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Chemical Engineering Journal 283 (2016) 285–292

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Chemical Engineering Journal
journal homepage: www.elsevier.com/locate/cej

Fenton pre-treatment of secondary sludge to enhance anaerobic
digestion: Energy balance and greenhouse gas emissions
Sridhar Pilli a, T.T. More a, S. Yan a, R.D. Tyagi a,⇑, R.Y. Surampalli b
a
b

INRS Eau, Terre, Environnement, 490, rue de la Couronne, Québec G1K 9A9, Canada
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 configurations for enhancing efficiency 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) efficiency. 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.
Ó 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/Ó 2015 Elsevier B.V. All rights reserved.

the near future is expected due to high water demand caused by
rapidly increasing population, industrialization, and urbanization,
as well as to higher levels of wastewater treatment. The cost
associated with sludge management is around 50–60% of the total
WWTPs operating costs [27,7]. In developed countries, the most
common sludge treatment methods are aerobic digestion, anaerobic digestion (AD) and composting [2,14]; and the most common
disposal methods are incineration, landfill, or land application.
Depending upon the environmental conditions during sludge
treatment and disposal, the organic matter present in sludge is
transformed to CO2, CH4, and N2O. These gases are considered as
the principal greenhouse gases (GHGs). Carbon dioxide was used
as the basis to compute the level of relative contribution to global
warming potential of each gas. The global warming potential of

suspended solids (SS). which consumed 35 L of diesel/100 km [11]. the same distance between the WWTPs and the land application site was adopted. According to Yasui et al. Next. respectively).16.9] and [10]. Fenton reagent. Sludge dewatering requires higher energy. Upon collecting the samples. therefore. 15.286 S.1. To remove the air from the headspace of the bottles and maintain the anaerobic conditions. and ozone are commonly used chemicals for advanced oxidation process [4. [32.21]. four treatment process configurations (Process 1–4) are considered in this study (Fig. 0. [28] concluded that thermal pre-treatment process was energetically self-sustainable and produced surplus energy at solids concentration greater than 30 g/L.2.35]. the digested sludge was returned into the bottles for further digestion and anaerobic conditions were maintained by sparging nitrogen. However. due to the energy recovery in the form of biogas and its very limited adverse environmental impact [1. The various pre-treatment processes that are studied with the aim of enhancing AD efficiency (increasing biogas production and achieving reduction in retention time) can be classified as chemical (Fenton pre-treatment.5. The total solids (TS) of the collected sludge after gravity settling was measured at 1. the pH of sludge samples was adjusted to pH 3 using 10 N–H2SO4. Sludge disposal Land application of dewatered sludge digestate was considered in this study (Fig. Wastewater sludge Secondary wastewater sludge was collected from municipal wastewater treatment plant (WWTP) Communauté urbaine de Québec (CUQ) (Beauport. 2. therefore. 20 and 30). aiming to increase the biogas production and to reduce digestion time various pre-treatment technologies have been studied by different authors [5]. / Chemical Engineering Journal 283 (2016) 285–292 CH4 and N2O for 100 years is about 28 and 265 times respectively. Among the biological treatment processes. To evaluate the energy balance. 5.9]. biological and physico-chemical treatment processes. Therefore. The WWTP consists of primary clarification.). (corresponding to Process 3 and Process 4. volatile solids (VS). Fenton treatment of sludge Initially. Fenton pre-treatment (FPT) increases biogas (methane and carbon dioxide) production [8. This process can follow the framework of new regulations and meet the Kyoto protocol requirement to reduce GHG emissions. The AD was carried out for 30 days. These radicals are stronger oxidants than hydrogen peroxide (+1. The CST was determined by using a CST instrument (Triton electronics. Each digester bottle was inoculated with anaerobic sludge (100 mL) collected from Valcartier. the nitrogen gas was sparged through sludge for 2 min. These chemicals are capable of oxidising the complex organic substrates. Moreover. The water level in the water bath was adjusted to the sludge height in the bottles. to evaluate the degradation.07 V) [25.9]. The initial pH of sludge was adjusted to 7 with NaOH solution (4 N). 