THERMAL INVESTIGATION AND FTIR

ANALYSIS OF SEWAGE SLUDGE

GENERATED FROM MUNICIPAL
WASTEWATER TREATMENT PLANTS IN
INDIA
Vipin Singh, Harish C. Phuleria, and Munish K. Chandel*

Centre for Environmental Science and Engineering

Indian Institute of Technology Bombay
Powai, Mumbai-400076, INDIA.
Email: [email protected]

ABSTRACT: The process of wastewater treatment produces sewage sludge for

which appropriate treatment is required for its disposal or effective utilization. Thermal
treatment of sewage sludge could be one of technology for its management. As the
quantity of wastewater has increased over the last few decades, the generation of
sludge also increased. In order to estimate energy potential of sewage sludge,
physical and chemical characterization of the sludge is the first stage. In this study,
the sewage sludge is characterized by thermal analyses Thermogravimetry
(TG)/Derivative Thermogravimetric (DTG) and elemental analysis (CHNSO). The DTG
curve of sewage sludge shows that the pyrolysis process occurs at 200 to 600 °C and
combustion at 180 to 600 oC. The mass loss could be attributed mainly due to the
decomposition of organic compound. The organic content in the sludge was found in range of
−1
37 to 21% and the calorific value of the sludge was 8.6 to 18.9 MJ kg (dry basis). This
study provides basic insight of the pyrolysis and combustion of sewage sludge.
Additionally Fourier transform infrared spectroscopy (FTIR) analysis was performed for
sludge samples, which shows that the main organic groups in the sludge samples were
aliphatic chains with double bonds, carbonyl, and hydroxyl and N–H groups.

Keywords: Sewage sludge, Pyrolysis, Combustion, Thermal analysis, Calorific value, FTIR.

1. INTRODUCTION

In the course of last many years, a number of technologies and approaches have
been come up in regard to municipal wastewater treatment globally. This is within the
framework that development as well as improvement of sewage treatment
technologies permitted the applicability of aerobic and anaerobic systems. The sludge
is a semi-solid residue of wastewater treatment systems which might contain toxins
or valuable products such as metals and nutrients. These valuable materials could be
recycled or reused according to end requirement.
 A few research studies have been focused on kinetic study of sewage sludge using
either only thermogravimetry or thermogravimetry combined with emerged gas
investigation. The thermal disintegration of sewage sludge at low temperature range
in inert atmosphere has been studied in these research works. According to Hernandez
et al., 2015 the nature of sewage sludge relates to the deterioration of three different
segments: biodegradable of organic components (200–300°C), polymers of organic
nature (300–450°C), and non-biodegradable organic components issue (>450 °C)

Conesa et al., (1998) has done thermogravimetry/ mass spectrometry (TG/MS)

study for the emission of gases occurs during primary pyrolysis of various sludges
produced at eight different WWTPs in Spain. Out of eight half of the WWTPs were
anaerobic and other half were aerobic in nature. They have reported the sewage
sludges produce chemicals of good qualities (~45% by wt.) during primary pyrolysis,
which are mainly hydrogen, water, hydrocarbons (saturated and unsaturated both),
CH3OH, chloromethane, CO2, and CH3COOH. Decomposition of sludge occurs in
three different stages (250°C, 350°C, and 550°C). During stage one, the preeminent
products emitted were CH4, CO2, H2O and CH3COOH. During stage two, the products
were alcohols and hydrocarbons, whereas in the third stage the products were H 2,
CH4, CO2 and also alcohols as well as hydrocarbons.

Font et al., (2001) has done a study for analysis of the combustion and pyrolysis of
various sewage sludges by TG with the heating rate of 15°C/min. In the study, the
thermal decomposition of sewage sludge, in both combustion as well as pyrolysis, for
seven different types of sewage sludge was observed. hey have reported that
aerobically stabilized sewage sludge samples, during combustion mainly occurred by
a first pyrolytic disintegration at 450 to 500 °C by the evolution of char and combustion
of char occurs at relatively higher temperature. For aerobically stabilized sludges the
combustion could be taken as a pyrolysis of oxidative nature, where there is no
significant char formation, which need to be burnet at high temperature.

