisms.
Ó 2016 Published by Elsevier Ltd.

1. Introduction model no. 1 (ADM1) has been considered as the most comprehen-
sive model, which is gaining increasing attention from researchers
Anaerobic digestion (AD) is a biological process that converts due to its wide applicability (Weinrich and Nelles, 2015). The
bio-degradable organic waste into biogas, which is attracting ADM1 model describes the physical and biochemical processes
increasing attention from researchers, not only as a mature tech- within the anaerobic digestion system in detail by clearly distin-
nique to treat organic wastes, but also as a potential approach to guishing the model components and establishing the correspond-
produce renewable energy (Li et al., 2014). However, the mecha- ing reaction kinetics equations. The schematic overview of ADM1
nism of AD process is very complex owing to the numerous is shown in Fig. 1 (Batstone et al., 2002). Though the ADM1 is based
microorganisms and complicated reactants and products involved on AD of sewage sludge in continuous stirred digester, it has also
during the whole reaction process, hence making it hard to explain been widely used in simulating AD of wastewater (Dereli et al.,
the reaction mechanisms only with the experimental data 2010), agricultural wastes (Antonopoulou et al., 2012), microalgae
(Batstone et al., 2002). (Mairet et al., 2011; Yuan et al., 2014) and other solid wastes like
In order to describe AD process in a more detailed way, numer- manure (Astals et al., 2011), and most of the simulation results
ous model studies on AD (Angelidaki et al., 1999, 1993; Gavala show that ADM1 can well simulate the AD processes by making
et al., 2003; Lyberatos and Skiadas, 1999) have been conducted some modifications of the structure or kinetic parameters of the
since the middle of the last century. Up to now, anaerobic digestion original ADM1 model. However, application of ADM1 to simulate
AD process of aquatic plants (like kelp or waterweeds) has been
⇑ Corresponding author. rarely reported.

http://dx.doi.org/10.1016/j.biortech.2016.03.002
0960-8524/Ó 2016 Published by Elsevier Ltd.
102 X. Chen et al. / Bioresource Technology 211 (2016) 101–107

Nomenclature

HV Hydrilla verticillata RF raw fiber


AD anaerobic digestion RP raw protein
ADM1 anaerobic digestion model no. 1 RL raw lipid
kdis disintegration constant I inert
khyd_ch hydrolysis constant of carbohydrates ADF acid detergent fiber
khyd_li hydrolysis constant of lipids ADL acid detergent lignin
khyd_pr hydrolysis constant of proteins NfE nitrogen free extract
km_aa Monod maximum specific substrate uptake rates of fli_Xc yield of lipids from complex particulates
amino acid fch_Xc yield of carbohydrates from complex particulates
km_ac Monod maximum specific substrate uptake rates of fpr_Xc yield of proteins from complex particulates
acetate fXi_Xc yield of inerts from complex particulates
km_h2 Monod maximum specific substrate uptake rates of Xaa amino acids degrading bacteria
hydrogen Xpro propionate degrading bacteria
km_su Monod maximum specific substrate uptake rates of Xac acetate degrading bacteria
monosaccharide Xc4 butyrate and valerate degrading bacteria
Ks_aa half-saturation constant of amino acid Xfa long fatty acids degrading bacteria
Ks_ac half-saturation constants of acetate Xsu monosaccharide degrading bacteria
Ks_h2 half-saturation constants of hydrogen Xh2 hydrogen degrading bacteria
Ks_su half-saturation constants of monosaccharide c4_H2 hydrogen inhibition for Xpro
Y yield of biomass on substrate ac_pH pH inhibition for Xac
COD chemical oxygen demand pro_H2 hydrogen inhibition for Xpro
TS total solids ac_NH3 NH3 inhibition for Xac
VS volatile solids
Xc COD of complex particulates
CH carbohydrates