2. Materials and methods 2. in the second step. therefore. and volatile suspended solids (VSS) were analysed for all processes (1-4) at different digestion times (day 0. Dewaterability Fenton pre-treatment of sludge enhances its dewaterability [25. The working volume of each digester bottle was 800 mL.36 V) and ozone (+2. The AD of the Fenton pre-treated digestate (i.1).e. AD is considered the most cost-effective. Capillary-suction-time (CST) was used to measure the dewaterability.4. ozone pre-treatment. having oxidation-reduction potential of +2. The sludge was stored at 4 °C for further use.31. Essex) with 10-mm diameter [29].33]. Pilli et al. Therefore. more powerful than CO2 (Stocker et al. solids concentration of 30 g/L was considered. physical. hydrogen peroxide. 1). it was considered that dewatered sludge was transported using 3-axle semi-trailers vehicles. etc. in this study. 10.17. The Fenton pre-treatment of the concentrated digestates generated from Process 2 and Process 1 was carried out as described in Fig.12 g . In Quebec.33 V.. 2013). Anaerobic digestion AD was performed in 1000 mL digester glass bottles placed in a water bath at 35 °C having a provision to collect biogas. 2. Fenton reagent produces highly oxidizing radicals.. Pre-treatment enhances the AD and reduces the retention time [27]. Canada). 2.3. Quebec City. 2. H2O2 and FeSO4 stock solution (60 g H2O2/kg TS and 0. mechanical. Moreover. total solids (TS). Dunmow. The sludge management accounts for 40% of the total GHG emissions from a WWTP [3. Pilli et al. The bottles were rotated manually twice a day to minimize the effects of settling during AD. Samples were collected for analysis by transferring the digested sludge from the bottles into a beaker.07 g Fe2+/g H2O2.5 g/L and TS concentration was increased by centrifugation at 1600  g for 3 min (Sorvall RC 5C plus Macrocentrifuge (rotor SA-600)). the total natural gas consumption can be reduced and a significant reduction in the annual GHG emissions can be achieved. Quebec. Therefore.30]. model 304 M CST. Alarming rates of global warming and climate change have made it obligatory to quantify GHG emissions from every source. by capturing the energy from the methane produced during AD. more than 80% of the farmers or agricultural lands are located no more than 50 km away from the industries [11]. 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. Process 3 and 4) was also performed in glass bottles (Fig. GHG emissions values corresponding to diesel use were equivalent to 2730 g CO2/L of diesel. the digestates produced from Process 1 and Process 2 after 30 days of digestion was centrifuged to achieve total solids concentration of 30 g/L. the samples were stirred at 150 rpm for 1 h at ambient temperature to carry out the Fenton oxidation. respectively) was added to the acidified sludge samples (of 1 L volume) to initiate the Fenton oxidation reaction. it was diluted with demineralised water to achieve the required TS concentration of 30 g/L. The non-availability of the easily biodegradable matter in sludge reduces biogas production and increases the digestion time during AD. The concentrated sludge obtained after centrifugation exceeded 30 TS g/L. According to Erden and Filibeli [9]. AD of sludge is a slow process due to the complex nature of sludge and requires longer retention time [5]. Hydrogen peroxide. secondary biological treatment (without nutrient removal) and tertiary treatment. 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. Thus the aim of the present study was to evaluate the effectiveness of Fenton pre-treatment of secondary sludge for enhancing the AD efficiency by computing energy balance and corresponding GHG emissions. as well as homogenized in a WaringTM blender for 30 s. in this study. 1. 2). dewaterability determination of the pre-treated anaerobic digested sludge was necessary for evaluating the energy balance and GHG emissions. Canada.

