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h i g h l i g h t s
" Microwave irradiation enhanced the disintegration and digestibility of microalgae.
" Algal biomass solubilisation increased by 800% with microwave pretreatment.
" The main parameter inuencing biomass solubilisation was the applied specic energy.
" Increased biogas production rate (2775%) and yield (1278%) with pretreated biomass.
" Linear correlation between microalgae solubilisation and biogas yield.
a r t i c l e
i n f o
Article history:
Received 2 October 2012
Received in revised form 14 February 2013
Accepted 17 February 2013
Keywords:
Anaerobic digestion
Biofuel
High rate algal pond
Methane
Renewable energy
a b s t r a c t
The aim of this study was to evaluate the effect of microwave pretreatment on the solubilisation and
anaerobic digestion of microalgaebacterial biomass cultivated in high rate algal ponds for wastewater
treatment. The microwave pretreatment comprised three specic energies (21,800, 43,600 and
65,400 kJ/kg TS), combining three output power values with different exposure times. Response surface
analysis showed that the main parameter inuencing biomass solubilisation was the applied specic
energy. Indeed, a similar solubilisation increase was obtained for the same specic energy, regardless
of the output power and exposure time (280350% for 21,800 kJ/kg TS, 580610% for 43,600 kJ/kg TS
and 730800% for 65,400 kJ/kg TS). In biochemical methane potential tests, the initial biogas production
rate (2775% increase) and nal biogas yield (1278% increase) were higher with pretreated biomass. A
linear correlation was found between biomass solubilisation and biogas yield. It can be concluded that
microwave irradiation enhanced the disintegration and digestibility of microalgae.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
During the last decade, there has been a growing interest in
investigating the energy potential of biofuels obtained from microalgae cultures [1]. The high lipid content of microalgae makes them
an alternative to terrestrial energy crops for biodiesel production.
However, microalgae cultures and energy production are at an initial research phase. According to the literature, the cultivation of
microalgae to produce biofuels has a number of requirements that
limit its current implementation at industrial scale [2]. To make it
economically feasible, massive biomass production and energy
generation technologies must be addressed.
The cultivation of certain specic strains of microalgae is not
viable in economic and environmental terms, since freshwater
and fertilizers are needed. In contrast, if microalgal biomass is
Corresponding author. Tel.: +34 934016463; fax: +34 934017357.
E-mail address: ivet.ferrer@upc.edu (I. Ferrer).
0306-2619/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2013.02.042
169
hydraulic retention time (HRT) (364 days). This value is commensurate with biogas production from other substrates. For instance,
the specic methane production of waste activated sludge, another
by-product of wastewater treatment, ranges between 0.15 and
0.3 L CH4/g VS [8]; and that of lignocellulosic agricultural crops,
such as maize, wheat, rice and sugarcane wastes, between 0.28
and 0.34 L CH4/g VS [9].
The complex cell wall structure of microalgae, composed by cellulose, hemicellulose and pectin, makes bacteria attack difcult
[1]; suggesting that biomass pretreatment is necessary for the feasibility of microalgae anaerobic digestion [10]. The pretreatment of
substrates to increase the anaerobic biodegradability has been the
subject of intense research in recent years. Physical, chemical and
biological processes have proven successful at improving the disintegration and anaerobic biodegradability of lignocellulosic biomass
[11]. Furthermore, waste activated sludge pretreatment using
mechanical, thermal and biological processes increased the specic
methane production, leading to positive energy balances, and is
currently applied in full scale facilities [12]. The few studies that
have so far been conducted with microalgae show an increased
methane yield after thermal and ultrasound pretreatments [13
16].
The electromagnetic radiation of microwaves has also been
investigated as a pretreatment process [1719]. Microwaves are
short waves of electromagnetic energy varying in a frequency from
300 MHz to 300 GHz, which can increase the kinetic energy of the
water leading to a boiling state [17]. The quantum energy applied
by microwave irradiation is not capable of breaking down chemical
bonds, however hydrogen bonds are or can be broken [20]. Induction heating and dielectric polarization result in changes in the secondary and tertiary structure of proteins and cause cell hydrolysis.
