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Accepted Manuscript

The combined effect of ultrasonic and microwave pre-treatment on bio-methane


generation from co-digestion of petrochemical wastewater

Md. Nurul Islam Siddique, Mimi Sakinah Abdul Munaim, Zularisam Bin Abdul
Wahid

PII: S0959-6526(17)30069-0

DOI: 10.1016/j.jclepro.2017.01.061

Reference: JCLP 8808

To appear in: Journal of Cleaner Production

Received Date: 29 September 2016

Revised Date: 11 January 2017

Accepted Date: 11 January 2017

Please cite this article as: Md. Nurul Islam Siddique, Mimi Sakinah Abdul Munaim, Zularisam Bin
Abdul Wahid, The combined effect of ultrasonic and microwave pre-treatment on bio-methane
generation from co-digestion of petrochemical wastewater, Journal of Cleaner Production (2017),
doi: 10.1016/j.jclepro.2017.01.061

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The Graphical Abstract.

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Highlights

 Assessment of biogas generations of co-digestion and individual-digestion.


 Use of microwave and ultrasonic pre-treatments.
 Previous studies do not provide specific data on pre-treatment and co-
digestion.
 Co-digestion improved the bio-methane production by 18–32%.
 Co-digestion and pre-treatment enhanced bio-methane generation by 53% and
25%.
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The combined effect of ultrasonic and microwave pre-treatment on bio-methane generation from co-
digestion of petrochemical wastewater

Md. Nurul Islam Siddique*, Mimi Sakinah Abdul Munaim, Zularisam Bin Abdul Wahid
*E-mail: mdnurul@ump.edu.my

Tel: +6095-492337; Fax: 609-5492689

Faculty of Engineering Technology, University Malaysia Pahang (UMP), Lebuhraya Tun Razak, 26300

Gambang, Kuantan, Pahang, Malaysia

Abstract

This work investigates the combined influence of ultrasonic and microwave pre-treatment on bio-methane

generation from anaerobic digestion of petrochemical wastewater and waste activated sludge. The results

revealed that co-digestion of waste activated sludge with petrochemical wastewater produced approximately

0.22 L CH4/g VSadded. However, the highest bio-methane generations from individual digestion of

petrochemical wastewater and un-pretreated waste activated sludge were 0.19 and 0.17 L CH4/g VSadded,

respectively. In addition, co-digestion enhanced bio-methane generation by 18%–32% relative to individual

digestion of the wastes. Using microwave and ultrasonic pre-treatments on the waste sludges before the co-

digestion process resulted in supplementary enhancement of bio-methane generation by 53% and 25%,

respectively, relative to co-digestion with un-pretreated waste activated sludges. The maximum biogas and

bio-methane productions, 0.47 L/g VSadded and 0.33 L CH4/g VSadded, were attained from the co-digestion of

30-min microwave pre-treated waste activated sludge and petrochemical wastewater, respectively. The

scientific contribution of the present work on the influence of microwave pre-treatment may play a role in

the development of an energy-efficient strategy for waste management.

Keywords: anaerobic co-digestion, petrochemical wastewater, microwave pre-treatment, methane

production, ultrasonic pre-treatment

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Nomenclature
PWW Petrochemical wastewater
AD Anaerobic digestion
ACD Anaerobic co-digestion
TS Total solids
VS Volatile solids
sCOD supernatant chemical oxygen
demand
WAS Waste activated sludge
HRT Hydraulic retention time
SE Specific energy
DDcod Disintegration Degrees

1. Introduction

Consumption of fossil fuels is increasing due to high demands for energy (Siddique et al., 2015a). A number

of petroleum refineries have been established to satisfy this demand (Guo et al., 2016). A huge quantity of

wastewater is generated during the petroleum refining process, which includes systems for crude oil

desalting, distillation, hydro-treating and water cooling (Siddique et al., 2016). It has been reported that 3.5–

5 m3 of petrochemical wastewater (PWW) is produced per ton of crude oil refined (Zhang and Fan, 2016).