08 g N2O/L of diesel [11]. The . and 0. CH4/L of diesel. Energy balance The energy balance was evaluated for Process 1 and Process 2. 2.287 S.25 Mg CO2/Mg of dry solids (negative sign indicate reduction of GHG emissions). FPT: Fenton pre-treatment. Four process configurations considered in this study for evaluating energy balance and GHGs. AD: anaerobic digestion. 1178–1185). and 0. 0. Anaerobic digestion setup. Sceptic glass bottles Biogas collection Water displacement Fig. the energy required during the land application of TDS was set at 351.07 Mg CO2 equivalent/Mg of TDS. 1.68 kWh/Mg of TDS [34].03 Mg CO2 equivalent/Mg of TDS respectively [3]. LA: land application. / Chemical Engineering Journal 283 (2016) 285–292 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. The CO2. For Process 3 and 4 the energy balance was evaluated for Stage 1 (AD of the control and Fenton pre-treated sludge) and Stage 2 (the digestate generated from Process 1 and 2) after 30 days was further Fenton pre-treated and digested for another 30 days). Pilli et al. 2.6. and N2O emissions due to the land application of digestate were evaluated based on 0. CH4. TP: transportation. Further.

and VSS) on the 5th.5 g/L.225  103 Mg of TDS/m3 of treated wastewater [12. A decrease in the solids solubilization was expected. soluble chemical oxygen demand (SCOD). wastewater treatment plant having treatment capacity of 47. as described in Fig. 20th. it is clear that the solids degradation was much faster for the Fenton pre-treated sludge. and VSS solids degradation which was assessed on the 5th.73% for Fenton pre-treated sludge (Fig. as they are considered (by convention) ‘‘carbon neutral’’ (global warming potential equal to zero) [26]. Thus the quantity of secondary sludge generated per day was 40 Mg.7 kWh/kg of H2O2 [23] and in Fe2+ 6. namely 0.07 Mg CO2 equivalent per Mg of TDS. Brown et al. and 30th day during AD (of Stage 2. and 0.2.7. 3b). The SS of the digestate (control) was reduced from 25. [3] provided factors for determining the potential GHG emissions for AD followed by land application of sludge. AD.03 Mg CO2 equivalent per Mg of TDS. dewatering. Fenton pre-treatment of the . The biogas produced during the AD was collected and analysed using Gas chromatograph (Shimadzu GC 14A) as per the procedure given in the Cui and Jahng [6]. / Chemical Engineering Journal 283 (2016) 285–292 parameters that were used for evaluating the energy balance are described below Total energy input ¼ X energy containing in the chemicals. 3c and d. VS. pH. The CO2. CH4.037 g H2O2/ g Fe2+/100 mL [24]. the biomass was biodegraded to CO2 and CH4. Moreover. it is clear that digestate (generated from Process 1 and 2) percentage solubilization of the SS and VSS was lower compared to the secondary sludge solubilization (raw sludge used in Process 1). 3b. in Process 1 there was not pre-treatment.e. The methane combustion generated CO2 (Eq. contributing to the GHG emissions.25 Mg CO2 per Mg of TDS (i. The increase of SCOD was due to the SS and VSS solubilization during the Fenton pre-treatment. From the results (Table 1) it is clear that solubilization of SS.27 g SS/L (21% solubilization).79 MJ/m3 CH4 [20]. GHG emissions The energy required for Fenton pre-treatment. 3 is less than 5%. VSS. Therefore. and N2O emissions from the land application of digestate were estimated using these factors. The percentage error of data presented in Fig. [8]. 15th.66 g SS/L to 23. Therefore.42 to 2.. 3a) was 9. as discussed later in this manuscript. For Fenton pre-treated digestate (generated from Process 2) the solubilization of SS was 8% only. 3.94 kWh/kg of Fe2+ [15] was considered in evaluating the energy input during Fenton pre-treatment. Further. Similar trend was observed by Dewil et al. the VS solids percentage degradation in the control (Fig. The energy embedded in the hydrogen peroxide was set at 7. The efficiency of Fenton pre-treatment was assessed in terms of SS. carbon dioxide emissions during AD were not taken into account in national protocols. Land application (forest land) of sewage sludge also generated GHG emissions. fuels. 