Case Studies in Chemical and Environmental Engineering 2 (2020) 100018

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Case Studies in Chemical and Environmental Engineering

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Influence of pyrolyzed sludge use as an adsorbent in removal of selected

trace metals from wastewater treatment
Anthony Njuguna Matheri a, *, Nicelette Shako Eloko a, Freeman Ntuli a, c, Jane Catherine Ngila b, d
a
Department of Chemical Engineering, University of Johannesburg, Johannesburg, 2028, South Africa
b
Department of Chemical Science, University of Johannesburg, Johannesburg, 2028, South Africa
c
Botswana International University of Science and Technology, Botswana
d
Riara University, Kenya

A R T I C L E I N F O A B S T R A C T

Keywords: The disposal of sludge processes accounts for 60% of the total operation and 40% of total emissions of greenhouse
Adsorbent gas from wastewater treatment plants operations. Moreover, sludge contains pathogenic microorganisms, or-
Biochar ganics, inorganics, trace metals and emerging micropollutants, which can be a public health menace. To comply
Pyrolysis
with the Environmental Protection Agency standards, sludge must be stabilized and detoxified before being
Trace metals
Wastewater treatment
disposed or reused. This study focuses on the use of sludge biochar (adsorbent) from the pyrolysis of wastewater
treatment sludge for the removal of selected trace metals (copper, cobalt and nickel) in aqueous solution by
optimization of the temperature and adsorbent particle sizes. The morphology of the surface at increased tem-
perature (400, 500 and 600 oC) showed an enhanced surface with space and structure (pores) that promoted the
adsorption of metal ions. A decreased of adsorbent particle size from 250 μm to 100 μm and an increased in
pyrolyzed biochar temperature from (400, oC, 500 oC and 600 oC) resulted in the removal of the trace metals
(77.86%, 75% and 56.25% of copper, cobalt and nickel respectively) from the aqueous solution. Biochar produced
from sludge can be an alternative adsorbent for the removal of trace metal in wastewater treatment processes.

1. Introduction to human health and detrimental to the environment [6]. Trace metals
contaminants can hardly biodegrade and gradually accumulates in the
The growth of industrialization, urbanization, population increase environment. They can cause serious health and environment problems
together with the significant growth of modern zones (fourth industrial to becoming ecotoxicological hazard if not properly treated. Beyond the
revolution), has increased issues related to sludge disposal and strict re- threshold, toxic metals such as nickel, copper and cobalt pose serious
quirements to achieve effluent permissible limits for the treatment of damages to human health such as chronic, nervous system, loss of
wastewater. Wastewater streams contain organic, inorganic, trace metals organic function and acute poisoning [7]. It is a great demand to elimi-
and micropollutants from the wastewater treatment processes units. nate these metals ions before discharge. Some of the established waste-
Sludge treatment is considered one of the most important and emerging water treatment process are; membrane filtration, chemical
issues in wastewater treatment, owing to the high demand for energy and precipitation, electrochemical reaction, coagulation and flocculation,
high costs related to its treatment [1–4. The removal of organic, inor- ion-exchange, oxidation and ozonation, adsorption and reverse osmosis.
ganic, trace metals, micropollutants and the treatment of industrial ef- Natural adsorption emerged as the most promising technology due to its
fluents are done through a series of processes (chemical, physical and applicability, versatility, economic feasibility, non-by-product genera-
biological) in a wastewater treatment plant [5]. Currently, there are tion and low toxic [8,9]. Activated carbon is the most prevailing adsor-
environmental concerns associated with the generation of sludge in bent because of the high adsorption capacity, high surface area, and high
developed and developing countries [5]. Many concerns have been raised degree of the surface reactivity, however, it must be regenerated and it is
with regards to sewage sludge disposal due to the rapid evolution of much expensive. Biomaterials support more advantages than activated
industries and rapid urbanization [5]. This is because sewage sludge carbon that includes cheaper synthesised organic and inorganic, the
contains toxic contaminants and pathogens that are potentially harmful chelating group with high concentration and better mechanical stability

* Corresponding author.
E-mail addresses: tonynjuguna22@gmail.com, anthonym@uj.ac.za (A.N. Matheri).

https://doi.org/10.1016/j.cscee.2020.100018
Received 14 May 2020; Received in revised form 13 June 2020; Accepted 15 June 2020
2666-0164/© 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
A.N. Matheri et al. Case Studies in Chemical and Environmental Engineering 2 (2020) 100018