As it carries a variety of impurities, direct disposal of PWW can pose severe health risks to the environment

(Uddeen et al., 2015). Additionally, PWW has a high chemical oxygen demand that can generate hazardous

pollution in the waterbodies (Siddique et al., 2014).

Anaerobic co-digestion (ACD) is a commercially attractive anaerobic wastewater treatment method because

the cost of heating, maintenance, and operation may be counterbalanced by methane production (Serrano et

al., 2013). In addition, the anaerobic process does not require an aeration phase that can consume up to 50%

of total energy input to organic wastewater treatment systems (Serrano et al., 2015). Therefore, several

research works have assessed anaerobic processes for the treatment of organic wastewaters (Neumann et al.,

2015). In particular, current works have focused on co-digestion, i.e., the simultaneous degradation of

varying organic substrates in a single digester, in order to produce more bioenergy (Koch et al., 2016). As to

petrochemical residues, a plentiful resource, ACD technology is the most applied ‘‘waste-to-energy” method

(Pan et al., 2015). The feedstocks most frequently used in anaerobic co-digestion are animal manure,

municipal waste, industrial waste, food waste, energy crops and agricultural wastes (Aboudi et al., 2016).

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Earlier researchers had reported that individual digestion of petrochemical wastewater was relatively

ineffective (Lakatos et al., 2014). Specifically, hydrolysis is the key phase in which waste is in particulate

form (Aboudi et al., 2015). Nevertheless, if feedstock waste is cellulose-poor, anaerobic digestion is

controlled by methanogenesis, rather than hydrolysis (Harsono et al., 2014). The key limitations for the AD

of industrial wastes, such as petrochemical residues, have been rapid acidification of the wastewaters via

generation volatile fatty acids that reduce the pH in the digester and prevent the methanogenic activity of

microbes (Anggarini et al., 2015). Additionally, PWW has a carbon-to-nitrogen ratio of 35–80, whereas the

carbon-to-nitrogen ratio optimum for the anaerobic process is approximately from 21 to 31 (Hassan et al.,

2016).

Currently, this deliberation has prompted several researchers to examine the efficiency of the ACD process,

i.e., combined digestion of organic substrates (Balapure et al., 2016). The ACD process increases digestion

performance due to the combined effects of different organic wastes (Li et al., 2016).

Simultaneous use of different wastewaters of sufficient nitrogen content is an easy technique for meeting the

nutrient demand required by the substrates (Wei et al., 2015). Waste activated sludge containing a low C/N

ratio is considered a significant co-substrate in the ACD of PWW (Zhang et al., 2015). Agyeman and Tao

(2014) found that combining sewage sludge, having a C/N ratio of approximately 5–18, with PWW can

produce a waste mixture with an optimal C/N ratio of 21–31 (Nkemka et al., 2015).

The anaerobic co-digestion system involves four phases: hydrolysis, acidogenesis, acetogenesis and

methanogenesis (Siddique et al., 2012). Among these phases, hydrolysis is considered to be rate-limiting

because wastewater is not readily soluble (Zheng et al., 2015).

The pre-treatment of sludge samples can accelerate the hydrolysis process (Zhang and Li, 2014). These pre-

treatment processes help decrease particle size of the substrates and consequently accelerate the ACD

process (Vallejo et al., 2015).

This study examines the synergistic influence of ACD and pre-treatment techniques on bio-methane

generation from PWW and waste activated sludge. Ultrasonic and microwave pre-treatment techniques were

used on the substrates before co-digestion to accelerate digestion efficiency. Previous studies do not provide

specific data on pre-treatment and co-digestion of both PWW and waste activated sludge in order to increase

bio-methane generation.

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2. Materials and Methods

2.1. Sample collection

Digesters were seeded with a digested sludge collected from an anaerobic digestion plant of Terenganu,

Malaysia. The sludge samples were collected from the return activated sludge stream of a water treatment

plant in Kuantan, Malaysia.