The polarization of macromolecules occurs by a consistent rotation
through an alternating electric eld. This process is inuenced by
microwave frequency, radiation time, biomass concentration and
penetration depth [18].
The literature on microwave pretreatment of waste activated
sludge under different conditions [18,2125], shows how the process enhanced sludge solubilisation and/or cumulative gas production in anaerobic batch tests (Table 1). Microwave irradiation can
produce both thermal and athermal effects. Some authors have
compared microwave and thermal pretreatments, observing higher volatile solids and hemicellulose solubilisation [19] and biogas
production [26] with the former. So far, the effect of microwave
irradiation on microalgae remains unexplored.
Thus, the objective of this study was to evaluate the effect of
microwave pretreatment on the disruption and anaerobic biodegradability of microalgal biomass from HRAP for wastewater
treatment.
Table 1
Effect of microwave pretreatment on activated sludge solubilisation and biochemical methane potential tests.
Pretreatment conditions
14.3 min; 400 W; 102 C; 2.3% TS
5 min; 800 W; 13,000 kJ/kg SS
5 min; 96 C; 5.5% TS
Progressive heating 1.21.4 C/min;
175 C
0.83 kJ/ml; 1000 W; 78% TS
1168 W; 90 C; 4% TS
Batch test
conditions
55 C; 32 d
33 C; 23 d
33 C; 18 d
35 C; 2025 d
35 C; 22 d
Results
Increase
Increase
rate*
Increase
Increase
References
of 17.9% in the CODs/COD ratio*
of 311% in the VSs/VS ratio and no difference in biogas production and production
[18]
[21]
of 143% in the CODs/COD ratio and 211% in the cumulative biogas production*
of 74.3% in COD solubilisation and 34% in biogas production*
[22]
[23]
[24]
[25]
Note: TS: total solids, SS: suspended solids, VS: volatile solids, VSs: soluble volatile solids, COD: chemical oxygen demand, CODs: soluble chemical oxygen demand.
Compared to control.
170
Table 2
High rate algal pond performance from March 2011 to March 2012. Mean values (standard deviation) from samples taken at 2 PM.
Parameter
% Removal
pH
Temperature (C)
DO (mg/L)
Turbidity (NTU)
TSS (mg/L)
COD (mg/L)
TKN (mg/L)
NH4N(mg/L)
6.8 (0.8)
22 (4)
0.5 (0.7)
60 (34)
250 (57)
50 (12)
35 (11)
8 (1.1)
20 (7)
8 (4)
12 (9)
400 (130)*
80 (49)
20 (6)
2 (1.2)
87
68
60
95
Note: DO: dissolved oxygen, TSS: total suspended solids, COD: chemical oxygen demand, TKN: total Kjeldahl nitrogen, NH4N: ammonia nitrogen.
Not ltrated sample.
Table 3
Harvested microalgal biomass characteristics.
Parameter
pH
TS (% (w/w))
VS (% (w/w))
VS/TS (%)
VSs (% (w/w))
VSs/VS (%)
COD (g/L)
CODs (g/L)
CODs/COD (%)
TKN (mg/kg)
NH4N (mg/L)
Lipids (% (w/gTS))
Proteins (% (w/g TS))
Carbohydrates (% (w/g TS))
7.5 (0.8)
1.65 (0.2)
0.98 (0.2)
60 (0.9)
0.012 (0.002)
0.89 (0.11)
16.7 (0.42)
0.12 (0.02)
0.72 (0.44)
800 (180)
12 (7)
17.4 (1.50)
49.3 (1.23)
19.5 (1.87)
Note: TS: total solids, VS: volatile solids, VSs: soluble volatile solids, COD: chemical
oxygen demand, CODs: soluble chemical oxygen demand, TKN: total Kjeldahl
nitrogen, NH4N: ammonia nitrogen.