[10]. This is with an advanced strategized novel engineered minimization and stabilization of sewage sludge is a major concern in
nano-material (bio-sorbent). To fulfil this study gap, a sludge absorbent most wastewater treatment. Anaerobic digestion is one of the biological
prepared using a range of pyrolysis temperature and particle sizes are processes used in the stabilization of sludge. It covers the thickening and
utilized with ultra-adsorptive performance and effectiveness. dewatering of sludge in a reactor with an aeration system. The level of
degradation in this process depends on the hydraulic and sludge reten-
1.1. Wastewater treatment processes tion time, temperature, C/N ratio, pH, system temperature among other
parameters. Anaerobic digestion can be achieved under mesophilic and
Wastewater is the fluid waste from domestic and industrial usages. thermophilic temperatures [14].
The wastewater treatment units comprise of the following: Screening; is Anaerobic digestion is reported to be effective in terms of cost since
the unit where course debris (screens etc.) are removed. Primary treat- energy can be recovered from biomethane with less impact on the
ment; is unit where sludge is separated from wastewater using a primary environment. It is used in most of the sewage treatment facilities at full
clarifier. Secondary treatment; this comprises of the activated sludge or scale. This technology is an essential stabilization system in modern
the biofilm process where nutrients are removed. Final treatment (ter- wastewater treatment plants. It assists in the decomposition of organic
tiary); this is the stage where the pathogens are eliminated (disinfection) matter into biogas with 60% bio-methane content. It degrades solids and
[11]. reduces the number of pathogenic substances. Although anaerobic
The sludge produced contains biomass and microbial cells from the digestion provides quite a lot of advantages, there are some disadvan-
wastewater processes. The insight of the wastewater treatment charac- tages associated with this technology i.e. relatively slow process, the
teristics of secondary sewage sludge, dewatered activated sludge, pri- complex materials require a long residence time, long hydrolysis step,
mary sludge, mixed primary and secondary sludge and raw sludge are requires large bio-reactor volume [14].
4195 mg/l (pH of 6.46), 158.31 mg/l (pH 7.82), 30.50 mg/L (pH of The other process used for the stabilization of sludge is composting. It
7.20), 4510 mg/L (pH of 6.61) and raw sludge dependent with the source is often used for the treatment of complex waste whose stabilized product
respectively [12]. could be used as organic fertilizer. Composting is operated under aerobic
Synman and Herselman, (2006) [13] reported that sludge manage- conditions where the aeration facilitates the hydrolysis of complex sub-
ment is still a major concern in South Africa. The conventional ways of stances into simple ones, due to the enzyme production and increase in
sludge disposal include utilization in combustion, anaerobic digestion the rate of growth microorganisms. It is achieved in three stages related
(AD), landfilling, and agronomy as organic fertilizer [5]. Sludge has been to temperature evolution. During the first stage, the temperature of the
also used as a great source of energy in incineration, pyrolysis, gasifica- system is increased due to the growth of mesophilic microbiota. The
tion, AD etc., [13]. This is because of the organic content that amounts to second stage is facilitated by the increase in temperature which activates
approximately 60% in a dry matter [5]. In addition to this, gas obtained the thermophilic microbiota and kills most of the pathogens. In the third
from sludge can also be used as a source of energy (biomethane) since the phase, a decrease in temperature results in the activation of mesophilic
heating value is reduced after the reduction of organic compounds in microbiota. However, this process requires an additional bulking agent
sludge (after anaerobic digestion) during biological biomass conversion such as sawdust. Composting is a stabilization process whose limitations
[5]. are the loss of temperature, the presence of unstable substances and
pathogens, etc., [14].
1.2. Sludge treatment and disposal
1.2.2. Thermochemical treatment: pyrolysis process
Sludge is the residue (solid) from wastewater treatment. It is poten- Although many researchers have been focusing on finding pre-
tially harmful since it contains organic, inorganic, trace metals, harmful treatment methods for the minimization of sludge, a certain quantity of
microorganisms and other toxic pollutants which could be a public health sludge is still produced at the end of the day. Since a zero waste (sludge) is
menace. Rapid modernization in conjunction with rapid industrialization practically not feasible, hence, there is a need for post-treatment of
in most developed countries has led to an increase in sludge production. sludge within the wastewater sector [16]. The thermochemical sludge
The treatment of sludge is therefore considered a major concern in technology such as pyrolysis has been getting attention among re-
wastewater treatment facilities: 60% of the operating cost of the most searchers due to the variety of by-products it generates. Pyrolysis is a
wastewater treatment facility is allocated to the disposal of sludge and process during which biomass (sludge) is heated at high temperatures in
costs related to its treatment [14]. the absence of oxygen to generate syngas, biochar and bio-oil [6]. Hos-
To comply with the environmental protection criteria, sludge from sain et al., (2011) [17] reported that the minimization of sewage sludge
wastewater treatment must be detoxified and stabilized before its final can be done in an ecologically and cost-effectively manner through the
disposal or application. Besides the traditional methods, like landfilling, conversion of sewage sludge by pyrolysis. Biochar, the solid by-products
land application after dry bed, ocean dumping, thermochemical (i.e. of pyrolysis, is a type of black carbon which usually contains traces of
incineration, pyrolysis, gasification) and biological (i.e. anaerobic digestion, polyaromatic carbon, elemental and graphitic carbon. It has been found
aerobic and composting) technologies have been developed for sludge useful in the restoration of destroyed soil, in the improvement of crop
treatment and minimization. yield as well as adsorbents of contaminants. Chen et al., (2014) [18]
report that the properties (chemical and physical) of the biochar obtained
1.2.1. Biological treatment of sludge after pyrolysis depend on the conditions of pyrolysis where temperature,
Traditional methods for sludge disposal have restrictions around the among other conditions, is an important factor that influences the
land application of sewage sludge since they contain toxic organics, in- characteristics of the biochar and bio-oil.
organics and trace metals that are harmful to the living organisms [15]. Pyrolysis is conducted to enhance the porosity of the material being
Incineration, on the other hand, generates an amount of ash which can treated. The decomposition reaction leads to the improvement of organic
only be disposed of in landfills due to the number of toxic substances they functional groups that remain with a carbonaceous skeleton. Chen et al.,
contain. Land applications are facing restrictions due to the shortage of (2014) [18] observed that the pyrolysis temperature increase leads to a
available land space along with the strict regulations around the decrease in the wavelength of the FTIR peaks. It simply indicates that the
permissible effluent limits [15]. Due to strict environmental laws related decomposition of chains of hydrocarbon takes place during pyrolysis and
to traditional disposal methods, biological treatment has drawn much that the functional groups of oxygen are reduced leaving the structure
attention among researchers. Composting, aerobic and AD methods are that provides π -electrons, strong bond with the cation of trace metals.
widely used to remove toxic substances, pathogenic microorganisms and The trace metal removal capacity by use of biochar was also observed
to reduce the sludge volume and sludge stabilization [14]. The and varies depending on pore size, pore-volume, surface area and fractal