As indicated by Francioso et al (2010), the thermal decomposition of thermolabile

components of organic matter (e.g. amino acids, carboxyl) results into exothermic reaction at
~300°C, while this reaction at further higher temperatures (∼450°C) start from the
disintegration of carbon refractories, e.g. long chain of N-alkyl, aromatic and aliphatic groups.
The DTA curve of UASB sludge of this study has been shown then exothermic reaction was
expressed at 453°C with 10% mass loss.

A study was done by Silva et al. (2012) on Thermal and FTIR investigations of sewage
sludge generated in WWTPs in Brazil. In this study, the physical and chemical characterization
of material was done utilizing thermal examinations i.e. Thermogravimetry, Differential
Thermal Analysis (DTA) and Differential Scanning Calorimetry DSC), as well as FTIR (for
Infrared Analysis) to decide the availability of major organic matter present in sewage sludge.
The calorific value (CV) of sludge was measured and observed to be 16.2 MJ/kg on dry basis.
Similar studies were additionally done with respect to energy content in sewage sludge. Dweck
et al. (2006) reported calorific value estimation of sludge in the range of 9.50 to 18.57 MJ/kg.
Andreoli et al. (2001) reported energy content somewhere around 6 and 13 MJ/kg sludge
generated in WWTP.
 Casajus et al. (2009) has done a study on thermal decomposition of sewage sludge in
France. The moisture content, ash, volatile matter, fixed carbons were 64.6, 44.1, 50.1 and
5.73% respectively. Whereas C, H, N, S and O were 53.8, 7.02, 7.6, 1.5 and 30.7%
respectively. The calorific value was accounted for in the range of 11.95 MJ/kg.

Bianchini et al. (2015) considered sewage sludge drying process integration with a waste-
to-energy power in Italy. The investigation of the study has demonstrated that sludge has a
water content somewhere around 71.8% to 79.0% in weight. The amount of water could be
removed by drying technology at temperatures around 100°C and 105°C temperature. The
range of calorific value accounted was from 12.7 to 15.5 MJ/kg. Jayaraman and Gokalp (2015)
in France have studied pyrolysis, gasification as well as combustion attributes of miscanthus
and sludge. Their outcomes reported moisture 6.2%, Ash 15.9%, V.M 58.9%, fixed carbon
19%, by proximate analysis and C 58.5%, H 9%, N 5%, O 27.45% and S 0.045% by ultimate
analysis, and heating value as calorific worth was 20.43 MJ/kg for sewage sludge.

An investigation of combustion of coal, sewage sludge and biomass was carried out by
Magdziarz and Wilk, (2013) using thermogravimetric analysis. It was reported that the sewage
sludge ash contains Pb (0.010%), Ni (0.056%), Hg (0.002%), Cu (0.112%), and Cr (0.083%)
trace components. The calorific value was found to be 23.53, 17.59, 17.20, 12.83 MJ/kg in
Coal, Wood biomass, Oat and Sewage sludge respectively. Their study has demonstrated the
substance of nitrogen additionally, which relies on upon the type of biomass. The wood
biomass contained less nitrogen content i.e. <0.05%, oat 1.7%, Coal 2.2 % and sludge has
essentially higher 4.1% which is significantly higher than all biomasses utilized in the study.
The ash content in sewage sludge had observed to be 33%.

Thermal analysis of sewage sludge is required in order to find out optimum

temperature for pyrolysis and incineration, which may benefit the efficient use of
sludge. The study also includes stability of sludge by decomposition process and
energetic content of sludge.