The response surface methodology was used to analyse the relation between pretreatment conditions and biomass solubilisation
by means of a second order polynomial expression, as proposed
by other authors [18,21]. Experimental results were evaluated by
tting the second order polynomial expression (Eq. (4)), where Yi
corresponds to experimental results (VSS/VS ratio); and X1 and X2
to the microwave output power (300, 600 and 900 W) and exposure time (19 min), respectively.
The anaerobic biodegradability of pretreated microalgal biomass was compared to the control (untreated biomass) by means
of mesophilic (35 C) batch tests. Pretreatment conditions are summarized in Table 4. The inoculum was mesophilic sludge from a
full-scale anaerobic digester located in a municipal wastewater
treatment plant near Barcelona (Spain). Each treatment was performed in duplicate.
Serum bottles had a total volume of 160 mL and a useful volume
of 100 mL. The concentration of substrate was 16.7 g COD/L, corresponding to 29.94 g microalgal biomass/bottle. As recommended
by Cho et al. [28], the substrate/inoculum ratio was 0.5 g COD/g
VS, corresponding to 43.48 g sludge/bottle. The bottles where
ushed with Helium gas (He), sealed with butyl rubber stoppers
and incubated at 35 C until biogas production ceased.
Biogas production was periodically determined by measuring
the pressure increase with an electronic manometer (Greisinger
GMH 3151). After each measurement gas was released until atmospheric pressure. Samples from the headspace volume were taken
every 23 days, to determine biogas composition (CH4/CO2) by gas
chromatography.
Accumulated volumetric methane production (mL) was calculated from the pressure increase and methane content in biogas,
expressed under standard conditions. The net values of methane
production and yield were obtained by subtracting the endogenous
production of the blank bottle.
2.5. Analytical methods
All analyses were triplicated and results are given as mean values. The following parameters were determined from the inuent
and efuent of the HRAP: total suspended solids (TSS), total chemical oxygen demand (COD), ammonia nitrogen (NH4N) and total
Kjeldahl nitrogen (TKN), according to Standard Methods [29].
Water temperature and dissolved oxygen (DO) were measured
in situ with an YSI 58 oxymeter. Turbidity was determined with
a Hanna Microprocessor Turbidity Meter HI93703 and pH was
determined with a Crison Portable 506 pH-meter.
Microalgal biomass was characterised by the concentration of
total solids (TS), VS, COD, CODs, NH4N, TKN, determined according
to Standard Methods [29]. The lipid content was determined by the
Soxhlet extraction method [29]. A TKN to protein conversion factor
of 5.95 was used [30]. Carbohydrates were determined by phenol
sulfuric acid method after acid hydrolysis and measured by spectrophotometry (Spectronic Genesys 8). Microalgae identication
171
Temperature (C)
VSs/VS ratio
Control
T1
T2
T3
T4
T5
T6
T7
T8
T9
21,800
21,800
21,800
43,600
43,600
43,600
65,400
65,400
65,400
300
600
900
300
600
900
300
600
900
3.0
1.5
1.0
5.0
3.0
2.0
9.0
4.5
3.0
50
58
56
81
86
92
95
98
98
0.0089
0.034
0.040
0.040
0.061
0.062
0.063
0.075
0.074
0.081
280
345
346
580
597
606
742
728
799
172
0,10
0,08
0,06
R2= 0,96
0,04
0,02
0,00
0
10000
20000
30000
40000
50000
60000
70000
Previous studies have adjusted a quadratic equation for describing the inuence of pretreatment conditions on biomass solubilisation, for instance the sludge thermal pretreatment [21] and
microwave pretreatment [18]. However, in our quadratic model
Pr values were all higher than 0.05. Since the interaction between
output power and exposure time coefcient (Xpower Xtime) was the
main factor inuencing biomass solubilisation, a simplied model
was proposed instead (Eq. (6)). In this simple model, both coefcient terms had Pr values lower than 0.05, indicating a signicant
tting (Table 5).
As summarized in Table 5, R2 values were similar for the quadratic and simplied models (0.98 and 0.96, respectively), indicating that the interaction between output power and exposure time
(Xpower Xtime) (i.e. simplied model) explained most of the variability. Moreover, the simplied model p-value (4.12 106) was
much lower than the quadratic model p-value (9.29 103).