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A.N. Matheri et al. Case Studies in Chemical and Environmental Engineering 2 (2020) 100018

dimension. The efficiency removal is directly proportional to the increase graphitic carbon. It has been found useful in the restoration of destroyed
in pyrolysis temperature on biochar preparation. It has been reported soil, in the improvement of crop yield as well as an adsorbent of con-
that an increase in fractal dimension indicates that pyrolysis temperature taminants [6]. Based on the principle of treating waste by waste, bio-
enhances the porosity of the biochar. When the biochar derived from char from sludge, like any other type of adsorbent, has been found
biomass is activated, it exhibits a higher adsorption capacity as compared useful for the treatment of wastewater. Effluents from various industries
to commercialized activated carbon [18]. A study conducted by Chen contain a wide variety of pollutants which are detrimental to the
et al., (2014) [18] reported that 2.5 mg of activated carbon can have a environment. Hence, there is a need to treat them before releasing to
maximum removal capacity of trace metals in wastewater. the water body. Aslan, (2016) [6] reported that the environmental
Hence, it is very important to determine the relationship between pollution problems which affect the aquatic system, as well as the soil, is
the pyrolysis temperature and the properties of the biochar. Several caused by trace metals in effluents. Since trace metals contained in in-
studies have been conducted and yet the uncertainty as to what is the dustrial effluents are considered a threat to the environment, re-
ideal or optimal temperature for pyrolysis remains a key question on searchers have been focusing on techniques to remediate this problem
how it affects biochar pore size, pore-volume, surface area and fractal [6].
dimension [18]. Zieli
nska, A. and P. Oleszczuk (2015) reported that the Various techniques for the removal of trace metals from aqueous
pyrolytic conversion of sewage sludge into biochar enhances the solution are reverse osmosis, oxidation, precipitation, ions exchange,
removal of a considerable number of contaminants in the sludge. They filtration, and adsorption. These techniques have been reported to be
further claim that trace metals bioavailability and ease of motion is expensive and inefficient in cases where the water contains trace metals
decreased in biochar in comparison with unprocessed sewage sludge in extremely low levels [6,21]. Hence, new methods have been investi-
[19]. It has also been reported that biochar from sewage sludge contains gated to treat wastewater. Adsorption is reported to be the preferred
a relatively high amount of minerals and elemental carbon. The biochar process for the removal of trace metals in very low concentrations [6,21].
is also said to have a high number of cations which could be exchanged Activated carbon is the most used adsorbent in the adsorption process.
and has high porosity. Hence, it can be used for the removal of con- Due to the fact that the use of activated carbon is expensive, the use of
taminants from wastewater [19]. Since activated carbon, the most used readily available, less expensive alternatives such as sludge has been
material for contaminants removal, is reported to be quite expensive, investigated [6,22]. Although commercialized activated carbon pos-
biochar derived from the readily available material such as sewage sesses better physical properties (high surface area, high pore volume) than
sludge is becoming an alternative adsorptive material to inexpensive those of biochar, the capability of biochar (from sludge) to adsorb both
processes [19]. organic pollutants and trace metals has been reported to be quite similar
Adsorbents are, amongst other application, used for the purification or even better than those of activated carbon [5,6]. The other advantage
of water. Sand is mostly used in the most filtration system. Owing to the of biochar from sludge, as an adsorbent, is that the process is done at a
limitations of sand to remove some contaminants, filters with multiple relatively low cost since no activation is required [6,18]. Hence, this
layers and various substances are used to trap contaminants. Coal is study will focus on the use of pyrolysis by-products (biochar) from sludge
mostly used in such multiple layer system, but its high cost and unsus- as an environmentally friendly process for wastewater treatment. The
tainability leave room for improvement [19]. Hence, Zieli
nska, A. and P. biochar will act as an innovative adsorbent for the treatment of waste-
Oleszczuk (2015) [19] reported that using waste from industrial sectors water utilizing sludge disposal.
could lead to the development of cost-effective and reliable water
treatment techniques. 1.3. Sludge pyrolysis parameters
Praspaliauskas and Pedisius, (2017) [5] reported that the use of
sludge as fertilizer is a method which is no longer supported or allowed. Parameters such as temperature, residence time and particle size have
Sludge is collected throughout the year while the soils need to be a direct effect on the quality of biochar. Chen et al., (2014) [18] reported
fertilized only once or twice a year. Therefore, the collected sludge must that the properties (chemical and physical) of the biochar obtained after
be kept until future use, which brings the same environmental menace pyrolysis depend highly on the conditions of pyrolysis.
and headspace costs. In addition to that, a hindrance to the use of sludge
in agriculture has led to an important decrease in the usage of sewage 1.3.1. Pyrolysis temperature
sludge in the agricultural sector [5]. Temperature has been reported to be the most important parameter in
The trace metals from sludge are still found in the ashes which are the pyrolysis process. It has a considerable effect on biochar quality.
released into the atmosphere along with exhaust gases (fly ashes). These Agrafioti et al., (2013) [12] reported that an increase in pyrolysis tem-
necessitate a proper treatment of the exhaust gases for the reduction of perature beyond optimum leads to a decrease in the yield of biochar. A
trace metals pollution since exhaust gases must comply with environ- yield decrease of 32% was observed from 300 oC to 500 oC which can be
mental regulations. This method is partially inefficient and therefore less justified by the first decomposition of the dry feed and the second
preferred [5]. A wide gap of research is open in utilization, beneficiation decomposition of the solid product [12]. A similar trend was observed by
and handling of sludge in most developed and developing countries. Hossain et al., (2011) [17].
Several alternatives have been developed for sludge minimization and Pyrolysis temperature also affects the pH of the biochar. Hossain
utilization. Amongst other techniques, pyrolysis of sludge has been re- et al., (2011) [17] observed that low pyrolysis temperature favours
ported to be a cost-effective and clean method [18]. acidic pH whereas biochar subjected to high temperature was alkaline.
Pyrolysis of sludge, unlike other methods, focuses on the recycling of A similar observation was made by Agrafioti et al., (2013) [12], they
valuable fuel substances (hydrocarbon) while decreasing the amount of concluded that biochar obtained at low temperature was appropriate
solid waste [18]. Among the various techniques developed for the utili- for agricultural applications whereas that obtained at high tempera-
zation of the wastewater residue, the production of biochar through ture was suitable for the removal of pollutants due to the highly
pyrolysis to treat the very same wastewater has been reported to be porous structure developed. Hence, the ideal pyrolysis temperature
economical and effective for the industrial effluent treatments. The most depends highly on biochar future applications [17]. Besides the effect
common substance used in the treatment of wastewater is activated it has on pH and the yield, increasing pyrolysis temperature reduces
carbon [20]. However, it is being rapidly replaced by other carbonaceous the amount of nitrogen, the capacity of water sorption and the ca-
materials (agricultural waste, sludge, etc.,) because they are readily pacity of cation exchange whereas the stability of heavy and carbon
available and affordable. content increases [10].
Biochar, the solid by-products of pyrolysis, is a type of black carbon To make sure of the trace metal stability, Agrafioti et al., (2013) [12]
which usually contains traces of polyaromatic carbon, elemental and performed a toxicity characteristic leaching procedure on sludge as well

