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Dept. of Civil Engineering, University of Nebraska-Lincoln, N104 SEC P. O. Box 886105, Lincoln, NE 68588-6105, United States
h i g h l i g h t s
Four treatment process congurations for enhancing efciency of anaerobic digestion of the sludge was evaluated.
Energy balance showed that the net energy is increased with Fenton pretreatment.
The increase in energy ratio was in the following order Process-3 > Process-4 > Process-2 > Process-1.
GHG emissions are reduced for the Fenton pre-treated sludge.
a r t i c l e
i n f o
Article history:
Received 27 February 2015
Received in revised form 13 July 2015
Accepted 16 July 2015
Available online 23 July 2015
Keywords:
Fenton treatment
Anaerobic digestion
Energy balance
Geenhouse gas emissions
a b s t r a c t
Laboratory scale experiments on Fenton pre-treatment (FPT) application to the secondary sludge (SS)
were carried out to determine its effect on the anaerobic digestion (AD) efciency. The effect of FPT on
AD was evaluated by computing energy balance and corresponding greenhouse gas (GHG) emissions.
Four treatment processes were evaluated: (i) Process 1 AD of SS (control); (ii) Process 2 AD of the
Fenton pre-treated SS; (iii) Process 3 Process 2 + Fenton pre-treatment of the digestate produced in
Process 2, followed by AD (iv) Process 4 Process 1 + Fenton pre-treatment of the digestate generated
in Process 1, followed by AD. The results revealed that the cumulative methane production was increased
by 15% in Fenton pre-treatment compared to the control. The methane production rate in the control
(Process 1) was 430 m3 CH4/Mg VS degraded and it was 496 m3 CH4/Mg VS degraded for Fenton
pre-treated SS (Process 2). The net energy was increased 3.1 times with Fenton pre-treatment (Process
2) when compared to the control (Process 1). The net energy for Process 4 increased 2.5 times compared
to Process 1. The GHG emissions were reduced in Fenton pre-treatment (Process 2) compared to the
control (Process 1). The lowest GHG emissions of 0.128 Mg CO2/Mg of total dry solids (TDS) were
observed in the Fenton pre-treated sludge (Process 2). Thus Fenton pre-treatment process (mainly
Process 2) is a cost-effective, due to energy recovery and decreased GHG emissions.
2015 Elsevier B.V. All rights reserved.
1. Introduction
In recent years, sewage sludge production during wastewater
treatment in wastewater treatment plants (WWTPs) has increased
dramatically with implementation of environmental programs to
improve the quality of discharges. The annual sludge production
of the existing WWTPs in USA and Canada is estimated at
6515 103 and 550 103 Mg total dry solids (TDS) per year,
respectively [18]. In China, sludge production steadily increased
from 11 106 to 21 106 Mg per year from 2005 to 2010 (sludge
with 80% water content) [19]. Sharp rise in sludge production in
Corresponding author. Tel.: +1 (418) 654 2617; fax: +1 (418) 654 2600.
E-mail address: tyagi@ete.inrs.ca (R.D. Tyagi).
http://dx.doi.org/10.1016/j.cej.2015.07.056
1385-8947/ 2015 Elsevier B.V. All rights reserved.
286
CH4 and N2O for 100 years is about 28 and 265 times respectively,
more powerful than CO2 (Stocker et al., 2013). Alarming rates of
global warming and climate change have made it obligatory to
quantify GHG emissions from every source. The sludge management accounts for 40% of the total GHG emissions from a WWTP
[3,30].
Among the biological treatment processes, AD is considered the
most cost-effective, due to the energy recovery in the form of biogas and its very limited adverse environmental impact [1,16,21].
According to Yasui et al. [32,33], by capturing the energy from
the methane produced during AD, the total natural gas consumption can be reduced and a signicant reduction in the annual
GHG emissions can be achieved. This process can follow the framework of new regulations and meet the Kyoto protocol requirement
to reduce GHG emissions. AD of sludge is a slow process due to the
complex nature of sludge and requires longer retention time [5].
The non-availability of the easily biodegradable matter in sludge
reduces biogas production and increases the digestion time during
AD. Therefore, aiming to increase the biogas production and to
reduce digestion time various pre-treatment technologies have
been studied by different authors [5].
Sludge pre-treatment facilitates the release of intracellular
matter by rupturing the cell walls in to the aqueous phase to
increase the biodegradability and biogas production. The various
pre-treatment processes that are studied with the aim of enhancing AD efciency (increasing biogas production and achieving
reduction in retention time) can be classied as chemical (Fenton
pre-treatment, hydrogen peroxide, ozone pre-treatment, etc.),
physical, mechanical, biological and physico-chemical treatment
processes. Hydrogen peroxide, Fenton reagent, and ozone are commonly used chemicals for advanced oxidation process [4,31,9].
These chemicals are capable of oxidising the complex organic
substrates. Fenton reagent produces highly oxidizing radicals,
having oxidation-reduction potential of +2.33 V. These radicals
are stronger oxidants than hydrogen peroxide (+1.36 V) and ozone
(+2.07 V) [25,9].