Hydrilla verticillata (HV) is a kind of submerged aquatic plant, with the well-established Weender analysis and van Soest method
which is usually used to treat the river pollution due to its good (Koch et al., 2009; Wichern et al., 2009).
adaptability and strong adsorption capacity of nutrient elements
(Mishra et al., 2014) and some heavy metals (Li et al., 2014). How- 2.1.2. Experiment set-up and operation
ever, the dead HV, without treatment, will release pollutants to the The batch experiments were carried out in 500 mL conical flask
water, and even aggravate the water pollution. Given the impor- incubated at 35 °C (see Fig. 2). In order to eradicate any discrepan-
tance of treating the dead HV, using anaerobic digestion technol- cies, the experiments were repeated three times and mean value
ogy to treat it will be an environmental and economic approach. was recorded. The experimental conditions referred to the litera-
Therefore, a model that could predict the biogas production pro- tures (Esposito, 2012; Ramos-Suárez and Carreras, 2014), and the
cess would be of great interest. The present study focused on using total solids of the digested slurry and the inoculums adding ratio
ADM1 model to simulate the AD process of HV and the aim is to were adjusted to 8% and 20% on the basis of dry weight, respec-
investigate the most sensitive ADM1 parameters during the reac- tively. The working volume of the conical flask digester was
tion process, and then to optimize these parameters by fitting 400 mL, and each digester was added with 10 g natural-dried HV.
the model equations to experimental data. The ADM1 with opti- Before the experiment beginning, the pH of the fermentation slurry
mized parameters will be used to simulate the evolution of organic was adjusted to 6.8–7.2 with 0.1 mol/L NaOH and HCl solutions,
acids, bacteria and inhibition effects caused during the process, and nitrogen were introduced into the digester to eliminate oxygen
which will give an insight into the internal reaction mechanisms. in the headspace. The digestion process lasted for 20 days, and dur-
ing this process, each digester was manually shaken for two times
each day.
2. Methods

2.1.3. Analytical methods


2.1. Batch experiment
Biogas production was measured with a 250 mL measuring
cylinder via water displacement method and recorded every day.
Batch experiments were carried out in order to determine the
Biogas composition was determined with a Gas Chromatograph
kinetic parameters for biogas production from HV.
(SP-2100, China) equipped with a thermal conductivity detector
(TCD) and a packed column. For the calibration, standard gases
2.1.1. Substrate and inoculums (H2, O2, N2, CH4, CO2: purity > 99.9%) were used. The temperature
HV used in the experiment was obtained from Dianchi Lake in of injector port, column and detector were maintained at 120 °C,
Yunnan Province, China. The inoculums used in the experiment is 95°C and 150 °C, respectively. Argon was used as the carrier gas
the anaerobic sludge from a mesophilic lab-scale continuously stir- at a flow rate of 40 mL/min.
red tank reactor treating pig manure at the School of Environment
Science and Engineering, Huazhong University of Science and 2.2. Mathematical modeling
Technology, Wuhan, China. Chemical oxygen demand (COD), total
solids (TS) and volatile solids (VS) of HV and sludge inoculums The ADM1 model employed in this study was almost same to
were conducted according to standard methods (APHA et al., the initial ADM1, except for the different setting of initial values
1995). The compositions of HV (see Table 1) were investigated of some parameters. The stoichiometric parameters and kinetic
X. Chen et al. / Bioresource Technology 211 (2016) 101–107 103

Composite particulate

Disintegration Inert particulate

Carbohydrates Proteins Lipids Soluable inerts

Hydrolysis

Sugars Amino acids LCFA

Acidogenesis

HPr, Hbu, HVa

Acetogenesis

Acetate
H2

Methanogenesis

CH4

Fig. 1. Schematic overview of ADM1. LCFA: long chain fatty acid, HPr: propionic acid, HBu: butyrate acid, Hva: valeric acid.

Table 1 teins and inerts from disintegration of complex particulates (fch_xc,


Characteristics of Hydrilla verticillata. fli_Xc, fpr_Xc, fXi_Xc,) were determined by experiments. Xc was deter-
Parameter Unit Value mined at 13.85 Kg COD/m3, and fch_xc, fli_Xc, fpr_Xc, fXi_Xc were deter-
Total solids (TS) [%] 92.0
mined by the method proposed by Koch et al. (2010), as shown in
Volatile solids (VS) [% TS] 72.4 the following equations
Raw fiber (RF) [% TS] 17.78      
Raw lipids (RL) [% TS] 1.20 CH % RP % RL %
Raw protein (RP) [% TS] 22.66 f ch Xc ¼ ; f Pr Xc ¼ ; f li Xc ¼ ;
VS % VS % VS %
Nitrogen free extracts (NfE) [% TS] 23.74  
Neutral detergent fiber (NDF) [% TS] 46.9 I %
f Xi Xc ¼ ;
Acid detergent fiber (ADF) [% TS] 40.0 VS %
Acid detergent lignin (ADL) [% TS] 3.80
where CH, RP, RL, I and VS represent the carbohydrates, raw pro-
teins, raw lipids, inerts and volatile solids contained in the dried
parameters remained at their default values, while the measurable H. verticillata. According to Table 1, there is no index can directly
parameters including the chemical oxygen demand (COD) of the represent carbohydrates and inerts, but Lübken et al. (2007) pointed
composite particulate (Xc), the yield of carbohydrates, lipids, pro- out that cellulose and lignin were assumed as not degradable

Fig. 2. Experiment set-up.