The waste activated sludge samples were fed into the digesters immediately after arrival. The petrochemical

wastewater was collected from Petronas Penapisan (Terengganu) Sdn Bhd, a petroleum refinery in

Terengganu, Malaysia. This PWW was preserved in a cold room at 4 C. All of the wastewater samples were

analysed for the total solids and volatile solids concentrations. The volatile portions of the sludge and

petrochemical wastewater ranged between 59.89 and 76.26 TS, respectively. In this experiment, a

ThermoFinnigan Flash EA 1112 fundamental analyser was selected to analyse the elemental proportions of

carbon and nitrogen concentrations of the wastewaters to determine the C/N ratios. The properties of

inoculum, sludge and petrochemical wastewater used in this experiment are listed in Table 1.

2.2. Methods

The individual and co-digestion trials were carried out in 7 replicated (total of 14) batch-fed digesters ran at

37 ̊C for 31 days.

Each digester has 2.5 L of total capacity and 1.6 L of working capacity. The inoculum to substrate

proportions were maintained at 1/1 on a weight basis. The digesters were fed with selected wastewaters and

inoculums, and then sealed to carry out the ACD method.

Biogas generation in the digesters was measured daily and properties determined weekly to observe the

degree of waste stabilization during this experiment. In each digester, the composition of the total biogas

production was determined by using a Fu-li instrument-GC9720 gas chromatography device (Zhejiang Fu-li

Analytical Instrument Co., Ltd, China) equipped with a Porapak N pillar and thermal conductivity detector.

Helium gas was the carrier gas with a flow rate of 30 mL per minute.

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Particle size determinations were performed with a particle size analyser (LS 13320 MW). This instrument

determines the size of particles by using laser diffraction. Water with a refractive index of 1.32 was the

dispersant liquid. The waste activated sludge samples had a refractive index of 1.4. Mixing speed was

adjusted to 60 rpm, the lowest speed for the reactor, to avoid possible damage to the sludge flocs.

In order to determine particle size, each sample was diluted in a diffusion container and subjected to the

measuring cell (Alagoz et al., 2015). Each sample was analysed in triplicate.

Total coliform (SM9222B), Escherichia coli (SM9222D) and faecal streptococci (SM9230C) assays were

carried out through membrane filtration method according to the Standard Methods of APHA, 2015

(Alagoz et al., 2015). The Standard Methods of APHA, 2015 were also used to analyse the chemical

parameters of the assays.

The Independent Sample t-Test was applied with a 95% confidence level to evaluate cumulative bio-

methane generation from each parallel digester. Pearson’s correlation coefficient (p) was applied to describe

linear relationships among the parallel digesters.

2.3. Reactor contents

The petrochemical wastewater and waste activated sludge were fed to the digesters. The preliminary TS

levels of the digesters were fixed to 7% based upon initial batch AD experiments on varying TS

concentrations (Wu, 2016). The pH levels of the digesters were maintained in the range of 7.0–7.5 by using

1 N NaOH and HCl in order to provide a suitable environment for methanogenic activity by microbes.

Subsequently, the digesters were purged with nitrogen gas for 5 minutes to ensure anaerobic conditions

(Astals et al., 2013). The operating conditions of the digesters are listed in Table 2.

Digester D1 with seed sludge was run as control digester. The combinations of PWW and WAS were made

on a weight basis. The digesters D2, D3 and D4 were run to evaluate the influence of co-digestion of PWW

and WAS on bio-methane generation and solid reduction. The digesters D5, D6 and D7 were run to observe

the combined influence of pre-treatment and co-digestion techniques on bio-methane generation.