2006). VS. energy balance computations still need to be carried out to determine the operation time at which AD can be energetically beneficial. SS. 2. the SCOD of the raw sludge increased from 0. 1) (Process 3 and 4)..53 kg CO2/kWh (developed by Environment Canada study based on the Resources for the Future (RFF) model). (4)). Carbon dioxide emissions generated from biological pathways were considered as biogenic emissions. it is clear that Fenton pre-treatment enhances solids degradation and reduces retention time. and 30th day during AD and the results are summarized in Fig. The biogas volume was measured based on the water displacement method. All the data are presented in Table 1. transportation and land application was generated from the fossil fuels. and total chemical oxygen demand (TCOD) were carried out for Process 1–4 following the standard methods (APHA. 15th.98 g SS/L to 21. i. 1) is represented in Fig. used in the Process for Fenton pre-treatment.82 g/L to 7. since most of the biodegradable solids were solubilized and degraded during AD. SS. Land application of sludge refers to the spreading of sludge on or just below the soil surface. Thus. Pilli et al. Fenton pre-treated sludge (Process 2). However.1. Solubilization of SS and Fenton pre-treated SS and anaerobic digestate (generated from Process 1 and 2) The characteristics of secondary sludge (control. based on these results. The solids degradation (TS.34 g SS/L (9% solubilization) and VSS solubilization was only 12%. As can be seen. The sludge production rate during secondary wastewater treatment was considered as 0. considering the heating value of methane of 31. solids are solubilized during Fenton pre-treatment and degraded during AD. The overall total solids degradation after 30 days increased by 3% for Fenton pre-treated sludge compared to the control. digestate generated from Process 1. and organic matter (SCOD) solubilization [22]. respectively. VSS. Results and discussion AD. carbon sequestration due to the land application of sludge). compared to 14. and electricity. 1) corresponding to energy utilization were computed using national emission intensity coefficient 0. 10th. From Fig. whereas. The energy from the methane was recovered by using cogeneration unit (combined heat and power). SS. 20th.288 S. and Fig. and VSS was decreased from 19. The GHG emissions in various process steps (Fig. During AD. Calgary. 3. In Process 2.e. Canada) was considered. Analytical methods The analysis of TS. Process 1). VS.13]. the Fenton pre-treated digestate (generated from Process 1) was more degradable compared to Fenton pre-treatment of the digestate generated from Process 2. Sludge yielded a considerable release of dissolved solids and organic matter in the liquid phase (three to four folds of the concentration in control) by addition of 0. 3.8 g/L. 0. The suspended solids of raw sludge were decreased from 26. Anaerobic digestion The AD efficiency was evaluated based on TS. with Fenton pre-treatment (50 g H2O2/kg DS) the SCOD increased from 0. transportation and land application ð1Þ Energy output = energy obtained from the methane produced. 3 is representative of all samples measured in triplicates.000 m3 of wastewater per day (corresponding to Bonnybrook WWTP. The energy recovered from the methane was evaluated by 3. digestate produced from Process 2 and Fenton pre-treated of the digestate (Process 3 and 4) are presented in Table 1. VSS and SCOD was improved by Fenton pre-treatment. Net energy ¼ energy output  energy input ð2Þ Energy ratio ¼ energy output=energy input ð3Þ For computing the energy balance. 10th.46 g VSS/L (25% solubilization). CH4 þ 2O2 ! CO2 þ 2H2 O þ energy ð4Þ 2. The digestate of the control and Fenton pre-treated sludge was further subjected to Fenton pre-treatment and AD (Fig. At operation time of 5 days. dewatering.8.31 g VSS/L to 14.74%.

