Fuel 232 (2018) 141–146

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Thermal characterization and pyrolysis of digestate for phenol production T

a,b a a,b,⁎
Yi Wei , Jijian Hong , Weirong Ji
a
College of Chemical Engineering, Zhejiang University of Technology, Zhejiang 310014, China
b
Zhejiang Province Key Laboratory of Biofuel, Zhejiang 310014, China

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Keywords: Digestate, the residue following of anaerobic digestion, had attracted great attention recently as potential
Digestate feedstock of pyrolysis. The results of component analysis verified that digestate was suitable for phenol pro-
Pyrolysis duction due to its considerable lignin content. The thermal degradation of lignin in digestate mainly occurred
Bio-oil around 350–450 °C in thermogravimetric analysis. The amorphous cellulose in digestate decomposed to short-
Phenol
chain acids, water and syngas rather than furfural at low temperature around 280 °C. Pyrolysis of digestate for
phenol production was conducted under different reaction temperature and pressure. High reaction temperature
contributed to phenol formation by facilitating the cleavage reactions of β-O-4 and C–C linkages among three
phenylpropane units in lignin. Pyrolysis pressure promoted secondary monomolecular dissociation reactions of
methoxyphenol to yield phenol and alkyl-phenol. The maximum phenolics (70.4%) and phenol (42.6%) contents
were achieved at 450 °C with 5 MPa pressure in this work.

1. Introduction
The conversion of biomass to energy sources such as biogas and
biofuel currently has drew great attention, since the limitation on sto-
rage of fossil fuels as our primary energy source [1,2]. Anaerobic di-
gestion is a well-developed technology owing several advantages over
other technologies on bio-fuel production, for waste treatment, its mild
reaction condition and considerable yield of gaseous products [3,4].
Nevertheless, the development of anaerobic digestion has been found in
a tight corner, because of the digestate byproduct during the fermen-
tation process. Digestate, the residue following anaerobic digestion of
feedstock, mainly consists of not biodegradable feedstock and pathogen
[5]. Currently, the digestate is widely used as fertilizer and fish feed,
which, however, cannot meet the requirement for industrial scale
treatment. In addition, there is a concern about spreading the heavy
metals and pathogen content in the digestate if not controlled properly
[6].
Researchers have put huge efforts on alternative uses of digestate in

⁎
Corresponding author at: College of Chemical Engineering, Zhejiang University of Technology, No. 18, Chaowang Road, Hangzhou, Zhejiang Province 310014, China.
E-mail address: weirong.ji@zjut.edu.cn (W. Ji).