Fenton pre-treatment (FPT) increases biogas (methane and
carbon dioxide) production [8,17,9] and [10], However, it is presently not clear whether the energy recovered from the produced
methane will be equivalent to the energy input required for the
pre-treatment process and AD. Thus the aim of the present study
was to evaluate the effectiveness of Fenton pre-treatment of secondary sludge for enhancing the AD efciency by computing
energy balance and corresponding GHG emissions. Moreover, four
treatment process congurations (Process 14) are considered in
this study (Fig.1).
287
Sludge
Anaerobic digestion
(AD)
Land application
(LA)
Transportation
(TP)
Dewatering
(i) Process-1
Sludge
Fenton pre-treatment
(FPT)
AD
Dewatering
(LA)
TP
(ii) Process-2
Sludge
AD
FPT
Digestate
FPT
Dewatering
AD
Stage -1
TP
LA
Stage -2
(iii) Process-3
Sludge
AD
Digestate
FPT
Dewatering
AD
TP
LA
Stage -2
Stage -1
(iv) Process-4
Fig. 1. Four process congurations considered in this study for evaluating energy balance and GHGs. AD: anaerobic digestion; FPT: Fenton pre-treatment; TP: transportation;
LA: land application.
Biogas collection
Water displacement
288
parameters that were used for evaluating the energy balance are
described below
289
Control
FPT
TS (g/L)
VS (g/L)
SS (g/L)
VSS (g/L)
TCOD (g/L)
SCOD (g/L)
30.05 (0.18)
21.76 (0.14)
26.98 (0.28)
19.31 (0.24)
33.84 (0.31)
0.82 (0.08)
30.86 (0.20)
21.21 (0.11)
21.27 (0.23)
14.46 (0.22)
33.02 (0.27)
7.80 (0.11)
Digestate
Control (A)
FPT (B)
31.04 (0.15)
18.94 (0.16)
25.66 (0.26)
17.85 (0.27)
33.83 (0.23)
1.50 (0.07)
30.81 (0.25)
18.79 (0.12)
27.88 (0.21)
17.44 (0.26)
34.05 (0.33)
1.80 (0.33)
30.76 (0.13)
17.21 (0.10)
23.34 (0.29)
15.77 (0.28)
33.65 (0.28)
6.54 (0.25)
30.64 (0.28)
18.38 (0.13)
25.53 (0.31)
15.65 (0.20)
31.33 (0.30)
7.43 (0.26)
Fig. 3. Solids degradation during anaerobic digestion. Note: (a) is the solids degradation of process 1; (b) is the solids degradation of process 2; (c) is the solids degradation for
second stage of process 3; (d) is the solids degradation for second stage of process 4.
290
VS added. Thus, Fenton pre-treatment enhanced methane production by 15% compared to the raw sludge digestion. These results
are in line with those reported by Erden and Filibeli [10], where
19.4% higher methane production was obtained compared to raw
sludge. The increase in the SCOD increases the methane production
[10]. Erden and Filibeli [9] concluded that the specic methane
production increased during the rst 20 days of digestion in the
digester containing Fenton pre-treated sludge. During Fenton
pre-treatment, cell lysis initially occurs and releases extra cellular
polymeric substance (EPS), which is further broken down into the
fractions (proteins, carbohydrates, lipids, etc.). These proteins are
degraded during the operation time in the digesters and produce
biogas. For the Fenton pre-treated sludge (Process 2), the methane
production for FPT was higher at all retention times compared to
the control (Process 1) (Fig. 4).
During Stage 2 AD (Fig. 1), higher methane production was
observed for Process 4 compared to Process 3 (Fig. 4). For Process
3, during Stage 1, FPT has solubilized the SS and has enhanced
the methane production (due to high solids degradation, Fig. 3b)
during AD. Furthermore, during Stage 2, the solids that are not
easily biodegraded were subjected to FPT, resulting in solubilization and methane production (due to biodegradation of solids, as
shown in Fig. 3c).On the other hand, during Stage 2, of Process 4
were subjected to AD and the methane production was not high
(due to low solids degradation, see Fig. 3a). The solids that are
not biodegraded during AD (Stage 1, for 30 days) were subjected
to FPT resulting in solids solubilization and increased methane production due to biodegradation of solids in second stage of AD
(Process 4). The cumulative methane volume produced during
Stage 2 AD of Process 4 at 30 days retention time was
3.57 103 m3 at an average production rate of 0.574 m3 CH4/kg
VS destroyed. In contrast, the cumulative methane volume produced during Stage 2 AD of Process 3 at 30 days retention time
was 2.48 103 m3 at an average production rate of 0.462 m3
CH4/kg VS destroyed. Therefore, from the results it is clear that
Fenton pre-treatment enhances methane production; moreover,
it enhances the solids degradation of the digestate as well as the
corresponding methane production. The efciency of four treatment processes in generating methane followed the Process
3 > Process 4 > Process 2 > Process 1 pattern. However, in terms
of the m3 CH4/kg VS destroyed, Process 3 > Process 2 > Process
4 > Process 1 was noted.