2.4. Sludge pre-treatments

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Pre-treatment of the samples was carried out with an ultrasonic homogeniser (FS-350T Ultrasonic

Homogenizer Sonicator Processor Cell Disruptor Mixer 350W 0.15- 200 ml) at a frequency of 20 kHz, 60%

amplitude and a supporting power of 350 W. Each sample was subjected to ultrasonic pretreatment for

fifteen and thirty minutes to attain specific energies of 15 and 25 MJ/kg TS (Alagoz et al., 2015).

Thermal disintegration was carried out with a Microwave Digestion System (TRANSFORM MW680). To

carry out the pre-treatment process, a staged temperature profile was used. In a previous work, it is reported

that optimal microwave temperatures were in the range of 155 to 185 ̊C, while treatment periods varied from

30 to 60 minutes (Feng et al., 2016). Pressures required to attain suitable temperatures were in the range of

600 to 2500 kPa (Feng et al., 2016). For the present work, microwave pre-treatments were carried out for 30

minutes at 175 ̊C and 2000 kPa, according to the outcomes of an initial microwave optimization study

considering various pressures, temperatures and treatment times (Tong at al., 2016). Sludge disintegration

was calculated in terms of Disintegration Degree (DD) and Specific Energy (SE). Disintegration Degrees

(DDCOD) of the samples were determined using the equation of Müller et al (1998). Alkaline hydrolysis

(sCODNaOH) was used to determine the supernatant chemical oxygen demand (sCOD) of the wastes and

samples were treated with 1 N NaOH for 24 h at room temperature (Bougrier et al (2015).

3. Results and Discussion

3.1. Influence of ultrasonic and microwave pre-treatments on sludge properties

The sCOD levels shown in Table 3 indicate the influence of ultrasonic and microwave pre-treatment on the

hydrolysis of organic matter. The effects of ultrasonic pre-treatments were measured by percent DD. The

DDCOD concentrations in Table 3 show that the transformation of COD from the grainy portion to the soluble

portion was noticeably improved with the use of both sludge pre-treatment methods. The sCOD

concentration was significantly enhanced from 0.93 mg/L to 2.08 g/L using the specific energy of 15 MJ/kg

TS. The degree of sCOD growth was higher for the Specific Energy of 25 MJ/kg TS. The value of the

microwave pretreated sCOD was higher than that of alkaline pretreated sludge (sCODNaOH = 3.02 g/L),

which improved the Disintegration Degree more than a hundred percent (Cesaro et al., 2014).

Particle size distributions of the samples before and after pre-treatment were calculated by cut-off diameters

d10, d50, and d90 which were subjected to different contact periods (Table 4). Table 4 shows that 10%,

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50%, and 90% of particles corresponding to d10, d50, and d90 had a diameter less than or equivalent to d10,

d50, and d90, respectively. The particle sizes in the sludge samples decreased sharply after the use of

ultrasonic pretreatment which verifies the influence of the disintegration effect (Table 4). A significant

reduction in the median diameter, d50, was observed with respect to time. Approximately 70% and 80%

reductions in the median diameter were observed for Specific Energy values of 15 MJ/kg TS and 25 MJ/kg

TS, respectively.

For the 30-minute microwave pre-treatment, the d50 was higher than for the un-pretreated sample and

indicates the re-flocculation of the particles. The dimensions of the particles enlarged steadily as the

temperature increase caused increased molecular motions and collisions among particles. For the 15-min

microwave pretreatment, the accumulation of smaller particles into bigger flocs was detected. According to

what Yu et al (2010) reported that flocs of the sludge samples were depositories for water and fragmented

into tiny particles after an abridged reaction period. The tiny particles might be re-flocculated into compact

particles by compacting agents in order to increase the dewater ability (Silvestre et al., 2015). Chang et al

(2011) reported that a steady increase in capillary suction period with the increase of contact period, which

could be due to disintegration of particle flocks by microwave pretreatment, resulted in the discharge of

intracellular and extracellular organics. In addition, Dogan and Sanin (2009) reported that the capillary

suction period values increased after both microwave (600 W, 16 min) and alkaline (pH 10.5–12) pre-

treatment.