https://doi.org/10.1016/j.fuel.2018.05.134
Received 12 March 2018; Received in revised form 3 May 2018; Accepted 27 May 2018
Available online 01 June 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
Y. Wei et al.
recent years. Pyrolysis is regarded as a technology with great potential
to treat the wastes. Related studies have found over 91% of the diges-
tate energy was transferred into products of bio-oil, solid and gaseous
[5]. Nowadays, scientists have concentrated on its solid product [7],
which shows good soil amendments properties [8]. However, the ac-
cumulation of ash in digestate sets up a barrier to improving the quality
of biochar product [9,10]. Bio-oil production opens a new horizon to-
ward digestate utilization, because the processes not only minimize the
limitation caused by ash, but also prevent ash appearing in the desired
product. Digestate pyrolysis oil shows promise as a biofuel source for
engine applications [11]. However, related studies on component of
pyrolysis oil are still lacking.
To achieve a better understanding of digestate pyrolysis, it is im-
portant to clarify the composition and properties of the feedstock.
During anaerobic digestion, the vast majority of cellulose and hemi-
cellulose takes decomposition accompany with methane generation.
Nonetheless, lignin has not been used during the process and is re-
garded as the main constituent of digestate [12]. Relevant researchers
have treated lignin as favorable feedstock for phenol production, be-
cause it mainly consists of three phenylpropenyl units: coumaryl al-
cohol, coniferyl alcohol, and sinapyl alcohol [13]. Catalytic pyrolysis on
lignin represented remarkable yield (66.9%) of phenolics in the ob-
tained bio-oil [14]. Nevertheless, tremendous literature studies on
lignin pyrolysis mainly base on the purified lignin feedstock derived or
extracted via specific methods, while only limited studies have been
conducted on residues, especially the digestate [15].
With the intention to further determine the concept of digestate
decomposition and phenol production, digestate was applied on pyr-
olysis to produce phenol rich bio-oil in this study. The digestate was
obtained from anaerobic digestion in laboratory. The composition
analysis and thermogravimetric analysis were conducted. Experiments
had been taken on investigating the impact of the reaction temperature
and pressure on digestate pyrolysis, as well as characterizing the yield
and quality of bio-oil product. Further objectives were to propose the
optimum reaction from digestate to phenol, and find a feasible foun-
dation of digestate decomposition mechanism for further utilization.
2. Methods
2.1. Materials
Cellulose (CAS 9004-34-6) was purchased from Aladdin (Aladdin
Bio-Chem Technology Co., LTD in Shanghai, China).
Chloroform (CAS 67-66-3, 99.0 wt%) was purchased from Aladdin
(Aladdin Bio-Chem Technology Co., LTD in Shanghai, China).
Digestate using sargassum horueri as fermentation feedstock was
obtained from mesophilic lab-scale biogas production in the laboratory.
Sargassum horueri, suitable for biogas fermentation, purchased from
Wenzhou, Zhejiang province, China. The digestate was oven-dried at
105 °C for 24 h, crushed by grinder and sieved into 20-mesh particle
before use.
2.2. Characterization of digestate
Cellulose, hemicellulose and lignin contents of the digestate were
determined as follows [16]: the digestate was boiled with 5 mL of 72 wt