12) 27. control digestion improved [9].22) 33.13)%.16) 25. Similarly.14) 26. / Chemical Engineering Journal 283 (2016) 285–292 Table 1 Sludge characteristics before and after Fenton pre-treatment. (d) is the solids degradation for second stage of process 4.07) 30. at 30 days operation time.86 (±0.31) 0.11) 21. whereas.28) 19. respectively. Note: (a) is the solids degradation of process 1.and two.43 (±0.15)% and 52.11) Digestate FPT of the digestate Control (A) FPT (B) Generated from (A) Generated from (B) 31.6  103 m3 at an average production rate of 0. therefore. After evaluating single. the cumulative methane volume is for the second stage of AD.26) Note: control is without pre-treatment.3. it is evident that the cumulative methane production was higher in the latter (Process 2). 1) was 52.04 (±0.28) 33. in the first stage solids reduction in the Fenton pre-treated sludge was twice as high as that in the control.25) 18.08) 30.05 (±0. the methane percentage for Process 3 and 4 (of Stage 2 AD.stage digestion of the Fenton pre-treated sludge.8 (±0. Cumulative methane production during anaerobic digestion. digestate generated from process 1 was degradable due to the availability of the biodegradable solids.28) 6.34 (±0.31 (±0. Erden and Filibeli [9] concluded that. respectively.79 (±0.26) 17.44 (±0.65 (±0.30) 7. during the second stage.27) 7.05 (±0. during Stage 2.20) 21.289 S.76 (±0.28) 18. 4.25) 30.29) 15.54 (±0.02 (±0. 4. The percentage total solids degradation (after 30 days of operation time) for Process 4 (Fig.6 (±0.496 m3 CH4/kg 3.33) 30.26) 34.21 (±0.15) 18. specifically.24) 33. 3c) was 28. More Fig. The biodegradable solids are degraded during Stage 1.98 (±0.88 (±0.84 (±0. the solids degradation was not high for Process 3 and 4.80 (±0.82 (±0.65 (±0.81 (±0.25%. Description Control FPT TS (g/L) VS (g/L) SS (g/L) VSS (g/L) TCOD (g/L) SCOD (g/L) 30.94 (±0. 3.32% was obtained for Process 3.18) 21. Pilli et al.20) 31.21 (±0. the cumulative methane volume for control was 4. while 19.80 (±0.85 (±0. Comparing control and Fenton pre-treated sludge.77 (±0.430 m3 CH4/kg VS added. However.21) 17. for Fenton pre-treated sludge the cumulative methane volume was 5.23) 14.27) 33.76 (±0. Fig. (b) is the solids degradation of process 2.64 (±0.83 (±0.66 (±0.13) 17.38)%.8  103 m3 at an average production rate of 0. (c) is the solids degradation for second stage of process 3.33) 1.23) 1.6 (±0. FPT is Fenton pre-treatment.4 (±0. Note: For process 3 and 4. for the control and Fenton pre-treated sludge was 56.33 (±0. as described in Fig.27 (±0. The increase in the methane percentage after Fenton pre-treatment was not substantial.23)% and 58. Methane production during anaerobic digestion The methane percentage obtained from the GC analysis. Solids degradation during anaerobic digestion.46 (±0. .53 (±0.31) 15.38 (±0.50 (±0. The cumulative methane production during AD for four treatment Processes is presented in Fig.13) 25.10) 23.