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A.N. Matheri et al. Case Studies in Chemical and Environmental Engineering 2 (2020) 100018

as the obtained biochar to assess the possibility of contaminants transfer and sulphur (CNHS). The proximate and ultimate analysis was in
to a liquid medium. Their findings revealed that the transfer of trace accordance to the ASTM D3173 (moisture content), ASTM D3302 (total
metals from biochar was not considered since their range was between solids), ASTM D3175 (volatile solids) and ASTM D3176-89 (elemental
zero (0) and 0.74 mg/kg whereas that of the raw material (sludge) was analysis) standard [23]. The pH of the sludge and metal ions were
between zero (0) to 5.5 mg/kg) [12]. measured. Scanning electron microscope (SEM)-(JSM 6360l VSEM,
The pyrolysis temperature also influences the BET surface area. An JEOM, Co, Japan) and X-ray fluorescence (XRF)-(Rigaku ZSX Primus II)
increase in the temperature results in an increase in surface area. An analysis were conducted on the sludge before pyrolysis to determine the
increase of 13.92 m2 has been observed by Agrafioti et al., (2013) [12] chemical composition and to observe the surface morphology for the
from a temperature of 300 oC–500 oC. This behaviour is attributed to the latter. Brunauer emmett teller (BET) analysis was conducted on the
fact that the chemical structure of the sludge (feed) was altered during sludge to determine its surface area as well as its pore sizes and volume.
pyrolysis. Furthermore, increasing the temperature of pyrolysis results in
an improvement of the aromaticity of the sludge, which promotes the 2.1.3. Biochar production using the pyrolysis process
formation of mesopores and micropores thus a high surface area is The sludge was pyrolyzed in a furnace for 10 min. A set of samples (50
observed. However, the formation of mesopores and micropores is hin- g each) was carbonized (pyrolyzed) in triplicate to assess the effect of
dered by the high content of the feed (sludge). Hence, the characteristics temperature (400 oC, 500 oC and 600oC) and particle size (100 μm and
of sludge, at any rate, determines the quality of the biochar [12]. 250 μm) on the yield of biochar [5] and bio-oil as a by-product. The
temperature variation was evaluated using TGA-FT on the degradation of
1.3.2. Residence time the samples. The yield of biochar was calculated using Equation (1) [24].
The other factor that influences the quality of biochar is residence
mbiochar
time. However, in the studies done by Agrafioti et al., (2013) [12] Biochar Yield ¼ x100 (1)
msludge
showed that the residence time did not have a much significant effect
on the yield of biochar on as there was no considerable yield change
among samples pyrolyzed at the same temperature for 30, 60 and 90 2.1.4. Characterization of biochar
min. Scanning electron microscope (SEM) and X-ray fluorescence equip-
This study aimed to utilize biochar generated from wastewater ment (XRF) analysis were conducted on the biochar after pyrolysis to
treatment sludge in the purification of wastewater. The adsorptive per- determine the chemical composition and to observe the surface
formance of biochar from sludge produced under different temperature morphology for the latter. Brunauer emmett teller (BET) analysis was
and particle size in the removal of trace metals (Co, Cu and Ni) was conducted on the biochar to determine its surface area as well as its pore
investigated. There are no studies for modified sludge as an adsorbent for sizes and volume.
selected trace metals removal (Ni, Co, Cu) under adsorbent modification
at a pyrolyzed temperature of 400 oC, 500 oC and 600 oC and at a particle 2.1.5. Adsorption process
size of 100 and 250 μm. A 0.125 g of the biochar (100 μm and 250 μm) obtained at 400, 500
and 600 oC was mixed with different 100 mL of prepared solution of trace
2. Methodology metals concentration. A prepared solution of 0.1 mmol of copper, cobalt
and nickel was used to investigate the adsorptive capacity of the biochar.
Sewage sludge was quantified and collected from a domestic waste- A thermostatic agitator (stirred batch adsorption systems) at 200 rpm
water treatment plant, Gauteng Province, South Africa. It was used for (constant agitation rate) was used to agitate the solutions for 10 hours at
the generation of biochar, which served as an adsorbent in the experi- both constant of 25 oC and 30 oC separately [5]. The batch solutions were
ment. The effect of pyrolysis temperature was assessed. The parameters filtered using a Buchner funnel. The metal concentration of both the
(temperature and adsorbent particle size) were investigated for the trace wastewater and the filtrate was determined using ICP-OES and AAS.
metals (copper, cobalt and nickel) removal from aqueous solution (SM
Figure A1). 2.2. Adsorption isotherm modelling