% H2SO4 solution for 4.5 h to hydrolyse the cellulose and hemicellulose.
The suspension remaining dried at 105 °C for 24 h and weighted, then
the residue heated at 600 °C for 5 h and weighted for lignin determi-
nation. The glucose and reducing sugar contents in filtrate from H2SO4
treatment were measured via HPLC and DNS method [17]. Then the
cellulose and hemicellulose contents were calculated according to the
contents of glucose and reducing sugar.
Moisture content in feedstock was determined gravimetrically in
oven at 110 °C according to ASTM D2216-98. Ash content was mea-
sured base on ASTM E1534-93, in which sample was heated in a muffle
142
Fuel 232 (2018) 141–146
Fig. 1. Schematic diagram of experimental system.
furnace at 600 °C, further repeat the heating for 30 min periods until the
weight is constant. The volatile matter determination according to
ASTM D3175-11 was carried by making sample heating in a muffle
furnace at 950 ± 20 °C for 7 min. Elements such as C, H, N, S were
determined by elementary analyzer “Elementar Vario Macro”. Proteins
content was estimated by multiplying total nitrogen content (N) by
6.25.
Thermogravimetric analyser (TG209F3, Netzsch, Germany) was
used to illustrate the thermal-dynamic properties of digestate.
Approximately 10 mg of samples were progressively heated from room
temperature to 800 °C, under a heating rate of 5 °C/min and a constant
Nitrogen flow.
2.3. Experimental procedure
The digestate sample (about 30 g) has been subjected to the process
of pyrolysis in a stainless steel reactor (Fig. 1). Ethylene glycol in water
solution was used as the condensate at -5 °C. Prior to each experimental
trial, the reactor was purged with N2 for 20 min to ensure oxygen free.
The pyrolysis heating rate was employed at 5 °C/min to specific tem-
perature. The pressure within the reactor was regulated by a valve at
the outlet of the reactor. Digestate within the reactor was held at spe-
cified temperature and pressure for 20 min, and then the volatiles was
released. The heavier volatiles were condensed as bio-oils and the rest
were treated as syngas and measured by wet-gas flowmeter. The char
left in the reactor was collected and weighted.
The bio-oil obtained in this work could be separated into two
phases, the oil-phase and the water-phase. Prior research had men-
tioned the organics in water-phase contained 52.25 wt% of phenol and
guaiacols, thus the bio-oil extraction had also been applied on our
project following the procedures listed in Wei et al. [18] work. The
organics extracted was distilled to remove the solvent, then mixed with
oil phase for further analysis.
2.4. Characterization of bio-oil product
The chemical composition of bio-oil was determined with an Agilent
gas chromatography–mass spectrometer (GC–MS; GC, Agilent 7890A;
MS, Agilent 5975C) with a HP-5MS capillary column
(30 m × 0.25 mm × 0.25 μm). The GC was programmed to heat to
50 °C for 6 min followed by heating to 200 °C at a rate of 3 °C/min and
maintained for 2 min. Afterwards, heating to 280 °C at a rate of 5 °C/
min and maintained for 2 min. A high-purity helium stream as the
carrier gas. The flow rate of the carrier gas (helium) was 1.0 mL/min.
Compounds were identified by comparing the spectral data with that in
the NIST Mass Spectral library [19,20]. Besides, the moisture content in
bio-oils was tested by the Karl Fischer titrator (Metrohm 870 KF Titrino
plus) accordance with ASTM E203-08.
Y. Wei et al. Fuel 232 (2018) 141–146