lipids.46% VS was degraded during AD). 3a). . ⁄indicates that for process 3 and 4.4% higher methane production was obtained compared to raw sludge. is presented in Table 2. During Fenton pre-treatment. during AD.).08 1.2 137 2040 2222 50. the amount of solids that remained after AD digestion for the control and Fenton pre-treated sludge was measured at 25. For the Fenton pre-treated sludge (Process 2).56 Mg of VS were digested. was 182 kWh/Mg of TDS total dry solids compared to 231 kWh/Mg of TDS for Process 4. the energy input (Table 2) for dewatering. The net energy increased 3. respectively.44 Mg. For Process 3. 3b) during AD. Moreover. While the solids degradation was higher in Process 2. carbohydrates. since the sludge temperature after Fenton pre-treatment increased from 12 (±2)°C to 25 (±3)°C. transportation and land application was not reduced for the Fenton pre-treated sludge (Process 2) as compared to the control (Process 1) (Table 2).4. transportation and land application was further reduced in Process 3 and 4 due to the lower digestate mass. Therefore. during AD. The net energy computed for Process 1 and 2. However. 4). see Fig. Energy required to increase the temperature of sludge to AD temperature ii. Process 3 > Process 2 > Process 4 > Process 1 was noted.8. On the other hand. where 19. resulting in solubilization and methane production (due to biodegradation of solids. Fenton pre-treatment (i. for Process 3 and 4.1 Mg of TDS.57  103 m3 at an average production rate of 0. the net energy increased. The energy input for the AD was higher for the control sludge compared to the pre-treated sludge. since the energy input for Fenton pre-treatment and AD is twice as high (Table 2) compared to that of Process 2.5 27.. For the control. Erden and Filibeli [9] concluded that the specific methane production increased during the first 20 days of digestion in the digester containing Fenton pre-treated sludge.4 Mg inert solids) and.96 Mg (and 11. AD: anaerobic digestion. With Fenton pre-treatment (for Process 2). Similarly. out of 25. 4).e. The energy required for dewatering.04 Mg inert Table 2 Energy balance for the different process. the cumulative methane volume produced during Stage 2 AD of Process 3 at 30 days retention time was 2. these results demonstrated that Fenton pre-treatment enhanced the AD efficiency and it was energetically beneficial. / Chemical Engineering Journal 283 (2016) 285–292 VS added. Therefore. The energy output from the methane was calculated based on the energy value given in Section 2.8 175.. for Process 4. Furthermore. stage 1 and stage 2 AD was combined during computations. At 30 days retention time. during Stage 2. the net energy for Process 3 (i. moreover. the solids that are not easily biodegraded were subjected to FPT. TDS is total dry solids. 30 days digestion for Stage 1 and further 30 days for Stage 2). Total energy input during AD (i + ii) Dewatering Transportation Land application (a) Total energy input (b) Energy output (heat (55%) and power (30%) recovered) Net energy = (b-a) Energy ratio Energy input/energy output 491 982⁄ 893 378 ⁄ 756 1271⁄ 50 943 49 427 98⁄ 854⁄ 99⁄ 1370⁄ 63. Therefore. as shown in Fig. The cumulative methane volume produced during Stage 2 AD of Process 4 at 30 days retention time was 3. Mg is mega gram. Fig. the total VS solids mass was 28.1 Mg of TDS (i.574 m3 CH4/kg VS destroyed. The energy balance of Stage 1 of Process 3 and 4 was evaluated by assuming 40 Mg of TDS. at 30 days retention time. the quantity of the digestate produced was high (due to the high percentage of inert solids) compared to the control.e. 3.. Fenton pre-treatment enhanced methane production by 15% compared to the raw sludge digestion. the total VS mass was 27. transporting the dewatered solids from the WWTP to the land application site and during land application was calculated. for Stage 2 the solids generated after 30 days of digestion (from Process 1 and 2.7 221 1271 1362 64.99 Mg of TDS (i. The net energy for Process 3 was lower than that obtained in Process 2.11 0 491 Note: negative sign indicates increase energy input.5 44. higher methane production was observed for Process 4 compared to Process 3 (Fig. These results are in line with those reported by Erden and Filibeli [10]. the net energy increased compared to Process 1. 