2. MATERIALS AND METHODOLOGY

2.1 Materials

Four sludge samples from two WWTPs were used in this study. The activated
sludge process treatment technology is used in these WWTPs and their capacity is
of 180 MLD (STP-1) and 202.5 MLD (STP-2). The plant consists inlet chamber,
screen chamber, grit chamber, primary settling tank, aeration, secondary settling tank
and chlorination system for wastewater treatment and, sludge thickener, anaerobic
digester, and belt filter press for sludge system unit.

2.2 Method

Proximate analysis: The proximate analysis of the sewage sludge samples was done
in accordance of ASTM D3172-89 procedure. This method gives proximate
examination of the sewage sludge samples i.e. moisture, volatile matter, fixed carbon
and ash contents.
Ultimate analysis: The elemental investigation (C, H, N, S and O substance) was done
in a FLASH EA 1112 series CHNS-O instrument to get the content of main
components available in the sludge samples. This method provides percentages of
C, H, N, S, (O) in a compound which are for the mostly combustible at 1800 °C.

Net Calorific Value: Dried sewage sludge samples were incinerated to obtain energy
by using bomb calorimeter (IKA C- 200). A combustion of each sample was done at
high oxygen pressure (30 bar) in a bomb, and the heat of combustion was calculated
in J/g.

Thermogravimetric analysis: TG (Thermogravimetric analysis) experiments was done

using a Shimadzu DTG 60 thermo analyzer from room temperature 30 to 1000 ◦C with
a heating rate of 10 ◦C min−1 under a nitrogen flow and air rate of 50 mL min−1. The
sample weight ranged ~10 to 15 mg. The DTG (Derivative Thermo-Gravimetric)
curves were obtained with respect to temperature.

3. RESULTS AND DISCUSSION

3.1 Proximate and ultimate analysis

The sewage sludge taken in this study are primary sludge which is undigested and
the belt filter press (BFP) sludge which is digested from two activated sludge process
based STPs in India. The two STPs are (i) 203 MLD ASP Kondli Delhi (ii) 180 MLD
ASP Ahmedabad. The calorific value of sewage sludge was analyzed experimentally
using bomb calorimeter. It was found to be in the range of 18 MJ/Kg to 18.9 MJ/Kg
for primary undigested sludge samples and in order to 8 to 9 MJ/Kg in digested sludge
samples (Table 1). The results obtained are supported by literature. Silva et al., (2012)
reported calorific value 16.2 MJ/kg on a dry basis. The digested sludge samples have
calorific value in the range of 8 to 9 MJ/kg. Andreoli et al., (2001) has reported an
energy content between 6 and 13 MJ/kg sludge. The reddish brown matter was
observed at the completion of combustion of sludge samples. This matter may contain
minerals.

The Total Solids (TS) in sewage sludge samples was found to be in the order of 3-
4% in primary undigested sludge and 22 to 37% in BFP digested sewage sludge. The
overall range for the VM% was found in order of ~75 to 78%, in sewage sludge
samples. The ash content in primary (undigested) sludge samples is 18 to 23% and
35 to 36 % in digested sludge. The digested sewage sludge samples obtained from
the STPs contain high ash content and relatively less calorific value. The reason
behind this is degradation of the organic matter during digestion process, which
results in low volatile matter as well as low carbon in remaining digested sludge.
(Table 1). We observed that the undigested sludge samples have more carbon
content (upto ~37%) and digested sludge has comparatively less ~20%. Similarly,
nitrogen was observed in the range of 1.2 – 1.9%. The samples have Hydrogen in the
range of ~ 6 to 9.7 in the sewage sludge. Which gets eventually evaporated in the
form of vapour and volatiles during thermal process. Sulphur content was reported
negligible in sludge samples.
 Table 1: Proximate and Ultimate analysis of sewage sludge samples

