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Fuel
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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 a tight corner, because of the digestate byproduct during the fermen-
tation process. Digestate, the residue following anaerobic digestion of
The conversion of biomass to energy sources such as biogas and feedstock, mainly consists of not biodegradable feedstock and pathogen
biofuel currently has drew great attention, since the limitation on sto- [5]. Currently, the digestate is widely used as fertilizer and fish feed,
rage of fossil fuels as our primary energy source [1,2]. Anaerobic di- which, however, cannot meet the requirement for industrial scale
gestion is a well-developed technology owing several advantages over treatment. In addition, there is a concern about spreading the heavy
other technologies on bio-fuel production, for waste treatment, its mild metals and pathogen content in the digestate if not controlled properly
reaction condition and considerable yield of gaseous products [3,4]. [6].
Nevertheless, the development of anaerobic digestion has been found in 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. Fuel 232 (2018) 141–146
Cellulose, hemicellulose and lignin contents of the digestate were The chemical composition of bio-oil was determined with an Agilent
determined as follows [16]: the digestate was boiled with 5 mL of 72 wt gas chromatography–mass spectrometer (GC–MS; GC, Agilent 7890A;
% H2SO4 solution for 4.5 h to hydrolyse the cellulose and hemicellulose. MS, Agilent 5975C) with a HP-5MS capillary column
The suspension remaining dried at 105 °C for 24 h and weighted, then (30 m × 0.25 mm × 0.25 μm). The GC was programmed to heat to
the residue heated at 600 °C for 5 h and weighted for lignin determi- 50 °C for 6 min followed by heating to 200 °C at a rate of 3 °C/min and
nation. The glucose and reducing sugar contents in filtrate from H2SO4 maintained for 2 min. Afterwards, heating to 280 °C at a rate of 5 °C/
treatment were measured via HPLC and DNS method [17]. Then the min and maintained for 2 min. A high-purity helium stream as the
cellulose and hemicellulose contents were calculated according to the carrier gas. The flow rate of the carrier gas (helium) was 1.0 mL/min.
contents of glucose and reducing sugar. Compounds were identified by comparing the spectral data with that in
Moisture content in feedstock was determined gravimetrically in the NIST Mass Spectral library [19,20]. Besides, the moisture content in
oven at 110 °C according to ASTM D2216-98. Ash content was mea- bio-oils was tested by the Karl Fischer titrator (Metrohm 870 KF Titrino
sured base on ASTM E1534-93, in which sample was heated in a muffle plus) accordance with ASTM E203-08.
142
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
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
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. Fuel 232 (2018) 141–146
Weight loss 5g
(tar in tubes of the systems)
Key Laboratory of Biofuel. [15] Peng C, Zhang G, Yue J, Xu G. Pyrolysis of black liquor for phenols and impact of its
inherent alkali. Fuel Process Technol 2014;127(Nov.):149–56.
[16] Ververis C, Georghiou K, Danielidis D, Hatzinikolaou DG, Santas P, Santas R, et al.
Appendix A. Supplementary data Cellulose, hemicelluloses, lignin and ash content of some organics materials and
their suitability for use as paper pulp supplements. Bioresour Technol
Supplementary data associated with this article can be found, in the 2007;98(2):296–301.
[17] Li C, Zhao Z. Efficient acid–catalyzed hydrolysis of cellulose in ionic liquid. Adv
online version, at http://dx.doi.org/10.1016/j.fuel.2018.05.134. Synth Catal 2010;349(11–12):1847–50.
[18] Wei Y, Lei H, Wang L, Zhu L, Zhang X, Liu Y, et al. Liquid–liquid extraction of
References biomass pyrolysis bio-oil. Energy Fuels 2014;28(2):1207–12.
[19] Dominguez A, Menendez JA, Inguanzo M, Bernad L, Pis JJ. Gas chromatographic
mass spectrometric study of the oil fractions produced by microwave assisted
[1] Lynd LR, Laser MS, Bransby D, Dale BE, Davidson B, Hamilton R, et al. How biotech pyrolysis of different sewage sludges. J Chromatogr A 2003;1012(2):193–206.
can transform biofuels. Nat Biotechnol 2008;26(2):169–72. [20] Samanya J, Hornung A, Apfelbacher A, Vale P. Characteristics of the upper phase of
[2] Tuck CO, Pérez E, Horváth IT, Sheldon RA, Poliakoff M. Valorization of biomass: bio-oil obtained from co-pyrolysis of sewage sludge with wood, rapeseed and straw.
deriving more value from waste. Science 2012;337:695–9. J Anal Appl Pyrol 2010;94(6):120–5.
[3] Chen S, Chen B. Sustainability and future alternatives of biogas-linked agrosystem [21] Monlau F, Sambusiti C, Antoniou N, Barakat A, Zabaniotou A. A new concept for
(BLAS) in China: an emergy synthesis. Renew Sustain Energy Rev enhancing energy recovery from agricultural residues by coupling anaerobic di-
2012;16(6):3948–59. gestion and pyrolysis process. Appl Energy 2015;148(3):32–8.