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. 35% VS was degraded).8 2123 2353 91 285 182 231 1. Thus. i.462 m3 CH4/kg VS destroyed. dewatering the digested solids.23 1. etc. respectively) were considered. process 4 is more beneficial compared to the control. the energy recovery for Process 3 (during the two stages) was not equivalent to the energy input. In contrast.7 34. Fenton pre-treatment. The solids that are not biodegraded during AD (Stage 1. in terms of the m3 CH4/kg VS destroyed. cell lysis initially occurs and releases extra cellular polymeric substance (EPS). solids) and. which is further broken down into the fractions (proteins. Process 2) will be energetically beneficial compared to two-step Fenton pre-treatment (Process 3). 14. during Stage 1. The efficiency of four treatment processes in generating methane followed the Process 3 > Process 4 > Process 2 > Process 1 pattern. Furthermore. the net energy was low compared to Process 2. from the results it is clear that Fenton pre-treatment enhances methane production. During Stage 2 AD (Fig.1 Mg and 25. The energy input for AD. In addition.6 Mg (and 12.9 Mg of VS were digested. 3c). These proteins are degraded during the operation time in the digesters and produce biogas. of Process 4 were subjected to AD and the methane production was not high (due to low solids degradation. it enhances the solids degradation of the digestate as well as the corresponding methane production.3 224 1250 1535 39.6 43. For the control (Process 1). The maximum net energy was observed in Process 2 (Table 2). while.e. out of 40 Mg of TDS 51. during Stage 2.On the other hand. Heat loss iii. and the digestate generated from Process 4 was measured at 19. the energy required for dewatering the solids generated from Process 3 and 4 was lower than that required for Process 1 and 2.e. 14.48  103 m3 at an average production rate of 0. Therefore.07 1. the net for the control (Process 1) was 91 kWh/Mg of TDS and was 285 kWh/Mg of TDS for Process 2. As a two-stage process. for the Fenton pre-treated sludge. The increase in the SCOD increases the methane production [10]. 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. Description Process-1 Process-2 Process-3 Process-4 Energy (kWh/Mg of TDS) Fenton treatment AD i..e. the methane production for FPT was higher at all retention times compared to the control (Process 1) (Fig. 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). Thus. The quantity of digestate generated from Process 1 was measured at 25. 1). FPT has solubilized the SS and has enhanced the methane production (due to high solids degradation. Pilli et al.1 times for Process 2 compared to Process 1.290 S.

3. at 15 days digestion (i. The energy reduction resulting from centrifuging the digestate after thus AD needs to be established. GHG emissions were lower compared to the control (Process 1). The release of sludge bound water due to the disintegration of sludge flocs. stage 1 and stage 2 are included.8 250. because the CST projections for centrifugation are not truly representative. 4. GHG emissions will be lower than those computed in this study due to land application of sludge. these factors were not measured in this study. 5. For example. Fenton treated digestate) Dewaterability.5 122.73 and was 0.6 94 95 58 75 192 128 366 356 Note: negative sign indicates reduction in GHG emissions. [35] observed a 97. More specifically. transportation and land application was evaluated for four processes considered in this study (Fig.6 392. at 20 days digestion. for Process 1. In contrast.6 354.5 511.7% CST reduction with Fenton pre-treatment (H2O2 178 mg/g of VSS and Fe2+ 211 mg/g of VSS). The CST of the Fenton pre-treated digestate generated from Process 1 and 2 was 145 (±12) s and 87 (±11) s.e. Zhen et al. / Chemical Engineering Journal 283 (2016) 285–292 The energy ratio was higher for the Fenton pre-treated sludge (Process 2) than the control (Process 1). Thus. additional water holding capacity of soil.3 7. AD. and photosynthetic absorption of CO2 by crops.69 for Process 4. 