STP-1 primary STP-1 STP-2 primary STP-2 BFP

Sludge sludge BFP sludge sludge sludge
Calorific Value (MJ/Kg)
HHV 18.9 8.6 18.0 9.3
Proximate analysis
VM (%) 77.5 59.4 75.2 57.1
Ash (%) 20.9 36.2 23.5 35.2
FC (%) 1.4 4.4 1.7 7.6
Ultimate analysis
C (%) 37.6 21.0 27.6 23.3
H (%) 9.7 6.5 8.1 6.3
N (%) 1.2 1.9 1.4 1.9
S (%) - - - -
O (%) 38.0 34.4 33.5 33.2
STP-1: ASP 202.5 MLD Kondli, Delhi, And STP-2: ASP 180 MLD, Ahmedabad

The study has been shown similar results as Magdziarz and Wilk (2013), which have been
done for the comparative study of sewage sludge, coal and biomass in Poland. All biomass
including sewage sludge (~13 MJ/Kg) has lower calorific value than coal. Nitrogen content in
the fuel mainly depends on the type of biomass. The wood biomass has very less nitrogen i.e.
<0.05%, oat, coal (2.2%) and sewage sludge (~4%) has comparatively more nitrogen content.
Although the sewage sludge has comparatively very high ash content than coal (~5%) and
biomass (~1%) and low calorific value than coal (LHV~ 24 MJ/Kg), but it is still have higher
volatile matter, high carbon content and good calorific value, so the proper combustion is still
possible for further utilization of sewage sludge.

3.2 TGA curves

TGA thermograms for the primary sewage sludge samples are shown in Figure 1(a, b). In
the TG curve, the mass loss was detected during two regions i.e. 250 to 350 °C which is ~ 9
% that could be due to release of CO2, CH4 and H2 during the heating process. Another distinct
region is found between temperature range of 650 to 750 °C for the loss of ~ 10% mass loss
in higher range of temperature the weight loss could be due to release of CO, CO 2, H2 (Shao
et al, 2008).
 Figure 1: TGA curve for (a) Combustion (Air) of primary sludge, (b) Pyrolysis (N2) of primary sludge,
(c) Combustion (Air) of BFP (digested) sludge, (d) Pyrolysis (N2) of BFP (digested) sludge

The weight loss for the Primary sludge of STP-1 is higher than the primary sludge of STP-
2 (Figure 1 a and b). The difference between both curves is due to the difference in the organic
content of both sludge samples. From the ultimate analysis of sludge, it can be seen that the
carbon content in the primary sludge in STP-1 is higher than primary sludge of ASP STP-2.
The maximum weight loss occurs in the temperature range of 200-800 °C in both
environments i.e. air and nitrogen. Figure 1 (c, d) show the thermal analysis of BFP sludge.
TGA curve for primary sludge (a) combustion (Air), (b) pyrolysis (N2). The weight loss curve
for both sludges is almost similar for the BFP sludge. The sludge samples are almost digested
and have less organic content left owing to the similar weight loss curve. The maximum weight
loss (40%) occurs in the temperature range of 200- 750 °C.

3.3 DTG Curves

Figure 2 (a, b, c and d) show the DTG profiles of the sludge in different environment. It can
be seen the rate loss curve for all sludge is higher in case of air (combustion) compared to
nitrogen environment (pyrolysis). Both of total mass loss and mass loss rate at air atmosphere
were remarkably higher for air environment. The similar results were found in case of final
digested sludge.
Figure 2: Pyrolysis vs Combustion (N2 vs Air) for (a) Primary sludge, STP-1 (b) BFP sludge STP-1(c)
Primary sludge, STP-2 (d) BFP sludge, STP-2

The comparative study of DTG profiles for pyrolysis and combustion has been shown in
Figure 3 for different sludge samples i.e. primary and digested sludge from both STPs, It can
be seen the rate loss curve for all sludge is higher in case of air (combustion) compared to
nitrogen environment (Pyrolysis). Both of total mass loss and mass loss rate at air atmosphere
were remarkably higher for air environment.