2.1. Experimental procedure Adsorption isotherm was studied using Langmuir and Freundlich
isotherm models at equilibrium. Langmuir isotherm model was used to
2.1.1. Sample preparation and preliminaries analysis predict the mono-layer adsorption surface of the active site. This involved
The sludge was crushed in a cone crusher to reduce its size. It was the interaction between the trace metal ions and the absorbent by
then screened to obtain two different particle sizes: 100 and 250 μm. employing excel data fitting to the linear Langmuir model in Equation (2)
Thermogravimetric analysis (TGA) was conducted on the sample to [25,26].
assess its level of degradation. Fourier transform infrared spectroscopy  
(FT-IR) was used to evaluate the degradation rate and composting of the Ce 1 1
¼ Ce þ (2)
sample. The trace metal concentration of the wastewater was determined Qe qr qr b
using Atomic Absorption Spectrometer (Thermo scientific ICE 3000 Se-
where Qe was the adsorption capacity at equilibrium, qr was the
ries) and inductively coupled plasma-optical emission spectrometry (ICP-
adsorption capacity of the maximum mono-layer, b was the Langmuir
OES) -(ICAP 6500 Duo, Thermo Scientific, UK). A solution of 0.1 mmol of
constant and was related to the energy of adsorption, Ce was the con-
copper, cobalt and nickel was prepared with initial concentrations of 28
centration of the metals at the equilibrium. The Langmuir parameters (b
ppm.
and qr) and coefficient of determination (R2) were determined from
linearization plotting of Ce/Qe Vs Ce.
2.1.2. Characterization of sludge
Freundlich isotherm model was used to describe the multi-layer
Sewage sludge characterization (proximate and ultimate analysis) was
physio-chemical adsorption on a heterogeneous surface (Equation (3))
done to ascertain the composition. The proximate analysis consisted of
[26,27].
the total solids (TS%), moisture content (MC%) and volatile solids (VS
%). Total solids and moisture content of sludge at 20 g were analysed in 1

triplicate using an oven for 24 hours at 105
C. Volatile solids were Logðqe Þ ¼ LogðCe Þ þ Log kf (3)
n
analysed in triplicate using a furnace at 550
C for 2 hours. The ultimate
analysis consisted of elemental analysis of carbon, nitrogen, hydrogen, where qe was the adsorption capacity at equilibrium (mg/g), Kf was the

4
A.N. Matheri et al. Case Studies in Chemical and Environmental Engineering 2 (2020) 100018

Freundlich constant that represented the adsorption capacity and the degradation rate and composition of the sewage sludge. The main
adsorptive bond (L/mg), n was the heterogeneity factor that represented functional group of the raw sludge and activated sludge were charac-
the relative distribution and adsorption intensity of the energy and het- terised by FT-IR as shown in Fig. 2.
erogeneity of the site of the adsorbate and Ce was the concentration of the The composition of the sludge samples affected the shape of the FT-IR
liquid phase equilibrium (mg/L). Freundlich parameters (Kf and n) and spectra. It reflected the chemical composition of the sample due to
coefficient of determination (R2) were determined from linearization degradation processes [32]. Spectra reflected a strong intensity of 3940
plotting of Log (Qe) Vs log (Ce). cm1 at the beginning of the analysis. This suggested that the compound
The mass balance of copper, cobalt and nickel adsorbed (qe) and the was much affected by the activated sludge capacity and chemical
efficiency removal (R) was determined using Equations (4) and (5) composition. The intensity, shape and appearance nitrate band at 1186
respectively [28]. cm1 for 400, 500, 600 oC was evident for sewage sludge-based compost
maturity. The results show a fraction of aliphatic phosphates, aliphatic
Ci  Ce carboxylic acids, alkynes monosubstituted, aliphatic hydrocarbons and
qe ¼ Vsolution (4)
Madsorbent primary aliphatic alcohols. An increase in peak ratio was due to the
decomposition of the sludge. There was a notable variation in relative
Ci  Ce intensity of the functional groups of the pyrolyzed sewage sludge using
R¼ (5)
Ci FT-IR spectra. The composition was supported by the activated sludge
analysis library by Grube, M et al. (2005) [32] and Kowalski, M et al.
where qe was the capacity of adsorption, Ci was the initial concentration
(2018) [33]. The FT-IR analysis appeared to be useful in composition
of the trace metal, Ce was the equilibrium concentration of the trace
monitoring of activated sludge and provided a useful indicator for the
metals, Vsolution was the volume of the solution and Madsorbent was the mass
change of sludge characteristics.
of the adsorbent.