Table 1 DTG
0.0 TG 100
Chemical composition of the digestate and sargassum horuer.
Analysis process Parameter Digestate (wt. Sargassum horuer (wt.
%) %)

-0.6 80
Component Cellulose 14.41 47.40

Mass(%)
analysis Hemicellulose 4.91 12.33

DTG
Lignin 30.36 17.43

Industrial analysis Moisture 13.39 17.56

-1.2 60
Ash 19.58 16.59
Volatile matter 55.07 59.45
Proteina 23.06 13.13

Elemental analysis C 37.28 34.74

H 5.53 4.93
N 3.69 2.10
S 0.56 1.39
Ob 33.35 40.25
a
Calculated by the difference.
b
Calculated by the difference in relative contents.
2.5. Characterization of syngas
The gas compositions, which contributed to getting better ac-
quainted with digestate pyrolysis, was determined by gas chromato-
graph. The gas chromatograph (Shimadzu GC2014, with TDX-01
column) with a thermal conductivity detector (TCD) was set at tem-
perature of 220 °C, for analyzing H2, CO, CH4, CO2. Another gas chro-
matograph (FULI GC9790SD, with Porapak Q column) with a flame
ionization detector (FID) was applied for the determination of C2H4,
C2H6, C3H6, C3H8 at 200 °C.
3. Results and discussion
3.1. Composition analysis of the digestate
Experimental results of chemical composition represented a sig-
nificant difference between solid digestate and general biomass, as
listed in Table 1. Cellulose and hemicellulose detected only reached
quite low level of 14.41 wt% and 4.91 wt%, respectively, compared
with raw biomass. The phenomenon was attributed to anaerobic di-
gestion, during which the microorganism consumed the great mass of
cellulose and hemicellulose in biomass feedstock. On opposite, a rela-
tively high lignin content of 30.36 wt% was observed in the digestate as
expected. The accumulated lignin in the solid digestate laid the foun-
dation for acquisition of phenol. Moisture and volatile matter contents
were 13.39 wt% and 55.07 wt%, respectively. Notably, high ash content
of 19.58 wt% was obtained in composition analysis and matched the
Stefaniuk’s [7] results well. The ash impeded carbonization during
pyrolysis by blocking the heat transfer in digestate. Meanwhile, the
elemental analysis was also applied to characterization the digestate. A
content of 37.28 wt% and 5.53 wt% were respectively determined for C
and H. The high N content of 3.69 wt% derived mainly by lig-
nocellulosic substrates and remaining of fermentation microorganism.
Besides, the composition of the digestate in our research was similar to
those of digestate from agricultural biogas plant [10,21].
3.2. Thermogravimetric analysis of the digestate
It is extremely important to investigate the thermal characterization
of digestate, which contributes to clarifying the potential relationship
between chemical components and degradation process. The thermo-
gravimetry (TG) and differential thermogravimetry (DTG) curves were
shown in Fig. 2. Four stages of weight loss had been observed and
approximately 60 wt% of weight loss was achieved. The first region
below 150 °C caused by vaporization of moisture. Second zone came as
a steady mass reduction in the range from 200 to 350 °C led to a major
-1.8 40
0 100 200 300 400 500 600 700 800
temperature( )
Fig. 2. TG and DTG thermograms of the digestate.
weight loss of nearly 30 wt%, including two weight loss peaks at around
250 °C and 280 °C, respectively.
To make sure of the assignments about the 250 °C and 300 °C
mentioned above, additional experiments had been conducted on pyr-
olysis of protein and cellulose and digestate samples. The pyrolysis
products such as 3,4-dimethyl-3-pyrrolin-2-one had been detected in
both of digestate and protein samples, which proved that protein in
feedstock also took part in pyrolysis. Meanwhile, more cellulose derived
acetic acid and 5-hexenoic acid, rather than products with nitrogen,
had also been generated in digestate pyrolysis, accompanied with
temperature rise to 300 °C. To support the hypothesis, TG-FTIR was
then carried out on digestate feedstock (Fig. 4). The spectra indicated
both of cellulose and protein decomposed mildly below 200 °C, because
the hydroxy group in branch was released in a form of water. However,
protein took further decomposition to release nitrogen compound since
200 °C, as CeN bonds was not stable against high temperature com-
pared with CeC bonds [22]. Slight absorption intensities between 3400
and 4000 cm−1 in both digestate and protein sample was found be-
tween 200 and 300 °C, while which was absence in spectra of cellulose.
Particularly, the peaks around 3500 cm−1 gradually increased when
temperature increased from 250 to 300 °C. This appear at 3520 cm−1
and 3400 cm−1 for the stretching band of NH2 in amide [23]. As amide
was reported as the product of protein pyrolysis, it is obviously that
cellulose tended to represent higher pyrolysis temperature than protein
in digestate. Besides, the absorption intensities were greatly increased
above 300 °C, indicating considerable decomposition rate of cellulose
and protein was obtained above the temperature. As a result, the phe-
nomenon on TG could be attributed to the thermal degradation of
protein in feedstock at 250 °C, and decomposition of cellulose fibers
which had not been utilized during fermentation at higher temperature.
Notably, the cellulose in digestate given lower decomposition tem-
perature compared with raw cellulose could be explained by decrys-
tallization. The microorganism in anaerobic digestion system made use
of cellulose as carbon and energy sources, and synthesized cellulase for
turning crystalline cellulose into amorphous one. The amorphous cel-
lulose had weak connection between molecule and performed poor
thermal stability against heating, which led to lower degradation
temperature than raw cellulose on TG. Furthermore, the amorphous
cellulose tended to form production of short-chain acids, water and
syngas rather than complex organics (such as furfural and 5-methyl
furancarboxaldehyde).
Additionally, the degradation of lignin could demonstrated the third
region around 350–450 °C [24]. Phenolics in bio-oil from thermal de-
gradation of lignin was mostly produced in the step. The last area at
temperature 550–650 °C was illustrated by the secondary reaction of
residual lignin, which began to release hydrogen and methane. It is
noteworthy that temperature of the secondary reaction of lignin was
also lower than the value reported in literature [25]. The phenomenon