3.2. Total solids and volatile solids removal

Preliminary levels of the digesters were maintained at pH 7. The ultimate pH of the digesters was observed

to range from 6.45 to 7.5. The preliminary and final alkalinity levels in the digesters varied from 2 to 3.6 g

CaCO3/L and 3.2–6.7 g CaCO3/L, respectively. Bouallagui et al (2009) reported on a small scale study on

mesophilic and thermophilic anaerobic co-digestion of organic wastewater and found that alkalinity

concentrations ranged between 2 and 4 g/L. In the present work, preliminary alkalinity levels of the digesters

varied in the specified ranges, whereas final values were marginally greater than the given limit. The

maximum alkalinity concentration was detected in the co-digestion digesters. As no additional buffer

solution was fed to the digesters, the rise in the final alkalinity concentration improved sludge-petrochemical

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wastewater treatment (Salehi et al., 2014). The WAS contains organic nitrogen and if ammonium nitrogen

concentrations in the reactor raise the content higher than pH limits, free ammonia nitrogen is generated and

has an inhibitory effect on methanogenesis (Yu et al., 2014). The NH4+–N levels in the digesters were

observed at the start and finish of the digestion process. After the digestion prriod, free ammonia levels were

observed to vary from 0.015 to 0.037 g/L; this level was less than that observed by Yenigun and Demirel

(2013). Co-digestion provides a variety of nutrients and increases buffering capacity. These factors stabilize

the C/N ratio of the substrates, thereby reducing the possibility of ammonia inhibition (Siddique et al.,

2015b). The effect of mono- and co-digestion was assessed by organic removal, biogas generation and

pathogen elimination.

In the beginning, cumulative bio-methane generation from each parallel digester was compared by the

Independent Sample t-Test with a 95% confidence level. No significant differences among the cumulative

volumes of bio-methane generation were identified in the parallel reactors. The Pearson’s correlation values

are shown in Table 6. The results from parallel digesters revealed that the mean of the attained values may

be considered the representative value. It has been observed that digesters with ultrasonically pre-treated

samples and co-substrates show organic solids removal efficiency higher than un-pretreated samples. The

volatile solids removal efficiencies in the reactors ranged between 39.4 and 54%. A maximum volatile solid

elimination of 54% was attained in digester D7, which contained a combination of petrochemical wastewater

and the 30-minute microwave pre-treated waste activated sludge. A minimum VS elimination efficiency of

39.4% was attained in digester D3, which contained only the petrochemical wastewater. Meyer and Edwards

(2014) reported that anaerobic co-digestion of pulp and paper mill wastewater achieved 22-55% VS

removal. In addition, Edelmann et al (2000) reported that co-digestion of sludge and vegetable wastes

increased degradation efficiency.

3.3. Stabilization

Outcomes of the microbiological experiments listed in Table 5 illustrated that the AD process established a

balanced equilibrium in all reactors. The mesophilic individual and ACD of the mixed waste activated

sludge and petrochemical wastewater achieved significant pathogen removal, e.g., a five-log decrease in the

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number of faecal coliforms and a four-log decrease in total coliforms. Similarly, faecal coliform

concentrations were virtually negligible after the anaerobic process.

3.4. Bio-methane generation outcomes

The individual and co-digestion experimental studies were carried out in identical batch digesters. The

assessment of experimental outcomes was made based on the mean value of bio-methane generation attained

from the identical digesters. Cumulative bio-methane generation is shown in Fig. 1. From this figure, it is

clear that the ACD of WAS and PWW (D4) increased bio-methane generation relative to individual

digestion of the respective wastes (D2 and D3). Co-digestion provides a proper C/N ratio by combining

nutrient and carbon-rich wastes. Dai et al (2016) reported that the positive influences of co-digestion that

provide improved bio-methane generation are stabilization of the C/N ratio and other key parameters during

the anaerobic process. The current study showed that bio-methane generation can be increased by the use of