3.4. Biochar composition

3. Results and discussions

The characterization of the biochar as a source of adsorbent from the

3.1. Sewage sludge characterization
pyrolyzed process is shown in Fig. 3. It was observed that the metals
reduced in concentration with the optimization of different temperature.
Sewage sludge characterization (proximate and ultimate analysis) was
The XRF results revealed constant trace metals concentration with an
done to ascertain the composition. The proximate analysis consisted of
increase in pyrolyzed temperature of the biochar production.
the total solids (TS%), moisture content (MC%) and volatile solids (VS
There was a significant decrease in the amount of Fe from 27.4 mg/L
%). The ultimate analysis consisted of elemental analysis of carbon, ni-
to 16.3 mg/L, Ca from 20.5 mg/L to 14.6 mg/L and Si from 3.63 mg/L to
trogen, hydrogen, and Sulphur (CNHS). The pH of the sludge and metal
6.2, mg/L, P from 11.2 mg/L to 9.4 mg/L, Mg 2.32 mg/L to 1.51 mg/L,
ions were measured.
with lowest recorded at Cr 0.17 mg/L to 0.12 mg/L when the temper-
The moisture content of 37.16% indicated less temperature required
ature raised from 400 oC to 600 oC (pyrolyzed temperature in prepa-
to remove water during the pyrolysis process. High total solids (37.18%)
ration of biochar) in the solution. Approximately 40-80% of metal
and volatile solids (62.82%) indicated a high organic content that gave a
contained in wastewater was fixed into the sewage sludge. This justifies
good thermo-chemical process. The C, N, H and S were 31.5, 2.81, 5.08
the high amount of certain metals in sludge. The concentration of
and 1.5 respectively. The carbon-nitrogen ratio of 11.2 indicated high
metals in sludge depends on the origin of the sludge sample. Trace
carbon content that was converted to biochar with lesser pollutant
metals (cobalt, copper and nickel) concentrations were too low to be
compound formation like hydrogen sulphide and carbon monoxide. The
detected using the XRF.
pH of the sludge was found to be 7.02, copper 6.5, nickel 6.8 and cobalt
6.9. The pH of the solution in the adsorption process played a role of
3.5. Biochar yield
particle diffusion (hydrophobic interaction) that modify the concentra-
tion of the metal ions and shape (surface charge).
Pyrolysis process was performed and optimized at three different
temperatures (400, 500 and 600 oC), with a particle size of 100 and 250
3.2. Degradation of the sludge μm at 10 min. Fig. 4 shows the biochar yield from the sludge in the py-
rolysis process.
The thermal analysis (degradation) of the sludge was determined At 500 oC, the yield for the 100 μm sample was 58% while the one for
by the use of thermogravimetric analysis (TGA), derivative thermog- 250 μm sample was 55%. This was in agreement with what was reported
ravimetry (DTG) and differential thermal analysis (DTA). This was the by Agrafioti et al., (2013) [12]. In this study, 10 min was sufficient for the
mass degraded per rate of change of temperature as showed in Fig. 1. pyrolysis reaction. The decrease in pyrolysis temperature increased the
The degradation assisted in the determination of the optimum yield of biochar with high-quality adsorbent produced at an increased
temperature of pyrolysis that was 200–650 oC due to mass loss and temperature of 600 oC. The yield of biochar at 400 oC reported as 82.8%
evaporation of moisture content. The derivative thermogravimetry while the yield at 600 oC was reported as 57.9%. This could be possibly
(DTG) indicated the gain/loss of the sample weight in the thermal due to further conversion during pyrolysis, that is, a better primary
transition. The differential thermal analysis (DTA) indicated the spe- decomposition of the sludge or the fact that the solid residue underwent a
cific temperature of reaction at which the specific changes (phase secondary decomposition [12]. A study by Agrafioti et al., (2013) [12]
transition) occurred within the sample (exothermic or endothermic) observed a decrease of 32.5% when the temperature was increased from
[29]. The devolatilization occurred at a threshold of 17.7 at biochar 300 oC to 500 oC. Another study by Hossain et al., (2011) [17], showed
combustion mass%/min. This enhanced accuracy, efficiency and pre- that the biochar produced through sewage sludge pyrolysis in a fixed bed
cision. The higher heating values and gross calorific values are ther- reactor yield was 72.3% of the same amount at 300 oC and decreased to
modynamic conversions that helped determine the condition of 52.4% at 700 oC.
biomass combustion [30,31].
3.6. Biochar surface area
3.3. Functional group analysis
The surface area of the biochar was determined as part of the charac-
Fourier transform infrared spectroscopy (FT-IR) was used to evaluate terization. It was observed that an increase in pyrolysis temperature

5
A.N. Matheri et al. Case Studies in Chemical and Environmental Engineering 2 (2020) 100018

Fig. 1. Thermo degradation of sludge using thermogravimetric analysis.