143
Y. Wei et al. Fuel 232 (2018) 141–146

Table 2 A 60
Pyrolysis product yields of the digestate. Bio-oil
Solid
Temperature (°C) Pressure (MPa) Solid yield Bio-oil yield Syngas yield 50
Syngas
(wt.%) (wt.%) (wt.%)

Product yield(%)
350 5.0 49.83 29.60 18.27
40
400 5.0 46.69 29.19 21.42
450 5.0 42.05 29.18 23.07 30
450 Atmosphere 43.16 31.05 23.02
450 2.5 44.91 28.85 23.64
450 6.5 43.69 26.86 27.09 20
450 8.0 43.81 27.59 26.50
500 5.0 41.69 23.44 32.17 10
550 5.0 39.65 18.57 37.05

0
350 400 450 500 550
probably could be explained by the catalytic effect of ash present in
Temperature(°C)
digestate, which facilitate the thermal cracking of the tar residues and Bio-oil
formation of pyrolysis gas [15]. In sum, the digestate was suitable for B 50 Solid
Syngas
phenol production by pyrolysis.
40
3.3. Effects of process conditions

Product yield(%)
3.3.1. Effects of pyrolysis conditions on product distribution 30
The experimental results regarding pyrolysis product yields were
represented in Table 2, and the effects of temperature on product dis- 20
tribution were shown in Fig. 3A. The yield of syngas product gradually
increased from 18.27 to 37.05 wt% accompanied with temperature
rising, while the solid yield dramatically dropped from 49.83 to 10
39.65 wt%. The syngas mainly consisted of CO2, CH4 and H2 with tiny
amount of CO and C2+ gases. CO2 and CO mostly derived from dec- 0
arboxylation and decarbonylation reactions. A lot of CO2 resulted from atmosphere 2.5 5 6.5 8.0
the cracking of amorphous cellulose and protein in digestate. Mean- Pressure(MPa)
while, quite constant yield of bio-oil around 29 wt% was observed
Fig. 4. A. The effects of temperatures on product distribution; B. The effects of
lower than 450 °C, but the yield nearly halved to 18.57 wt% beyond the reaction pressure on product distribution at 450 °C.
temperature. As a result, the temperatures from 350 to 450 °C were
considered the optimum conditions for maximum yield of bio-oil.
Higher temperature promoted decomposition of the feedstock and
contributed to more H2 and CH4 generation. Besides, the ash in agri- products kept at rather constant level. For bio-oil, a constant yield was
cultural wastes favored solid production and inhibited the yield of bio- observed below the 5.0 MPa pressure, followed by a slight decrease
oil as Li et al. [26] reported. beyond the pressure. The maximum bio-oil yield of 31.05 wt% was
The relationship between product distribution and reaction pressure obtained at atmospheric pressure. The pressure would not cause influ-
at 450 °C were presented in Fig. 3B. The yields of solid and syngas ence on product distribution in this work, which was strongly agreed

0.05

0.04

0.03
Abs

0.02

0.01

0.00
120
210
300
390
480
570
660
750
Temp.( C)
500 1000 1500 2000 2500 3000 3500 4000
-1
Wavenumber(cm )
Fig. 3. TG-FTIR spectra of the digestate.

144
Y. Wei et al. Fuel 232 (2018) 141–146

with Melligan et al. [27] attitude. 100

3.3.2. Effects of pyrolysis conditions on composition of bio-oil 80

The bio-oil obtained from pyrolysis of digestate including organics
and water, in a approximate rate of 3/7. High content water resulted
from the moisture in feedstock, dehydration and secondary cracking
60

