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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy
Star Agroenergy Research Group, University of Foggia, 89-91 Via Gramsci, 71122 Foggia, Italy
INRA, UMR 1208 Ingnierie des Agropolymres et Technologies Emergentes 2, place Pierre Viala, F-34060 Montpellier, France
c
Biomass Group, Chemical Engineering Department, Aristotle University of Thessaloniki, Un. Box 455, 54124 Thessaloniki, Greece
b
h i g h l i g h t s
Heat surplus from AD process can fully cover solid digestate drying.
Digestate pyrolysis (500 C) results to 9 wt.%, 58 wt.%, and 33 wt.% of gas, oil and char.
Coupling AD with pyrolysis produces more electricity (42%) compared to stand-alone AD.
a r t i c l e
i n f o
Article history:
Received 15 August 2014
Received in revised form 2 March 2015
Accepted 4 March 2015
Available online 25 March 2015
Keywords:
Anaerobic digestion
Biochar
Bio-oil
Digestate
Electricity
Pyrolysis
a b s t r a c t
In a full-scale anaerobic digestion plant, agricultural residues are generally converted into biogas and
digestate, the latter usually produced in large amount. Generally, biogas is converted into heat, often lost,
and electricity, which is completely valorized or it is sold to the public grid. In this context, the aim of this
study was to investigate the feasibility to combine anaerobic digestion and pyrolysis processes in order to
increase the energy recovery from agricultural residues and the sustainability of the anaerobic digestion
plant. Results revealed that heat excess produced during anaerobic digestion could cover the drying
needs for the solid digestate, while pyrolysis of digestate at 500 C resulted in 8.8 wt.%, 58.4 wt.% and
32.8 wt.% of syngas, oil and char, respectively. The LHV of syngas was 15.7 MJ N m3, whereas pyrolysis
oil exhibited a HHV of 23.5 MJ kg1 after water extraction. The hybrid system operating in symbiosis
could increase the production of electricity from 9896 kWhel day1 to 14,066 kWhel day1 corresponding
to an increase of 42% compared to AD stand-alone plant.
2015 Elsevier Ltd. All rights reserved.
1. Introduction
According to an integrated biorenery concept, the development of renewable energy generation, as biomethane, through
anaerobic digestion (AD) process appears to be one of very promising alternative to the depletion of fossil fuels and worldwide
Abbreviations: AD, anaerobic digestion; CHP, Cogeneration Heat and Power; EDD,
energy requirement for drying; EHeat, energy requirement for heating; EEvaporation,
energy requirement for evaporation; FM, fresh matter; HHV, higher heating value;
LHV, lower heating value; TS, total solids; VS, Volatile Solids; Cp, water specic
heat; Lv, latent heat of vaporization.
Corresponding author at: INRA, UMR 1208 Ingnierie des Agropolymres et
Technologies Emergentes 2, place Pierre Viala, F-34060 Montpellier, France.
Tel.: +33 (0)4 99 61 25 81; fax: +33 (0)4 99 61 30 76.
E-mail address: omonlau@hotmail.fr (F. Monlau).
1
Present address: INRA, UMR 1208 Ingnierie des Agropolymres et Technologies
Emergentes 2, place Pierre Viala, F-34060 Montpellier, France.
http://dx.doi.org/10.1016/j.apenergy.2015.03.024
0306-2619/ 2015 Elsevier Ltd. All rights reserved.
33
materials (biochar) can be produced; the latter is proposed as carbon sequestration agent by land application [1921]. Alternatively,
biochar, due to its high porous reactive surface and structural characteristics, may also be used for environmental depollution applications and detoxication of lignocellulosic hydrolysates,
including the removal of large toxic molecules (such as phenanthrene or dyes and furans or phenolic compounds, respectively)
[2224]. To date, only few studies investigated pyrolysis process
fueled with the solid digestate derived from agricultural digesters;
they are mainly focused on biochar production [19,25]. However,
pyrolysis of solid digestate can contribute not only to the reduction
of the digestate cost management, but also to the generation of
biofuels (gas, bio-oil), making the overall process more energy sustainable [26,27]. Nonetheless, data about the energetic benet of
coupling AD with pyrolysis process are still scarce in literature.
In this context, the aim of this study was to investigate the feasibility of a hybrid dual system, which combines anaerobic digestion
and pyrolysis aiming to increase the energy recovery from agricultural residues and the sustainability of the anaerobic digestion
plant. For this purpose, the physico-chemical characteristics of
the solid digestate were rstly determined. Then, pyrolysis experiments at various temperatures (400, 500 and 600 C) were carried
out, followed by the pyrolysis products (syngas, bio-oil) characterization. Finally, a preliminary energy balance was drawn to state
out the sustainability of coupling AD and pyrolysis processes.
Fig. 1 depicts the symbiotic concept of the study.
2. Materials and methods
2.1. Feedstock materials
Solid digestate was obtained from a full-scale biogas plant
located in South of Italy (Puglia region). The plant was fed with
56 t FM day1, composed of 5 wt.% of chicken manure, 9 wt.% of
groats, 29 wt.% of olive oil cake and 57 wt.% of triticale. Once collected, digestate sample was further dried at 105 C, followed by
biochemical analysis and pyrolysis experimentation. Table 1
depicts the main operational characteristics of the anaerobic digestion plant.
