Biomass Conversion and Biorefinery

https://doi.org/10.1007/s13399-023-04710-y

ORIGINAL ARTICLE

Adsorption of methylene blue dye by animal dung biomass–derived

activated carbon: optimization, isotherms and kinetic studies
Senthilkumar Kandasamy1 · Neeraja Madhusoodanan1 · Prathap Senthilkumar1 · Vasant Muneeswaran1 ·
Naveenkumar Manickam2 · Venkata Ratnam Myneni3

Received: 24 May 2023 / Revised: 30 July 2023 / Accepted: 3 August 2023

© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2023

Abstract
Industrial wastewater like textile dye effluent contains dye mixed with a variety of contaminants at varying ranges. Therefore,
proper treatment of wastewater before discharge into the environment is mandatory. The major objective of the present study
is to investigate the ability of sheep and goat dung–derived activated carbon as adsorbents for methylene blue dye removal
from aqueous solution in a batch mode. The activated carbon was synthesized from sheep and goat dung, by an easy batch
procedure using carbonization and hydrothermal techniques. The surface morphological studies were performed using Field
Emission Scanning Electron Microscope. Batch adsorption studies were done by an approach, a mathematical and statistical
approach, known as Response Surface Methodology (RSM) where the correlation of parameters includes pH (2–6), adsorbent
weight (0.5–1.5 g) and contact time (5–60 min). The adsorption showed pH-dependent profile and the pH was found out
to be 6 as the optimum value. The percentage of methylene blue dye removal was analyzed to be 99.6% and the maximum
adsorption capacity was found to be 24.81 mg/g for the adsorbent of goat dung activated with potassium hydroxide (KOH).
The models developed using RSM have given a successful interpretation of the experimental values in accordance with the
operating variables. Also, the predicted and experimental values of RSM experiments were found out to be very similar.
The equilibrium adsorption isotherm modelling has shown that the equilibrium data fitted best for the Freundlich model for
­ZnCl2-activated adsorbents, for instance the Langmuir model for KOH-activated adsorbents and Dubinin–Radushkevich
model for hydrothermally carbonized adsorbent. The value of correlation coefficient (R2) for methylene blue dye removal
was determined as 0.9961 for 60 ppm concentration and in fact, the predicted R2 value says how good the regression model
assumes and properly predicts the responses for the experiments. The kinetic data perfectly suited to pseudo-2nd-order kinetic
model for all the five adsorbents.

Keywords Biomass · Biomass valorization · Adsorbent · Animal manure biomass · Effluent treatment

* Senthilkumar Kandasamy Venkata Ratnam Myneni

uksen2003@gmail.com mvratnam81@gmail.com
Neeraja Madhusoodanan 1
Department of Chemical Engineering, Kongu Engineering
neerajalive1002@gmail.com
College, Erode, Tamil Nadu, India
Prathap Senthilkumar 2
Department of Civil Engineering, Easwari Engineering
03prathap@gmail.com
College, Chennai, Tamil Nadu, India
Vasant Muneeswaran 3
Department of Chemical Engineering, MVJ College
vasantrajan60@gmail.com
of Engineering, Bengaluru, Karnataka, India
Naveenkumar Manickam
er.naveenmanick@gmail.com