Fig. 2. FTIR spectra of raw sewage sludge and activated sewage sludge.

increased biochar surface area. The BET specific surface area was deter- of adsorption sites and increased capacity.
mined to be 355 m2/g. There was an increase of about 30 m2 per gram when
the temperature was increased from 400 to 600 oC. This was in agreement
with a study by Agrafioti et al., (2013) [12] that observed an increase of 13 3.7. Surface morphology of raw sludge and biochar
m2 when the temperature was increased from 300 to 500 oC. This was
justified by the fact that there was a change in the structure of the initial The surface morphology of the raw sludge and the biochar at different
feed (sludge). The atomicity of biochar increased with an increase in py- temperature (400, 500 and 600 oC) was analysed using scanning electron
rolysis temperature, hence the formation of micropores and mesopores microscopy (SEM) and micrograph shown in SM Figure A2. It was
which are linked to high surface areas. Besides the pyrolysis temperature observed that the surface morphology of the raw sludge showed pores on
and the characteristics of the feed, BET surface areas were affected by the the surface of the residue, whereby the entire surface was covered by the
process of production, the rate of heating and time of reaction [34,35]. white contaminates that could be inorganic and trace metals attached to
According to Erto, A. et al.,. (2013) [36], BET area is not the key parameter the sludge as confirmed by SEM. The morphology of the surface at
for adsorption. High BET surface area was useful support to a great number increased temperature (400, 500 and 600 oC) showed an enhanced sur-
face with space and structure (pores) because of temperature increase.

6
A.N. Matheri et al. Case Studies in Chemical and Environmental Engineering 2 (2020) 100018

Fig. 3. Adsorption of trace metals solution under different pyrolyzed temperature and particles sizes of biochar.

produced from sludge particle size (100 μm and 250 μm) and pyrolysis
temperatures of 400 oC, 500 oC and 600 oC, at the adsorption temperature
of 25 oC, in 10 hours and 200 rpm was undertaken and the results pre-
sented in Fig. 5.
It can be observed that the highest rate of removal was achieved with
the 100 μm biochar pyrolyzed at 400 oC, 500oC and 600 oC with the
lowest registered at 600 oC of biochar particle size of 250 μm. The effi-
ciency of removal at 25 oC of the three trace metals was high at 77.86%
(600oC, 100 μm), 56.25% (600oC, 100 μm) and 75% (600oC, 100 μm) for
the cobalt, nickel and copper respectively with low efficiency removal
recorded at 59% (400oC, 250 μm), 40% (600oC, 250 μm), 59% (400oC,
250 μm), for cobalt, nickel and copper respectively. This indicated that
the biochar produced had a strong affinity for trace metals (copper, cobalt
Fig. 4. Biochar yield from the sludge in the pyrolysis process. and nickel). Cobalt and copper were compatible with the adsorption pa-
rameters, unlike nickel. The trace metal distribution reflects an interac-
The intervening space and structure promoted the adsorption of metal tion during the adsorption and adsorption capacity within the particles.
ions. Bio-sorbent showed a selective adsorption capacity towards the three
metals ion (Ni, Co and Cu) A study by Hossain et al., (2011) [17] reported
that the effectiveness of the immobilization of trace metals by biochar
3.8. Effect of temperature increase on the trace metal removal rate was highly dependent on the type of contaminant found in the aqueous
(adsorption) solution. A similar conclusion was drawn by Inyang et al., (2012) [37],
with an observation of high efficiency of removal for copper (98%) and
3.8.1. Adsorption at 25
C low removal of nickel by 26% that was attributed to the high sorption of
Trace metals (Co, Ni and Cu) removal rate (RR%) using adsorbent

Fig. 5. Trace metal removal rate using sludge biochar particle size (100 μm and 250 μm) and temperature (400, oC, 500
C and 600
C) at agitation temperature of 25


C in 10 hours.

7
A.N. Matheri et al. Case Studies in Chemical and Environmental Engineering 2 (2020) 100018

Fig. 6. Trace metal removal rate by optimization of the particle size (100 μm and 250 μm) and temperature (400, oC, 500
C and 600
C) at agitation temperature of
30
C in 10 hours.