According to this, the applied specic energy (Eq. (2)) was the main
factor inuencing biomass solubilisation. Therefore, the simplied
model could be expressed in terms of specic energy (Eq. (7)) by
introducing the total solids into Eq. (6), where Xspecic energy is the
applied specic energy and XTS the total solids content in biomass.
Table 5
Comparison between quadratic and simplied model coefcients.
Parameters
Estimate value
Std. error
t value
Pr
Quadratic model
Simplied model
Intercept
X 2power
X 2time
Xpower
Xtime
Xpower Xtime
Intercept
Xpower Xtime
1.627e02
3.100e02
0.525
0.636
2.579e08
4.200e08
0.614
0.583
1.422e07
1.316e07
1.081
0.359
6.726e05
7.002e05
0.961
0.408
1.519e04
1.337e04
1.136
0.338
2.043e07
1.406e07
1.453
0.242
2.022e02
3.272e03
6.18
0.000454
3.589e07
2.805e08
12.80
4.12e06
Quadratic model: R2 = 0.98, p-value = 0.009289, F = 29.7; simplied model: R2 = 0.96, p-value = 4.122e06, F = 163.8.
173
Table 6
Microwave pretreatment conditions and biogas production in biochemical methane potential tests. Mean values (standard deviation).
Trial
Output power
(W)
Temperature
(C)
Control
T1
T2
T3
T4
T5
T6
T7
T8
T9
21,800
21,800
21,800
43,600
43,600
43,600
65,400
65,400
65,400
300
600
900
300
600
900
300
600
900
50
58
56
81
86
92
95
98
98
50.08
63.69
68.50
73.25
66.06
68.16
67.44
78.65
84.11
87.76
172.48
194.06
207.47
219.54
222.63
238.83
244.50
275.76
295.97
307.11
68.2
68.4
68.4
68.5
68.3
68.3
68.4
68.3
68.2
68.4
(1.16)
(1.70)
(0.34)
(0.83)
(0.39)
(3.36)
(0.78)
(4.67)
(0.24)
(1.70)
(2.95)
(5.84)
(4.67)
(3.36)
(3.06)
(2.04)
(1.31)
(0.58)
(1.17)
(2.92)
(0.11)
(0.31)
(0.21)
(0.03)
(0.07)
(0.03)
(0.01)
(0.08)
(0.06)
(0.23)
174
320
300
280
R= 0,85
260
240
220
200
180
200
300
400
500
600
700
800
900
biomass cultivated in HRAP. The main parameter inuencing biomass solubilisation was the applied specic energy. A similar solubilisation increase was obtained for the same specic energy,
regardless of the output power and exposure time (280350% for
21,800 kJ/kg TS, 580610% for 43,600 kJ/kg TS and 730800% for
65,400 kJ/kg TS). This pretreatment increased the biogas production rate (2775%) and nal biogas yield (1278%) in BMP tests.
Therefore, microwave irradiation enhanced microalgae solubilisation, accelerating the anaerobic digestion rate and increasing the
methane production potential. However, the pretreatment of concentrated biomass seemed imperative to obtain a positive energy
balance. Besides, less energy consuming pretreatment techniques
ought to be investigated.
Acknowledgements
Table 7
Energy ratio of microalgal biomass under different microwave pretreatment
conditions.
Trial
VS content (%
(w/w))
Energy input
(kJ/kg VS)
Energy output
(kJ/kg VS)
Energy ratio
(Ei/Eo)
T1
T2
T3
T4
T5
T6
T7
T8
T9
0.98
0.98
0.98
0.98
0.98
0.98
0.98
0.98
0.98
36,700
36,700
36,700
73,400
73,400
73,400
110,200
110,200
110,200
525.3
851.8
1145.6
1220.9
1615.2
1753.3
2514.2
3006.2
3277.4
69.9
43.1
32.0
60.1
45.4
41.9
43.8
36.7
33.6
175