As indicated by the DTG curve of sludge, the process of pyrolysis can be classified into
three different stages e.g. volatilisation of water molecules, disintegration of less molecular
weight matter (~70–200°C), the disintegration of assertive organic fraction (~200–600°C) and
the decay of inorganic fraction as well as fixed carbon’s combustion (~600–800°C).
 Figure 3: Comparison between primary and BFP (digested sludge) (a) Pyrolysis (N2) of sludge from
STP Kondli, Delhi, (b) Pyrolysis (N2) of sludge from STP Ahmedabad, (c) Combustion (Air) of sludge
from STP Kondli, Delhi (d) Combustion (Air) of sludge from STP Ahmedabad

According to DTG curve the combustion of sludge samples take place in following stages:
The first stage corresponds to the dehydration or drying process that takes place upto 180°C.
The main decomposition takes place between 180-600°C. Two peaks are observed during
this period one at 350°C and other at 500°C. Both the curves are overlapping for most of the
cases suggesting simultaneous combustion. The mass loss can be attributed to the
decomposition of an organic compound. First, the organics decompose than the combustion
of char formed will begin. Finally, at temperature range 600-800°C, the decomposition of
organics takes place (Conesa et al., 1998; Bianchini et al., 2015).

3.4 FTIR spectra of the sludge

Fourier transform infrared spectroscopy (FTIR) analysis was done for the sewage sludge
samples collected from STPs. It is found in graph some absorption bands region from 3600
cm−1 to 3000 cm−1, the area between 3400 cm−1 and 3000 cm−1 demonstrates stretch of OH
groups available in alcohol and acids. Likewise in some sludge samples another spectral
region, in 3440 cm−1 is an absorption band identified with the stretch of the N–H bonding of
organic compunds. These compounds likewise exhibit characteristics in region of 1000 cm−1
to 1300 cm−1 and identified with C-O groups of carboxylic acids and esters (Hernandez et al.,
2015; Grube et al., 2006).
 Figure 4: FTIR spectra for (a) Primary sludge from STP-2 (b) BFP sludge from STP-2, (c)
Primary sludge from STP-1(d) BFP sludge from STP-1

The other band of absorption in the spectral region of 3000 to 2800 cm−1 are demonstrating
the chain of hydrocarbon (C-H) in the organic matter of the sewage sludge. The bands in
vicinity of 2963 cm−1 and 2920 cm−1 could be stretching of asymmetric C–H bonds of methyl
and methylene respectively, while the band in 2851 cm−1 is identified with the symmetrical
extending of C–H from methylene. The band in 1460 cm−1 also express nature of the C-H
band. The region between 720 to 725 cm−1 express rock nature of CH3-R. The region between
1250 and 1020 cm−1, indicates C-N stretch of aliphatic amine groups. The halides are also
observed in the sludge samples in the absorbance range of 850–550 and 690–515 cm−1. The
results in present study for FTIR was found similar to previous studies Silva et al., (2012).

In this study the sewage samples were collected from the STPs at two different locations,
STP-1 is situated in Delhi (Northern zone India) and STP-2 is situated in Ahmedabad, Gujarat
(Western zone of India). There is no significant difference found in the results of Thermal as
well as FTIR characterization of sludge samples of both STPs.

4. CONCLUSIONS

The thermal behaviour of sewage sludge was studied during slow combustion and pyrolysis
at the heating rate of 10°C/min using thermogravimetric analysis. The results show that the
major loss was experienced during the pyrolysis process at ~ 200 to 750 °C and for
combustion at ~180 to 600 °C i.e. 40%. The sewage sludge samples (mainly primary sludge)
used in this study has significant calorific value, volatile matter and organic content, which are
similar to biomass that has energy potential. The results of FTIR demonstrated that the major
groups in the sewage sludge were aliphatic chains with double bond, carbonyl, and hydroxyl
groups and N–H bonds in the organic compound. There were no significant differences found
for characterization of sludge in terms of location of the STPs.

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