Table 1 in the removal of the trace metals. It was observed that a small range of
Comparison of the Langmuir and Freundlich isotherm model constants and adsorption temperature (25 oC and 30 oC) did not have a significant effect
analysis errors of different metals by activated sludge adsorbent. on the rates of removal of trace metals concentration before and after the
Parameters Langmuir Isotherm Freundlich Isotherm Model adsorption process. The high rate of pyrolysis temperature had a great
Model effect on the adsorption process of the trace metals. Adsorption capacity
qr b R2 1/n n kf R2 increased with increase in adsorbent prepared from 400 to 600 oC due to
the diffusion of the molecules across the layers of the external bound-
Cobalt
Pyrolyzed 9.24 0.29 0.96 0.23529412 4.25 3.26 0.97 aries, internal pores of the particles of the adsorbent that decreased the
sludge at viscosity for the high concentration solution and change of the equilib-
400
C rium capacity of the adsorbent. A decrease of adsorbent particle size from
Pyrolyzed 9.73 0.32 0.96 0.24096386 4.15 3.26 0.96 250 μm to 100 μm and an increase in pyrolyzed biochar temperature
sludge at
500
C
from (400, oC, 500 oC and 600 oC) resulted in a high rate of removal of the
Pyrolyzed 10.60 0.39 0.95 0.23809524 4.20 3.19 0.93 trace metals from the aqueous solution. The efficiency of removal at 30 oC
sludge at of the three trace metals was high at 72% (600oC, 100 μm), 54.11%
600
C (600oC, 100 μm) and 71.96% (600oC, 100 μm) for the cobalt, nickel and
Nickel
copper respectively with low efficiency removal recorded at 60% (500oC,
Pyrolyzed 5.53 0.29 0.97 1.01010101 0.99 9.12 0.98
sludge at 250 μm), 41.61% (600oC, 250 μm), 63% (500oC, 250 μm), for cobalt,
400
C nickel and copper respectively. The low-cost natural adsorbent (sludge)
Pyrolyzed 5.67 0.15 0.97 1.03092784 0.97 8.93 0.97 can be used as an adsorbent due to its capacity of the metal binding.
sludge at
500
C
Pyrolyzed 5.27 0.14 0.96 1.04166667 0.96 11.30 0.94
sludge at 3.9. Adsorption isotherm modelling
600
C
Copper Adsorption isotherm was studied using Langmuir and Freundlich
Pyrolyzed 9.40 0.50 0.97 0.53191489 1.88 5.60 0.95
isotherm models at equilibrium. Langmuir isotherm model was used to
sludge at
400
C
predict the mono-layer adsorption surface of the active site. This involved
Pyrolyzed 10.13 0.34 0.97 0.48309179 2.07 5.22 0.98 the interaction between the trace metal ions and the absorbent by uti-
sludge at lizing excel data fitting to the linear Langmuir model. It assumed that
500
C there no interaction among the adsorbed molecules on the adsorption
Pyrolyzed 11.08 0.44 0.94 0.40816327 2.45 5.46 0.97
sites neighbouring. Langmuir parameters; qr (adsorption capacity of the
sludge at
600
C maximum mono-layer) and b (Langmuir constant that was related to the
energy of adsorption) and coefficient of determination (R2).
Freundlich isotherm model was used to describe the multi-layer
certain trace metal from solutions due to their high constant of electro- physio-chemical adsorption on the heterogeneous surface. It assumed
negativity. Inyang et al., (2012) [37] on the other hand, suggested that that binding sites were occupied first and adsorption strength decreased
the electronegativity alone does not give a complete explanation to the with the occupation degree. Freundlich parameters; Kf (Freundlich con-
rate removal. stant that represented the adsorption capacity and adsorptive bond), n (het-
erogeneity factor that represented the relative distribution and
3.8.2. Adsorption at 30
C adsorption intensity of the energy) and coefficient of determination (R2)
Trace metals (Co, Ni and Cu) removal rate (RR%) using adsorbent were determined. Table 1 shows the comparison of the Langmuir and
produced from the sludge of particle size (100 μm and 250 μm) pyrolyzed Freundlich isotherm model parameters and analysis errors of metals (Co,
at a temperature of 400 oC, 500 oC and 600 oC, at the adsorption tem- Ni and Cu) by activated sludge adsorbent at 400 oC, 500 oC and 600 oC.
peratures of 30 oC, in 10 hours and 200 rpm was undertaken and pre- Freundlich and Langmuir isotherm model described the distribution
sented in Fig. 6. of adsorption energy into the adsorbent heterogeneous surface. Adsor-
Temperature was an important parameter for the adsorption process bent at high concentration was well described by the Langmuir isotherm

8
A.N. Matheri et al. Case Studies in Chemical and Environmental Engineering 2 (2020) 100018

while Freundlich isotherm model described the adsorbent at low con- Declaration of competing interest
centration. Adsorption was directly proportional to the surface fraction of
the adsorbent as described by Langmuir model [27,38,39]. Isotherm The authors declare that they have no known competing financial
model with equilibrium data was well represented by the Freundlich interests or personal relationships that could have appeared to influence
model with a high coefficient of the correlation that defined the distri- the work reported in this paper.
bution exponential of active sites and surface heterogeneity. According to
the Bhandari V.M. et al., (2014) [8], and Sahoo, S. et al. (2013) [38], 1/n Acknowledgement
that is a function of the adsorbent strength indicates affinity between the
adsorbate and adsorbent. The value of 1/n < 1 implies that the The authors wish to acknowledge the Water Research Commission
adsorption process is a chemical process, 1/n > 1 implies that the (WRC) in South Africa, Project No. K5/2563 for funding. University of
adsorption process is a physical process, 1/n approaches zero when the Johannesburg (UJ), Process, Energy, Environmental Technology Station
surface was heterogeneous. The adsorption process of the cobalt and (PEETS) funded by Department of Science and Technology (DST)
copper was a chemical process and that one for nickel was a through Technology Innovation Agency (TIA), City of Johannesburg
physio-chemical process. The value of n > 1 as showed in cobalt and (CoJ), Gladtech International, South Africa wastewater treatment plants,
copper indicated a favourable adsorption process. The value of n and Kf Innovation Hub and water utilities managements and staffs for capacity
increased with an increase of the adsorbent pyrolyzed temperature in the building and knowledge transfer.
removal of the trace metals. The variation of Kf indicated that the
adsorption energies (bonding energy of the adsorption reaction) between Appendix A. Supplementary data
the metal ions (adsorbate) and adsorbent were different. High Kf that is
correlated with fast adsorption was observed in the physio-chemical Supplementary data to this article can be found online at https://
process of the nickel removal. The qr indicated limiting adsorption ca- doi.org/10.1016/j.cscee.2020.100018.
pacity when the adsorbent surface was fully covered metal ions
(adsorption capacity of the maximum mono-layer) [28]. The correlation References
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