[4] Prochnow A, Heiermann M, Plöchl M, Linke B, Idler C, Amon T, et al. Bioenergy [22] Mutsukura N, Akita KI. Infrared absorption spectroscopy measurements of amor-
from permanent grassland – a review: 1. Biogas. Bioresour Technol phous CNx films prepared in CH4/N2 r.f. discharge. Thin Solid Films
2009;100(21):4931–44. 1999;349(1):115–9.
[5] Neumann J, Binder S, Apfelbacher A, Gasson JR, García PR, Hornung A. Production [23] Kaufman JH, Metin S, Saperstein DD. Symmetry breaking in nitrogen-doped
and characterization of a new quality pyrolysis oil, char and syngas from digestate – amorphous carbon: infrared observation of the Raman-active G and D bands. Phys
introducing the thermo-catalytic reforming process. J Anal Appl Pyrol Rev B: Condens Matter 1989;39(18):13053–60.
2015;113(4):137–42. [24] Gómez X, Cuetos MJ, García AI, Morán A. An evaluation of stability by thermo-
[6] Govasmark E, Stäb J, Holen B, Hoornstra D, Nesbakk T, Salkinoja-Salonen M. gravimetric analysis of digestate obtained from different biowastes. J Hazard Mater
Chemical and microbiological hazards associated with recycling of anaerobic di- 2007;149(1):97–105.
gested residue intended for agricultural use. Waste Manage 2011;31(12):2577–83. [25] Kyunga J, Seunghan W, Seongrin L, Jongmoon P. Pyrolytic production of phenolic
[7] Stefaniuk M, Oleszczuk P. Characterization of biochars produced from residues from compounds from the lignin residues of bioethanol processes. Chem Eng J
biogas production. J Anal Appl Pyrol 2015;115:157–65. 2015;259:107–16.
[8] Monlau F, Francavilla M, Sambusiti C, Antoniou N, Solhy A, Libutti A, et al. Toward [26] Li W, Dang Q, Brown RC, Laird D, Wright MM. The impacts of biomass properties on
a functional integration of anaerobic digestion and pyrolysis for a sustainable re- pyrolysis yields, economic and environmental performance of the pyrolysis-bioe-
source management. Comparison between solid-digestate and its derived pyrochar nergy-biochar platform to carbon negative energy. Bioresour Technol
as soil amendment. Appl Energy 2016;169:652–62. 2017;241:959.
[9] Kratzeisen M, Starcevic N, Martinov M, Maurer C, Müller J. Applicability of biogas [27] Melligan F, Auccaise R, Novotny EH, Leahy JJ, Hayes MHB, Kwapinski W.
digestate as solid fuel. Fuel 2010;89(9):2544–8. Pressurised pyrolysis of miscanthus using a fixed bed reactor. Bioresour Technol
[10] Wiśniewski D, Gołaszewski J, Białowiec A. The pyrolysis and gasification of di- 2011;102(3):3466–70.
gestate from agricultural biogas plant. Arch Environ Prot 2015;41(3):70–5. [28] Alvarez J, Amutio M, Lopez G, Bilbao J, Olazar M. Fast co-pyrolysis of sewage
[11] Hossain AK, Serrano C, Brammer JB, Omran A, Ahmed F, Smith DI, et al. sludge and lignocellulosic biomass in a conical spouted bed reactor. Fuel
Combustion of fuel blends containing digestate pyrolysis oil in a multi-cylinder 2015;159:810–8.
compression ignition engine. Fuel 2016;171:18–28. [29] Asmadi M, Kawamoto H, Saka S. Thermal reactions of guaiacol and syringol as
[12] Sasaki K, Okamoto M, Shirai T, Tsuge Y, Fujino A, Sasaki D, et al. Toward the lignin model aromatic nuclei. J Anal Appl Pyrol 2011;92(1):88–98.
complete utilization of rice straw: methane fermentation and lignin recovery by a [30] Liu JY, Wu SB, Rui L. Chemical structure and pyrolysis response of β-O-4 lignin
combinational process involving mechanical milling, supporting material and na- model polymer. Bioresources 2011;6(2):1079–93.
nofiltration. Bioresour Technol 2016;216:830–7. [31] Custodis VBF, Bährle C, Vogel F, Bokhoven JAV. Phenols and aromatics from fast
[13] Bu Q, Lei H, Wang L, Wei Y, Zhu L, Zhang X, et al. Bio-based phenols and fuel pyrolysis of variously prepared lignins from hard- and softwoods. J Anal Appl Pyrol
production from catalytic microwave pyrolysis of lignin by activated carbons. 2015;115(1):214–23.
Bioresour Technol 2014;162(162):142–7. [32] Ren Q. NOx, and N2O precursors from co-pyrolysis of biomass and sludge. J Therm
[14] Bu Q, Lei H, Ren S, Wang L, Zhang Q, Tang J, et al. Production of phenols and Anal Calorim 2013;112(2):997–1002.
biofuels by catalytic microwave pyrolysis of lignocellulosic biomass. Bioresour
Technol 2012;108(2):274–9.
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