104 X. Chen et al. / Bioresource Technology 211 (2016) 101–107

during the anaerobic digestion process. Therefore, in the present parameters was used to simulate the concentration of organic
model, inerts (I) was represented by the sum of lignin and cellulose. acids, bacteria and inhibition effects during the whole digestion
Cellulose was considered as the difference between acid detergent process, which would be helpful to explain the reaction
fiber (ADF) and acid detergent lignin (ADL). The sum of raw fiber mechanisms.
(RF) and nitrogen free extract (NfE) represents the total carbohy-
drate content, while in ADM1, carbohydrate content means the
3. Results and discussion
degradable part, therefore, cellulose and lignin must be subtracted
from the total carbohydrate (Lübken et al., 2007; Naumann and
3.1. Experimental results and discussion
Bassler, 1993). Table 2 shows the initial values of these calculable
parameters.
Fig. 3A shows the daily biogas production of HV during the
The ADM1 model with modified parameters was implemented
20 days anaerobic digestion. The biogas production rapidly
in AQUASIM 2.0 software, as a constant volume mixed-liquid com-
occurred from day 1, and peaked on day 7 with the highest daily
partment and a gas compartment linked by a diffusive link. The
biogas production of 228 mL. After day 7, daily biogas production
evolution of each variable in the course of a simulation in real time
began decreasing except that another peak was found on day 12.
will be monitored and exported with figure or spreadsheet.
This might be attributed to that some components were refractory
to be degraded in the beginning, and along with the digestion,
2.3. Sensitivity analysis and parameter estimation
these components might undergo various reactions, such as enzy-
matic and biochemical reactions, and became biodegradable,
In order to define the most sensitive ADM1 parameters during
therefore, additional biogas production occurred.
the production of biogas, a parametric sensitivity analysis was per-
formed. The parameters analyzed were disintegration constant of
the composite particulate (kdis), hydrolysis constants of carbohy-
drates, proteins and lipids (khyd_ch, khyd_pr and khyd_li, respectively), A 250
Monod maximum specific substrate uptake rates of amino acids,

daily biogas production [mL]


acetate, monosaccharide and hydrogen (km_aa, km_ac, km_su and 200
km_h2, respectively), half-saturation constants of amino acids, acet-
ate, monosaccharide and hydrogen (Ks_aa, Ks_ac, Ks_su and Ks_h2,
150
respectively) and yield of biomass on substrate (Y). Methane con-
centration was set as the focused variable to measure sensitivity
100
and the sensitivity index (SI) is defined as follows:
@y 50
SI ¼ da;r
y;p ¼ p ;
@p
where y is methane concentration and p is the analyzed parameter. 0
0 2 4 6 8 10 12 14 16 18 20
SI means the absolute change in y for a 100% change in y for a 100% T[d]
change in p.
The sensitive parameters determined by the sensitivity analysis B
were estimated by minimizing the sum of the squares of the 2000
biogas accumulation [mL]

weighted deviations between measurements and calculated model


results. Parameters were optimized with measured experiment
1500
data of daily biogas production and methane concentration. The
following function was used for parameter estimation:
1000
n 
X 
ymeas;i  yi ðpÞ 2
v ðpÞ ¼
2
;
i¼1
rmeas;i 500
where ymeas,i is the ith measurement, rmeas,i is its standard deviation,
yi(p) is the calculated value of the model variable corresponding to 0
the ith measurement and evaluated at the time of this measure- 0 2 4 6 8 10 12 14 16 18 20
ment, p = (p1;. . .. . .; pm) are the model parameters, and n is the num- T[d]
ber of data points.
The experimental data were used to calibrate the model by fit-
C 80

ting the experimental data to the simulated data. Through sensitiv- 70


biogas composition [%]

ity analysis and parameter estimation, sensitive parameters were 60


selected and estimated, and then the ADM1 model with optimized 50
40
30 CH4
Table 2 CO2
Changed parameters in ADM1. 20
H2
Parameter Unit Value 10
Xc Kg COD/m3 13.85 0
fch_xc – 0.0718
fli_Xc – 0.0166
0 2 4 6 8 10 12 14 16 18 20
fpr_Xc – 0.313 T[d]
fXi_Xc – 0.55
Fig. 3. Experimental results.
X. Chen et al. / Bioresource Technology 211 (2016) 101–107 105