2.2. Digestate analysis
All chemical analyses were realized in duplicate. Total Solid
(TS), Volatile Solids (VS) and ash content were determined using
the TGA 701 (LECO). Digestate pH was measured after the
Fig. 1. Sustainable energy recovery from agricultural residues by coupling anaerobic digestion and pyrolysis process.
34
Cellulose%TS Glucose%TS=1:11
Hemicelluloses%TS Xylose%TS
Arabinose%TS=1:13
Table 1
Main operational characteristics and biogas production of the anaerobic digestion
plant.
3720
56
64.5
62
7.57.8
45
Biogas production
Biogas (Nm3 day1)
Methane (%)
Methane (Nm3 day1)
Total energy (kWh day1)a
5150
61
3142
31,415
The produced pyrolysis gas was analyzed ofine in a gas chromatographer (Model 6890N, Agilent Technologies) tted with two
columns, HP-Plot Q and HP-Molesive type reference [15]. The produced pyrolysis bio-oil was subjected to physical and chemical
analyses, including density, water content and elemental analysis.
The water content of the bio-oil was measured with Karl-Fischer
titration [31]. The water/aqueous phase present in the bio-oil, was
isolated from the organic phase using an organic solvent
35
(dichloromethane). The organic phase of the bio-oil was then subjected to elemental analysis with an elemental CHN LECO-800
analyzer.
2.4. Energy calculations
First, energy requirement for drying solid digestate was estimated based on data provided by the owner of the AD plant
(Table 5). The energy requirement EDD (kWhth day1) for drying
daily solid digestate in daily basis was calculated using the modied equation from Barakat et al. [6].
Table 2
Chemical composition of solid digestate after mechanical screw separation.
Parameters
Values (S.D)
TS (%)
VS (% TS)
Ash (% TS)
pH
C (g 100 g1 TS)
H (g 100 g1 TS)
N (g 100 g1 TS)
Carbohydrates (g 100 g1 TS)
Cellulose (g 100 g1 TS)
Hemicelluloses (g 100 g1 TS)
Proteins (g 100 g1 TS)
Klason lignin (g 100 g1 TS)
29.7
72.1
12.7
9.05
42.5
6.08
1.43
35.0
17.0
10.1
8.9
31.9
(1.1)
(0.9)
(1)
(0.08)
(0.2)
(0.12)
(0.03)
(6.0)
(0.9)
(1.3)
(0.2)
(1.8)
1
7
1
36
Table 3
Pyrolysis product yields of the solid digestate pyrolysis at 400 C, 500 C and 600 C
and gas composition.
Table 5
Energy balance of solid digestate drying.
Temperature
400 C
500 C
600 C
35.7
53.0
11.3
32.8
58.4
8.8
34.0
55.8
10.2
15.8
51.6
17.5
11.6
2.5
1
63.1
0.22
670
69.8
15.7
12.3
40.5
3.4
41.4
1.7
0.7
81.9
1.02
750
75.2
15.5
a
b
c
of the gas produced was ranging from 9.5 to 15.7 MJ N m3 and
were in agreement with the study of Troy et al. [27] that reported
a HHV of 11.7 MJ m3 after pyrolysis at 600 C of anaerobically
digested pig manure bers [27].
The bio-oil produced is of primary interest as it can replace diesel in internal combustion engine [18]. Pyrolysis oil has several
environmental advantages over fossil fuels, since it is CO2/GHG
neutral. However, the lack of established or approved standards
for pyrolysiss oil quality and properties prohibits the general use
of pyro-oil as fuel. Bio-oil is expected to contain char particles,
waxy materials, aqueous droplets, droplets of different nature,
oxygenated compounds and water, which constitute an aqueous
and an organic phase [35]. Aiming to explore the suitability of pyrolytic oil as liquid fuel, the aqueous phase (45.02% w/w of pyrolysis
bio-oil) was separated from the organic phase. Then the organic
phase was subjected to elemental analysis presented in Table 4.
Characteristics of bio-oil obtained at 500 C (where the maximum
yield of bio-oil was obtained) were also provided in Table 4. As it
can be seen, pyrolysis oil density is higher than that of light fuel
oil (0.85 kg L1) [36]. The bio-oil oxygen content, density and water
content were found higher than those of conventional hydrocarbon
oils (diesel, gasoline). Pyrolysis oil has shown an HHV of
23.5 MJ kg1, which is much higher than the HHV of bio-oil from
the anaerobically digested pig manure pyrolysis (15.3 MJ kg1),
reported in the international literature [27].
Parameters
Values
C (g 100 g1)
H (g 100 g1)
N (g 100 g1)
Oa (g 100 g1)
Empirical Formula
Density (kg L1)
HHV (MJ kg1)
58.25
5.52
1.2
34.78
CH1.13O0.45N0.017
1.12
23.5
Dened by difference.
5150
31,415
35
50
10,995
15,708
10
15
9896
13,351
23.8
70.3
16.7
2209
11,041
13,249
37
Fig. 3. Energy balance of coupled anaerobic digestion and pyrolysis on one-day running process (adapted from [18]).
residues but also for enhancing sustainability of anaerobic digestion. However, prior to any commercial application, a pilot scale
implementation is needed along with verication of benecial
properties of char as soil amendment.
Acknowledgments
The authors gratefully acknowledge the European Commission,
Directorate-General for Research & Innovation, for funding the project STAR AgroEnergy (FP7 Regpot 2011-1, Grant Agreement No.
286269). Authors are grateful to the owner of the biogas plant for
providing characteristics and production data.
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