a suitable pre-treatment process. Statistical evaluation of the reactor results was carried out by examining

differences between the elemental ratios and other parameters in the duplicate digesters. The analysis

indicates that parameters from each type of digestion, individual and ACD/pretreatment, were statistically

disparate and these results assure the positive influence of ACD and pre-treatment. Among the first set of

digesters D1, D2 and D3, the same yield of bio-methane volume was attained. Likewise, bio-methane yield

volume was identical among the subsequent set of digesters including D5, D6 and D7. Though digester D4

initially generated a yield pattern similar to the first set, the pattern became more similar to the subsequent

set at the end of the 8th day of AD. This transition reflects the positive influence of ACD. The results

revealed that an HRT of 31 days was sufficient to evaluate the combined influences of ACD and pre-

treatment processes. In particular, a 21-day period of digestion was found to be adequate for the first set of

digesters (D1, D2 and D3) since no significant change in bio-methane yield of ACD was found at the end of

the 18th day. As this steady state condition was observed at the end of the 20th day of ACD, the HRT for the

second set of digesters should not be maintained for less than 31 days.

In the present work, the primary objective of ultrasonic and microwave pre-treatments was to accelerate the

solubility of organic solids and increase bio-methane generation. The results showed that the use of both

substrate pre-treatments enhanced cumulative bio-methane generations. Enhancement of bio-methane

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generation was clearly observed from the beginning of the AD process (from 1 to 3 days) (Fig. 1). Table 7

lists the key operating parameters of the mesophilic batch reactors. Specific methane production attained

from individual-digestions of PWW and WAS were 0.19 and 0.17 L CH4/g VSadded, respectively.

Alternatively, the ACD of WAS and PWW (D4) generated 0.22 L CH4/g VSadded. It has been observed that

the use of ACD resulted in 18%–32% enhancement in specific methane production relative to the mono-

digestions of PWW and WAS. Using ultrasonic and microwave pre-treatment on the samples before ACD

led to the disintegration of sludge particles and increased bio-methane generations by 25% and 53% relative

to ACD with un-pretreated samples. The maximum enhancement in bio-methane production was attained

from reactor D7, which contained co-digestion of microwave pre-treated WAS and PWW. Because the

sludge in D7 was microwave pre-treated, bio-methane production from reactor D4 increased to 0.33 L CH4/g

V. Quiroga et al (2014) reported an experiment on the influence of ultrasonic pre-treatment on ACD of

manure, food waste and sewage sludge and, after 20 and 18 days of digestion, achieved a 14%–31%

improvement in specific methane yields relative to un-pretreated sludge. Zheng et al. (2015) studied that co-

digestion of dairy manure with switchgrass improved methane production by 39% over individual digestion

of the substrates. Yao et al. (2014) studied an experiment on anaerobic co-digestion of vegetable processing

waste and cattle manure and obtained a 17-35% increased methane production relative to mono-digestion of

the substrates. Abouelenien et al. (2014) studied that ACD of chicken manure and agricultural waste

increased cumulative methane generation up to 42%. Cesaro and Belgiorno (2013) carried out an experiment

on the effect of sonolysis and ozonation for increasing anaerobic digestibility of organic wastes. They

observed that pre-treatment effects enhanced the solubility of organic wastes; however, ultrasonic

pretreatment was more effective than ozonation and produced a 24% increase in methane production. Ebner

et al. (2016) studied the characterization of ACD parameters and synergistic effect of ACD of food waste

and cattle manure and found that food waste bio-methane potentials ranged from 0.16 to 0.49 L CH4/g VS.

Al-Mallahi et al. (2016) performed an experiment on NaOH-pretreated two-phase olive processing effluent

for co-digestion with organic waste in the mesophilic range and obtained the high methane production level

of 0.45 L CH4/g VS. The CO2 and CH4 content of the biogas in an anaerobic process depends on the

quantity of stabilized decomposable organics and on the methanogenic activity of microbes (Zhang et al.,

2016). In this study, methane contents of the biogas varied from 62% to 69.1%. The methane contents

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attained in this study were in line with common bio-methane generation levels of 59%–81%, as reported in

the previous studies of Ponsá et al., 2011.