Biogas production accumulation is shown in Fig. 3B. In the first 3.2. Simulation results and discussion
seven days, biogas accumulation dramatically increased, and the
tendency became slower between day 7 and day 14, while after 3.2.1. Sensitivity analysis and parameter estimation
day 14, biogas accumulation almost became constant, and only The sensitivity analysis results are shown in Fig. 4. High sensi-
120 mL biogas was produced in the last six days, which means that tivity values were observed for kdis and khyd_pr (Fig. 4A), km_aa, km_ac
most biodegradable components was digested in the first fourteen and km_h2 (Fig. 4B) and Ks_aa and Ks_ac (Fig. 4C). High values of kdis,
days with those non-biodegradable compounds remaining in the khyd_pr, km_aa, km_ac and km_h2 caused fast decomposition of sub-
reactor. Total biogas production in the 20 days was about strate and rapid growth of biomasses in the digester, which
2020 mL, and biogas potential of HV was 219.56 L/Kg TS. resulted in quick degradation of LCFA and organic acids, and there-
The measured values of biogas composition are shown in fore higher methane production. The opposite is found for Ks_aa and
Fig. 3C. Biogas compositions fluctuate strongly in the first 7 days, Ks_ac which showed that lower values of Ks_aa and Ks_ac could result
and become rather constant in the following 13 days. Hydrogen in higher methane production. This might be due to that lower
content is very low during the whole process, and no hydrogen half-saturation constants of microorganisms mean that biomasses
can be measured after day 7. This might be due to that hydrogen could grow quicker. Low sensitivity was found for Y, which was
generates from hydrogen-production acetogenesis stage, which also reported by Jeong et al. (2005) and Mendes et al. (2015).
might mainly occur in the first 7 days during the batch experiment. Based on the sensitivity results, kdis, khyd_pr, km_aa, km_ac, km_h2,
With the conversion of hydrogen to methane, the content of hydro- Ks_aa and Ks_ac were used for parameter estimation. These sensitive
gen decreased, and after day 7, less hydrogen was produced and parameters were estimated in comparison with the experimental
even all the hydrogen produced was converted to methane. data, and Table 3 shows the initial and estimated values of the sen-
sitive parameters.

3.2.2. Comparison of simulation results with experimental results


Fig. 5A–C presented the comparison between experimental
A 5 results and initial simulation results. A bad agreement between
kdis simulation results and experimental data was found for biogas pro-
4 khyd_ch
duction, and only biogas composition after day 7 could be well pre-
khyd_li
khyd_pr dicted when there was no parameter optimization. This
3
disagreement might be due to that the kinetic parameter values
SI

2 in the original ADM1 model are not suitable for this study.
Mendes et al. (2015) also reported that the ADM1 model without
1 parameter optimization could not well predict the experimental
results. However, after parameter optimization, the discrepancies
0
between the simulations and measurements became much less,
-1 and the simulation results with optimized parameters showed
0 2 4 6 8 10 12 14 16 18 20 good fit with the experiment results, indicating that ADM1 model
T[d] with optimized parameters could well predict the biogas produc-
tion process from HV. Similar results were also reported by
B 5 Thamsiriroj et al. (2012), who found that the ADM1 model modi-
km_aa
km_ac fied through assessment of lactic acid could well predict the
4 km_h2 mono-digestion of grass silage, and allowed close fit to experimen-
km_su
tal data.
3
SI

2 3.2.3. Simulation of evolution of variables by calibrated ADM1


The simulation results of the evolution of organic acids, bacteria
1 in the digester and inhibition effects during the reaction process
are shown in Fig. 6. Simulation results of organic acids (Fig. 6A)
0 revealed that in the first 7 days, the generation rate of organic acids
0 2 4 6 8 10 12 14 16 18 20 was higher than the degradation rate, showing that there were
T[d] enough substrates for the growth of bacteria, which could be seen
from Fig. 6B, and therefore resulted in quickly increasing biogas
C 0.5 production and methane concentration. On day 7, generation rate
and degradation rate of organic acids (except for propionate)
0.0
tended to be equal, and on day 12, no propionate could be moni-
-0.5 tored, showing that generation rate of propionate was equal to
-1.0
SI