13
Vol.:(0123456789)

1 Introduction
It is known that the basic necessities for human beings
are food, water, cloth and shelter while the most basic
necessity for every living and non-living entity is water.
We cannot imagine our life without water and it is our
responsibility to not pollute our water resources and in
turn our environment [1]. There are two types of water on
this Earth–that is, freshwater and saline or brackish water.
From this, freshwater is basically used for all our basic
day-to-day needs, whereas saline water is the one which
forms seas, oceans and also some of the rivers and lakes.
But what makes it the interesting matter is that only 2.5 to
2.75% of the total water found on the Earth makes up to
freshwater availability. The remaining 97% is saline water.
This is why it is an alarming issue for the conservation of
freshwater bodies so that the living organisms on land can
sustain their lives [2, 3].
Most of us are aware of the fact that all types of indus-
tries require basic utilities to function their industry starting
from water and land resources to electricity and plant opera-
tion utilities. Since water is the first and foremost need,
majority of the production industries look for land near to
a freshwater body so that they can utilize the water without
any extra charges to be paid for it. Resultantly, the pro-
duction industries use this water for all their processes and
hence the effluents from these industries are let out to the
environment where the contaminants can also flow and dis-
solve into the same water body thereby polluting their water
source. This is why necessary treatment operations are to be
strictly carried out to remove the contaminants and harmful
substances prior to discharge of the industrial wastewater
effluent. Water pollution severely affects ecosystems and the
environment as a whole. When poorly treated wastewater is
released into the water resources, it completely disrupts the
functioning of the ecosystems present in the water body and
degrades them [2–5]. The effect of this damage is unimagi-
nable that it destroys individual species to larger biological
communities. Initially, we think of the destruction of the
ecosystems when water pollution is of concern but water
pollution can also lead to water-borne diseases like gastroin-
testinal diseases and pathogenic infections in humans when
polluted water is used for the basic needs of the people. The
main pollutants that can degrade the quality of water are
suspended solids, biodegradable organic matter, pathogens,
nutrients, non-biodegradable organic matter and insoluble
dissolved solids [3–7].
Textile and dye industries are such industries that pro-
duce effluents with humungous quantities of wastewater
containing high concentrations of colouring substances.
This wastewater requires proper efficient treatment prior
to their discharge into the environment by removing the
13
Biomass Conversion and Biorefinery
colour-imparting materials to a greater extent up to which it
may not pose any vicious threats to the nature. Textile man-
ufacturing includes an important step which is the dying
process. During this process of dying, colour or pigment is
imparted to the fabric fibre where different types of chemi-
cals are mixed with this dye to stabilize them so as to make
the adsorption process easier between the colour and fibre
[3]. After the finishing process of the final product, some of
the leftover dyes and stabilizers become a part of the textile
wastewater effluent. This effluent will contain enormous
amounts of toxic chemicals within unacceptable ranges
which when discharged locally will definitely pollute the
soil, surface water as well as ground water. Therefore,
stringent methods are to be implemented to get treated the
textile wastewater before their discharge into local water
bodies. If this gets implemented, the treated water can be
recycled for many other purposes like irrigation and also
for reuse of the water in the same textile factory operations.
Textile wastewater constituents vary from factory to factory
and from country to country. It also depends on various
other factors like the type of process, type of the fabric
they produce, equipment used for the factory operations
and also the trend in fashion. These effluents will contain
metal contaminants like chromium, zinc, mercury and lead
[4–6] and additives like caustic soda and sodium carbonate
salts other than dyes and pigments. Their concentrations
vary from time to time according to the factors which are
mentioned above. From this, we can clearly understand that
treatment of textile wastewater is indeed a very big deal so
that the effluent concentrations can be considerably reduced
thereby causing less pollution [7–9].
Dye effluent can be primarily treated using chemical, bio-
logical or physical treatment methods depending upon the
constituents of the effluent where the metal contaminants and
salts can be removed. After properly treating the dye waste-
water using chemicals, next it is to remove the pigmentation
that is imparted to the water. From this stage onwards, acti-
vated carbon plays a major role in removing the colour from