4. Conclusions

This study examined the improvement of bio-methane generation by the use of ultrasonic and microwave

pretreatments in ACD of Petrochemical wastewater and waste activated sludge. The results demonstrated

that the combined application of ACD and proper sludge pre-treatments produced better stabilization of

nutrients, effective pathogen removal and increased bio-methane productions relative to individual digestion

of these wastewaters. ACD produced 0.22 L CH4/g VSadded, while the highest productions from the

individual digestions of petrochemical wastewater and waste activated sludge were 0.19 and 0.17 L CH4/g

VSadded, respectively. The use of ACD improved bio-methane generation by 18%–32%. In addition, the

ultrasonic and microwave sludge pre-treatments improved the methane yields by 25% and 53%,

respectively, relative to un-pretreated substrates. The maximum yields, 0.47 L biogas/ g VSadded and 0.33 L

CH4/g VSadded, were attained from digester D7, which contained 30-minute microwave pre-treated

substrates. It is clear that petrochemical wastewater and waste activated sludge are potential sources for the

ACD process. In addition to the enhanced bio-methane production, the ACD of these wastes may provide an

energy efficient green technology for the discharge of petrochemical wastewaters and waste activated

sludge. The use of this anaerobic co-digestion technology with sludge pretreatment may play a part in

degradation of petrochemical wastewater and development of an energy-efficient strategy for waste

management.

Lastly, this environmentally friendly technology may be a more economical technology for industrial

petrochemical waste-to-energy conversion.

Acknowledgements

The authors are thankful to the Faculty of Engineering Technology at the University of Malaysia, Pahang for

permitting continuous access to their lab facilities. The present investigation was made possible by the

RDU-140307 grant.

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List of Figures

Fig. 1. The cumulative bio-methane generations in the reactors

1
List of Tables

Table1

Chemical composition of petrochemical wastewater, waste activated sludge and active inoculum used during this experiment * values are the mean + S.D. of the
3 observations

Parameters PWW WAS Inoculum

sCOD (g/L) 8.54±0.03 1±0.02 5.16±0.02


VS (g/L) 51.33±0.3 12.37±0.5 25.37±0.30
Nitrogen weight (%) 1.43±0.02 2.36±0.04 2.63±0.03
Carbon weight (%) 52±0.5 31±0.06 26.33±0.01
C/N ratio 40±0.02 11.73±0.04 11.17±0.01
TS (g/L) 65.4±0.2 20.98±0.5 38.32±0.20

1
Table2

Operating conditions of the reactors

Reactor PWW WAS Inoculum 15 min ultrasound pre-treated 30 min ultrasound pre-treated Microwave pre-treated VSadded
(g) (g) (g) sludge (g) sludge (g) sludge (g) (g)
D1 - - 1800 - - - 4.8
D2 - 900 900 - - - 9.2
D3 900 - 900 - - - 11.3
D4 450 450 900 - - - 14.3
D5 450 - 900 450 - - 13.5
D6 450 - 900 - 450 - 13.6
D7 450 - 900 - - 450 13.3

2
Table 3

Influence of ultrasonic and microwave pre-treatments on the solubility of sludge

Sample Treatment time (m) SE (MJ/kg TS) sCOD (g/L) DDCOD (%)
Un-pretreated sludge 0 - 0.93 -
Ultrasonicated sludge (D5) 15 15 2.08 55.18
Ultrasonicated sludge (D6) 30 25 2.89 94.04
Microwaved sludge (D7) 30 - 3.24 111.34

3
Table 4

Influence of sludge pre-treatment on the particle size.