3.4. Energy balance of the different process
Energy balance of Process 1 and 2 was evaluated by assuming
40 Mg of TDS per day to be treated during AD process. The energy
input for AD, Fenton pre-treatment, dewatering the digested solids,
transporting the dewatered solids from the WWTP to the land
application site and during land application was calculated. The
energy output from the methane was calculated based on the
energy value given in Section 2.8. The net energy computed for
Process 1 and 2, is presented in Table 2. The energy balance of
Stage 1 of Process 3 and 4 was evaluated by assuming 40 Mg of
TDS, while, for Stage 2 the solids generated after 30 days of digestion (from Process 1 and 2, respectively) were considered.
The energy input for the AD was higher for the control sludge
compared to the pre-treated sludge, since the sludge temperature
after Fenton pre-treatment increased from 12 (2)C to 25 (3)C.
For the control, the energy input for increasing sludge temperature
that required for digestion was 893 kWh/Mg of TDS while it was
378 kWh/Mg of TDS for the Fenton pre-treated sludge. The energy
required for dewatering, transportation and land application was
not reduced for the Fenton pre-treated sludge (Process 2) as compared to the control (Process 1) (Table 2). For the control (Process
1), the total VS solids mass was 28.96 Mg (and 11.04 Mg inert
Table 2
Energy balance for the different process.
Description
Process-1
Process-2
Process-3
Process-4
491
982
893
378
756
1271
50
943
49
427
98
854
99
1370
63.6
43.7
221
1271
1362
64.5
44.3
224
1250
1535
39.5
27.2
137
2040
2222
50.7
34.8
175.8
2123
2353
91
285
182
231
1.07
1.23
1.08
1.11
491
Note: negative sign indicates increase energy input; Mg is mega gram; TDS is total
dry solids; AD: anaerobic digestion; indicates that for process 3 and 4, stage 1 and
stage 2 AD was combined during computations.
291
The energy ratio was higher for the Fenton pre-treated sludge
(Process 2) than the control (Process 1). Evaluation of the energy
ratio at different solids retention times revealed that Process 2 is
more benecial compared to Process 1 (Fig. 5). For example, at
20 days digestion, for Process 1, the energy ratio was 0.78, while
it was 0.96 for Process 2. More specically, the total energy input
for Process 1 was 1308 kWh/Mg of TDS and the energy recovery
was 1011 kWh/Mg of TDS. In contrast, for Process 2, the total
energy input was 1291 kWh/Mg of TDS and the energy recovery
was 1238 kWh/Mg of TDS. The energy ratio of Process 3 and 4
was high compared to Process 1. For example, in Process 3, at
15 days digestion (i.e., 30 days digestion during Stage 1 + 15 days
digestion for Stage 2), the energy ratio was 0.73 and was 0.69 for
Process 4. The increased energy ratio was due to higher solids
degradation and methane production. More specically, for
Process 3, the solids have degraded from 40 Mg of TDS to
15.03 Mg of TDS during the two-stage digestion. Thus, in order
for the energy ratio to exceed one and the net energy to be positive,
a minimum of 30 days operation time is required. The following
order was observed with respect to increasing the energy ratio:
Process 2 > Process 4 > Process 3 > Process 1.
3.5. Dewaterability of sludge (control, FPT, Fenton treated digestate)
Dewaterability, measured in terms of CST, was 1006 (12) s and
120 (15) s, for the control and Fenton pre-treated respectively.
Zhen et al. [35] observed a 97.7% CST reduction with Fenton
pre-treatment (H2O2 178 mg/g of VSS and Fe2+ 211 mg/g of VSS).
The release of sludge bound water due to the disintegration of
sludge ocs, cell lysis and breakdown of the EPS during Fenton
pre-treatment has reduced the CST [35,9]. It is clear that the
Fenton pre-treatment process reduces the CST and hence increases
the sludge dewaterability. The dewaterability of anaerobic digestate after 30 days digestion for the control and the Fenton
pre-treated sludge was 820 (19) s and 106 (8) s, respectively.
AD of sludge (both control and Fenton pretreated sludge) further
improved sludge dewaterability (reduced the CST). The increase
in sludge dewaterability after AD was due to the solids reduction
(% VS degradation for the control after 30 days digestion was
51.46%). The CST of the Fenton pre-treated digestate generated
from Process 1 and 2 was 145 (12) s and 87 (11) s, respectively.
The CST of the digestate generated after AD in Process 1 and 2 was
further reduced to 138 (6) s and 80 (8) s, respectively. Fenton
pre-treatment of digestate has reduced the CST value as well as
increased dewaterability. The increase in dewaterability (or reduction in the CST value) after the AD process will reduce the energy
Table 3
GHG emissions evaluated for different process.
Description
Process-2
Process-3
Process-4
48.0
150.7
96.5
122.2
304.8
250.6
392.5
511.4
314.6
354.5
513.3
543.6
19.3
19.3
7.5
9.6
94
95
58
75
192
128
366
356
Note: negative sign indicates reduction in GHG emissions; Mg is mega gram; TDS is
total dry solids.
Fig. 5. Energy ratio at different solids concentration. Note: for process 3 and 4, stage
1 and stage 2 are included.
292