Table 3
-1.5
Initial and estimated values of sensitive parameters.
Ks_aa
-2.0 Ks_ac Parameter Unit Initial value Optimized value
Ks_h2
-2.5 Ks_su kdis (d1) 0.5 0.18
khyd_pr (d1) 10 0.62
-3.0 km_aa (Kg COD Kg COD1 d1) 50 35
km_ac (Kg COD Kg COD1 d1) 8 5
0 2 4 6 8 10 12 14 16 18 20
km_h2 (Kg COD Kg COD1 d1) 35 28
T[d] Ks_ac (Kg COD m3) 0.15 0.26
Ks_aa (Kg COD m3) 0.3 0.58
Fig. 4. Sensitivity indices (SI) of parameters.
106 X. Chen et al. / Bioresource Technology 211 (2016) 101–107

A 250 A 0.8
acetate
0.7 butyrate
valerate
daily biogas production [mL]

200 0.6 propionate

C[kgCOD/m3]
monosaccharide
0.5 animo acid
150 0.4
0.3
100
simulation with 0.2
parameter optimization 0.1
50 simulation without
parameter optimization 0.0
experiment 0 2 4 6 8 10 12 14 16 18 20
0 T[d]
0 2 4 6 8 10 12 14 16 18 20
T [d] B
0.4
Xaa
B 2500 Xpro

C[kgCOD/m3]
0.3 Xac
Xc4
biogas accumulation [mL]

2000 Xfa
0.2 Xsu
Xh2
1500
0.1
1000 simulation without
parameter optimization 0.0
0 2 4 6 8 10 12 14 16 18 20
500 simulation with
parameter optimization
T[d]
experiment C 1.0
0
0 2 4 6 8 10 12 14 16 18 20
0.8
T [d]

C 80
Inhibition

0.6

70 c4_H2
0.4 ac_pH
60 pro_H2
biogas composition [%]

ac_NH3
50 0.2

40 0.0
0 2 4 6 8 10 12 14 16 18 20
30 experiment H2 CH4 CO2
T[d]
simulation without parameter optimization
20 H2 CH4 CO2
Fig. 6. Simulation results for (A) concentration of organic acids; (B) concentration
simulation with parameter estimation of bacteria; (C) inhibition effects during reaction based on the calibrated ADM1.
10 H2 CH4 CO2
0 3.3. Future work
0 2 4 6 8 10 12 14 16 18 20
Batch experiments are usually conducted to obtain experimen-
T [d]
tal data for model modification. However, in order to investigate
Fig. 5. Comparison between experimental results and simulation results. the real biogas potential of HV in actual process conditions, only
batch experiments are not enough, continuous AD reactions are
still needed. The ADM1 model with modified kinetic parameters
the degradation rate, which explained for the main biogas produc- as described above can be used to simulate the AD process of HV
tion peak on day 7 and a small peak on day 12, as is shown in in continuous digester only by changing the input variables, which
Fig. 3A. After day 7, biogas production began decreasing, which will help to predict the reaction process and prevent the failure of
might be due to that biomass tended to be saturated (Fig. 6B) the AD process (for example, the dramatic decrease of pH will ter-
and substrates were no more enough, and therefore anabolism of minate the AD reaction) in advance. Using of modeling to predict
bacteria might be greater than catabolism, resulting in decreasing the digestion processes and to aid design of digestion system has
biogas production. already been reported by Thamsiriroj et al. (2012), who used a ser-
Simulation of inhibition effects (Fig. 6C) revealed the reason for ies of mathematical models to simulate the digestion process of
the different evolution of propionate. Hydrogen inhibition (pro_H2) grass silage in a two-phase digestion system, and found that model
for propionate degrading bacteria (Xpro) was found to be the most simulation could well predict the reactor performance and help the
important inhibition effect, which caused slow growth of Xpro, and researchers to avoid the failure of digestion system. Therefore, the
thereby accumulation of propionate. As H2 was monitored in the future work will focus on application of the modified ADM1 model
first 7 days (Fig. 3B), the growth of Xpro was inhibited in the first to simulate the continuous AD processes of HV, and the future
7 days, which could also be found from Fig. 6B. work-related points can be grouped as follows:
X. Chen et al. / Bioresource Technology 211 (2016) 101–107 107

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