Sample Treatment time (m) Surface weighted Volume weighted d10 (μm) d50 (μm) d90 (μm)
mean D(3,2) mean D(4,3)
Un-pretreated sludge 0 36.6 81.94 18.77 63.04 145.38
Ultrasonicated sludge (D5) 15 6.14 32.41 2.66 19.31 59.73
Ultrasonicated sludge (D6) 30 3.42 38.75 1.18 11.68 109.65
Microwaved sludge (D7) 30 67.03 146.12 38.55 113.01 262.16

4
Table 5

Microbiology results of the reactors.

Reactors Total coliform Total coliform final Fecal coliform Fecal coliform Fecal streptococ Fecal streptococ
initial (kob/100 mL) initial final initial final
(kob/100 mL) (kob/100 mL) (kob/100 mL) (kob/100 mL) (kob/100 mL)
D1 1.01 x106 1.71 x102 5.01 x105 1.81 4.01 x104 69
D2 1.41 x106 1.31 x102 4.71 x105 3.71 3.61 x104 52
D3 7.31 x106 6.01 x102 4.21 x105 2.1 2.01 x104 23
D4 3.21 x106 2.01 x102 2.61 x105 1.71 5.01 x104 12
D5 2.31 x106 8.01 x102 1.01 x105 1 3.01 x104 19
D6 3.12 x106 ≤1 2.01 x105 ≤1 3.01 x104 ≤1
D7 2.51 x106 1.01 x102 1.51 x105 ≤1 3.31 x104 ≤1

5
Table 6

The Pearson’s correlation values for different reactors for first 5days

Parameters Reactors
cumulative bio- D1 D2 D3 D4 D5 D6 D7
methane generation 0 0 0 0 0 0 0
(L) 0 0.04 0.09 0.17 0.2 0.21 0.247
0.02 0.09 0.12 0.34 0.4 0.42 0.49
0.04 0.18 0.24 0.51 0.6 0.63 0.74
0.06 0.27 0.36 0.68 0.8 0.84 0.99
Pearson’s 0.99 0.99 0.99 0.99 0.99 0.99 0.99
correlation values

6
Table 7

Performance of batch mesophilic anaerobic digester* values are the mean + S.D. of the 3 observations

Parameters Reactors
D1 D2 D3 D4 D5 D6 D7
VSadded (g) 4.61±0.02 9.2±0.02 11.30±0.2 14.21±0.2 13.4±0.2 13.6±0.2 13.4±0.2
VSremoved (g) 2.04±0.02 3.63±0.01 4.43±0.02 6.45±0.02 6.56±0.02 6.82±0.02 7.2±0.02
VS removal (%) 44.81±0.2 40±0.2 39.4±0.2 45.04±0.2 48.91±0.2 50.5±0.2 54±0.2
CH4 percentage (%) 68±0.2 65.01±0.2 68.81±0.2 62.04±0.02 67.1±0.2 63.04±0.2 69.1±0.2
Cumulative biogas 0.42±0.02 2.26±0.02 3±0.02 4.8±0.02 5.18±0.2 5.68±0.02 6.1±0.02
production (L)
Cumulative CH4 0.28±0.02 1.45±0.02 2.04±0.02 2.92±0.02 3.47±0.02 3.58±0.02 4.2±0.02
production (L)
Specific biogas yield 0.21±0.02 0.63±0.01 0.69±0.01 0.75±0.02 0.8±0.01 0.85±0.01 0.87±0.01
(L/g VSremoved)
Specific biogas yield 0.1±0.01 0.26±0.01 0.28±0.02 0.35±0.02 0.4±0.01 0.42±0.01 0.47±0.01
(L/g VSadded)
Specific CH4 yield (L 0.15±0.01 0.41±0.01 0.46±0.02 0.47±0.02 0.54±0.01 0.52±0.01 0.6±0.01
CH4/g VSremoved)
Specific CH4 yield (L 0.07±0.01 0.17±0.01 0.19±0.01 0.22±0.02 0.27±0.01 0.27±0.01 0.33±0.01
CH4/g VSadded)

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