5). cell lysis and breakdown of the EPS during Fenton pre-treatment has reduced the CST [35. The energy recovery and land application are the factors responsible for the reduction in GHG emissions (Table 3) in Process 2. The sludge solids solubilization and solids degradation was enhanced by Fenton pre-treatment. improved tillage and workability of soils.5 513. For example. The increased energy ratio was due to higher solids degradation and methane production. Conclusion Fig. Pilli et al. In the calculation performed here.3 19.2 304. Description Net GHG emission due to energy input and out put GHG emissions during AD (biogenic emissions) GHG emissions during CH4 combustion GHG emissions during transportation GHG emissions during land application Total GHG emissions without considering biogenic CO2 emissions GHG emissions (kg CO2/Mg of TDS) Process-1 Process-2 Process-3 Process-4 48.5. carbon sequestration in soil. if factors such as fertilizer value of sludge. for Process 1 and 3. was 1006 (±12) s and 120 (±15) s. For Process 3 and 4.513 Mg CO2/Mg TDS.192 Mg CO2/Mg of TDS and 0. respectively.. GHG emissions for the control and Fenton treated sludge The GHG emissions corresponding to energy utilization for Fenton pre-treatment. The increase in sludge dewaterability after AD was due to the solids reduction (% VS degradation for the control after 30 days digestion was 51. the energy output (generated from methane) was greater than the energy input.5 9. the GHG emissions corresponding to methane combustion are high compared to Process 1 and 2 (i. The GHG emissions for the control (Process 1) and for Fenton pre-treated sludge (Process 2) were 0. However. increase in dewaterability was not considered. the solids have degraded from 40 Mg of TDS to 15. respectively. Thus. for Process 2. Mg is mega gram. 1) and the results are summarized in Table 3.46%). TDS is total dry solids.96 for Process 2. respectively. Fenton pre-treatment of digestate has reduced the CST value as well as increased dewaterability. while it was 0. 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.e. the energy ratio was 0. the GHG emissions corresponding to methane combustion were measured at 0. Evaluation of the energy ratio at different solids retention times revealed that Process 2 is more beneficial compared to Process 1 (Fig.0 150. requirement during dewatering.3 543. for the control and Fenton pre-treated respectively. the following order was observed: Process 2 > Process 4 > Process 3 > Process 1.6 19. 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. for Process 3.6. measured in terms of CST.4 314. 30 days digestion during Stage 1 + 15 days digestion for Stage 2). FPT. are considered [28].78. More specifically. in Process 3. respectively). AD of sludge (both control and Fenton pretreated sludge) further improved sludge dewaterability (reduced the CST).03 Mg of TDS during the two-stage digestion. Dewaterability of sludge (control. Energy ratio at different solids concentration. in terms of reducing GHG emissions. a minimum of 30 days operation time is required.314 Mg CO2/Mg TDS and 0.7 96. It is clear that the Fenton pre-treatment process reduces the CST and hence increases the sludge dewaterability. The energy ratio of Process 3 and 4 was high compared to Process 1. The CST of the digestate generated after AD in Process 1 and 2 was further reduced to 138 (±6) s and 80 (±8) s. The increased energy input (during Stage-2) in Process 3 and 4 resulted in increased GHG emissions compared to Process 2.496 m3/kg VS destroyed. The minimum GHG emission levels were was observed in Process 2. the energy ratio was 0. Cumulative methane production increased with Fenton pre-treatment and the methane production rate for the Fenton pre-treated sludge was 0.. 3. With Fenton pre-treatment (Process 2).9].291 S.128 Mg CO2/Mg TDS. respectively. The energy balance showed that the net energy . which resulted in a reduction in the GHG emissions pertaining to Process 2 compared to Process 1. The following order was observed with respect to increasing the energy ratio: Process 2 > Process 4 > Process 3 > Process 1. the total energy input was 1291 kWh/Mg of TDS and the energy recovery was 1238 kWh/Mg of TDS. the total energy input for Process 1 was 1308 kWh/Mg of TDS and the energy recovery was 1011 kWh/Mg of TDS. as the fertilizer value of the sludge was not determined. in order for the energy ratio to exceed one and the net energy to be positive. dewatering. Moreover. Note: for process 3 and 4.

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