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Chen 2016
Chen 2016
Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech
h i g h l i g h t s
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
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
Composite particulate
Hydrolysis
Acidogenesis
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.
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,
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.
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
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]
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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modeling of methane production from acidified sweet sorghum extract in a two
continuous stirred tank reactor (CSTR) or an upflow anaero-
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bic sludge blanket (UASB). APHA, Awwa, WPCF, 1995. Standard Methods for the Examination of Water and
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uous AD processes of HV in CSTR or UASB reactor, and to Works Association, Water Environment Federation, Washington, DC, USA.
Astals, S., Ariso, M., Galí, A., Mata-Alvarez, J., 2011. Co-digestion of pig manure and
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the National High Technology Research and Development Program Naumann, C., Bassler, R., 1993. Die Chemische Untersuchung Von Futtermitteln,
third ed. VDLUFAVerlag, Darmstadt, Germany.
(863 Program) of China (No. 2012AA101809), the Major Science Ramos-Suárez, J.L., Carreras, N., 2014. Use of microalgae residues for biogas
and Technology Program for Water pollution Control and Treat- production. Chem. Eng. J. 242, 86–95.
ment (2013ZX07102-005) and the China Postdoctoral Science Thamsiriroj, T., Nizami, A.S., Murphy, J.D., 2012a. Use of modeling to aid design of a
two-phase grass digestion system. Bioresour. Technol. 110, 379–389.
Foundation (2015M580644). In addition, the authors would like Thamsiriroj, T., Nizami, A.S., Murphy, J.D., 2012b. Why does mono-digestion of grass
to thank the Analytical and Test Center of Huazhong University silage fail in long term operation? Appl. Energy 95, 64–76.
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