GC-MS(%)
reaction [28]. The chemical composition of organics could be classified
into phenolics, nitrogen-containing compounds, guaiacols(methox-
yphenol), ketones (including aldehyde), hydrocarbon and alcohols as
shown in Fig. 4. The major compounds were phenol and phenol deri- 40
vatives from depolymerization of lignin. Bio-oil obtained at 350 °C only
contained 45.4% phenolics and 3.3% guaiacols (methoxyphenol) of
organics individually. The reason was that low temperature cannot 20
afford to complete the decomposition process except breaking β-O-4
linkages. Higher temperature (over 400 °C) facilitated the degradation
of lignin, primarily the cleavage of C-C linkages among three phenyl-
0
propane units of lignin [29,30], resulted in the increasing phenolics 350 C 400 C 450 C 450 C 450 C 450 C
content from 45.4% to 70.4%. However, the trend reversed when the 5.0 MPa 5.0 MPa 2.5 MPa 5.0 MPa 6.5 MPa atmosphere
temperature above 450 °C, maximum content of phenol production was others esters ethanols hydrocarbon ketones
nitrogan-containing compounds Guaiacols phenols
obtained at 450 °C. The contents of phenolics and phenol were 70.4%
and 42.6% in organics respectively. Besides, 4.5% of ketones at 350 °C Fig. 5. The chemical composition of organics in bio-oil.
had been detected in organics and was declining as the temperature
rise.
Furthermore, different reaction pressures led to variation on che-
mical composition of organics in bio-oil. Low selectivity to the phenol
and phenolics was observed at atmospheric pressure, with only 6.5% 3.3.3. The mass flow of digestate on phenol production
and 10.9% of organics, respectively, whereas high contents of phenol An overall mass flow of digestate accounting for the phenol pro-
and phenolics were achieved when the reaction pressure rise. However, duction was described in Fig. 6. The input of fixed mass of digestate as
with a further increase in pyrolysis pressure above 6.5 MPa, production well as output for all the phenol was calculated. Generally, 100 g dry
of phenol was not favored. The maximum content of phenolics (70.4% feedstock (with water content around 13.5 wt%) was put into the pyr-
in organic) and phenol (42.6% in organic) were obtained at 5.0 MPa olysis systems and converted into 30 g of bio-oil, 23 g of syngas and
pressure. It is noteworthy that guaiacols appear in high content (35.2% around 42 g of char each time. Meanwhile, there was a weight loss of
of organic) at atmospheric pressure, which, however, were almost took 5 g observed in the research, which mainly could be attributed to
place by phenolics in the pressurized pyrolysis bio-oil, as shown in polymerization of guaiacol compounds in bio-oil. The tar formed in the
Table 3. The results implied that high pressure promoted secondary tubes of the system and would not be utilized. The bio-oil obtained took
monomolecular dissociation reactions of methoxyphenol to yield centrifugation to collect 8.09 g organic compound, while the water was
phenol and alkyl-phenol. The methoxyl group(s) was removed effec- removed with acid, ethanol, and ketones (20.91 g), which would be
tively by formation CH4. Additionally, ketone content decreased dra- pumped into the fermentation systems again. In sum, 5.66 g of phenol
matically from 10.8% to 2.2% with pressure change (Table 3), which and 0.21 g of guaiacols was generated in the process. Besides, the ni-
could be attributed to ketone consumption. The ketone and alkoxy trogen content occupied 16.7 wt% (1.35 g) in final organics. The pre-
group with less molecular weight took polymerization reaction and treatment on nitrogen was indispensable, since the ammonia group in
formed phenol products [31] (see Fig. 5). digestate had high activity in pyrolysis and in consequent set barriers
In addition, the nitrogen in digestate had transformed into bio-oil for utilization of products.
product to form nitrogen-containing compounds, especially at low
temperature as mentioned above. However, content of nitrogen-con- 4. Conclusion
taining compounds decreased with raising temperature to 500 °C,
which probably due to proteins release in form of NH3 during pyrolysis Digestate from anaerobic digestion of sargassum horueri was a
Ren. [32]. However, the detail conversion mechanism of nitrogen lignin-rich feedstock. The TG analysis indicated that cellulose in di-
during digestate pyrolysis was quite complex, and more efforts focused gestate had lower temperature of decomposition compared with raw
on nitrogen compounds would be devoted in our future study. cellulose, because of decrystallization during fermentation. The de-
gradation of residual lignin mainly occurred around 350–450 °C.
Results of pyrolysis presented that temperature and pressure played
significant role in the process. High pressure promoted secondary
monomolecular dissociation reactions of methoxyphenol to yield
phenol and alkyl-phenol, while had no influence on bio-oil yield. The
Table 3 bio-oil contained considerable levels of phenol and phenolics at op-
GC/MS analysis of major products of organics in bio-oils from pyrolysis of di- timum reaction condition.
gestate at different conditions.
Reaction conditions Phenol (%) Phenolics (%) Guaiacols (%) Ketones (%) Acknowledgments

350 °C, 5.0 MPa 20.4 45.4 3.3 4.5 This study gratefully acknowledges the financial support from
450 °C, atmosphere 6.5 10.9 35.2 10.8
Zhejiang Ocean Economic Innovation Achievements Transformation
450 °C, 2.5 MPa 37.9 66.9 4.1 4.3
450 °C, 5.0 MPa 42.6 70.4 2.6 2.2 and Industrialization of Development Area Demonstration Projects,
China (2015–83) and Natural Science Foundation of Zhejiang Province,
Phenolics include phenol and the alkyl substituent products of phenol. China (Grant No. LQ18B060006), and supported by Zhejiang Province

145
Y. Wei et al.
(tar in tubes of the systems)
Digestate 100g Pressurized
(moisture 13.5 wt.%) pyrolysis
pump into the
fermentation system
Water phase 20.91g Phenol
(moisture 97wt.%) 5.66g
Fig. 6. Mass flow of digestate on phenol production at 450 °C, 5 MPa.
Key Laboratory of Biofuel.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.fuel.2018.05.134.
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146
Fuel 232 (2018) 141–146
Weight loss 5g
Syngas 23g
(CO 2,CO,CH 4,H 2...)
Bio-char and ash
42g
Bio-oil 30g
(moisture 70wt.%)
Guaiacols Nitrogen compounds
0.21g 1.35g
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