the wastewater [9–11]. We all know that biomass-derived
activated carbon is widely used in every aspect of our day-
to-day life such as drinking water treatment to air pollution
and bioenergy with wastewater treatment [12–14]. To over-
come the drawbacks of the existing treatment methods such as
physicochemical methods, activated carbon is being used for
adsorption process due to their pore structure and characteris-
tics, high surface area and more adsorption capacity, and also
they can be synthesized from different biomass and different
carbonaceous materials. Activated carbon can be synthesized
from animal manure because of its easy availability and eco-
nomically very cheaper and animal waste biomass–derived
activated carbon has unquestionably been one of the prefer-
able techniques for treating industrial effluent [15–17].
Biomass Conversion and Biorefinery
2 Materials and methods
2.1 Preparation of biomass adsorbent
The goat and sheep dung were collected from a local
herdsman in Perundurai, Erode, Tamil Nadu. The samples
were then cleared off of straws, grass and mud and they
were sun dried for 2 days, then again a hot air oven was
used for a day to lose a significant amount of moisture
content. The activated carbon was synthesized by an easy
batch procedure where the dried dung was carbonized at
550 °C initially [1, 5]. Next, equal amounts of carbonized
dung and the chemicals used for carbonization are mixed
in a 500-mL beaker and stirred for 2 h in a magnetic
stirrer. The chemicals like zinc chloride and potassium
hydroxide are used for activation in the present study.
All the chemicals used in the present study are analytical
grade and purchased from a scientific company located
at Erode, Tamil Nadu. After the impregnation, the mix-
ture was filtered and the residue obtained was dried and
carbonized again at 400 °C (activation temperature) and 2
h. The obtained activated carbon after carbonization was
allowed to cool down and was washed according to the
simple reported procedure. Finally, the washed sample
was filtered and dried at 120 °C overnight in a hot air
oven, ground completely in a mortar and pestle and stored
in a clean zip lock cover. The hydrothermal carbonization
is a thermo-chemical method in which saturated water and
vapour pressure are used to convert animal waste dung/
biomanure/biomass into carbon-rich products. The hydro-
thermal carbonization of goat dung involves the thermal
treatment of carbon-containing biomanure organic com-
ponents along with water at the temperature conditions
of 180 °C and autogenous pressure. During hydrothermal
carbonization process, endocrine disruptors are removed
and the organic components undergo hydrolysis, dehy-
dration and polymerization, during which oxygen and
hydrogen contents are decreased, and carbon and energy
contents of the organic material are increased [28]. The
product from HTC process is very much useful in adsorp-
tion process and energy storage applications [28].
2.2 Preparation of stock solutions
Five stock solutions of 20, 40, 60, 80 and 100 mg/L of meth-
ylene blue dye were prepared by adding appropriate amounts
of concentrated dye (from a 2500 mg/L containing tank) and
were diluted in 1000-mL standard measuring flasks using
distilled water. The necessary chemicals are of analytical
grade and they are used in the present study [6].
3 Results and discussion
3.1 Surface characterization by Scanning Electron
Microscopy (SEM)
Scanning Electron Microscopy (SEM) image of animal
waste–derived activated carbon authenticates the surface
morphology and microstructure of the adsorbent and also
SEM results will point out the presence of pores and nature
of distribution of pores on the surface of the adsorbent. The
surface morphology of goat and sheep dung biomass was
activated by zinc chloride and potassium hydroxide as well
as goat (hydrothermally carbonized) were examined using
Scanning Electron Microscopy at the magnification of 200
nm (Fig. 1a–e). From the surface morphology of the sam-
ples, it is observed that they appear to be uneven and rough
and the interior surface is loose. This may be due to the fact
the presence of the indigestible and stodgy roughages and
concentrate in the samples. The uneven surface of the dung
may cause inhomogeneity of ground dung particle size. Vis-
ible morphological dissimilarities in the configuration of the
micropores are spread on the surface of almost all images of
dung and also it shows a large surface area and distribution
of pores causing the better capacity of the activated car-
bon for adsorption. However, a lot of regular and noticeable
pores well spread over the adsorbent surfaces which causes
porous-like structure in potassium hydroxide–activated coat
dung. This kind of porosity is extremely favoured in adsorp-
tion of macromolecules such as methylene blue dye for a
significant adsorption. Besides, bigger and well-developed
pores were attained as the result of pore development dur-
ing the pyrolysis process which supports the diffusion of
potassium hydroxide into the cavity of the adsorbents, pro-
motes the reaction with carbon and ultimately produces more
pores on the surface of the adsorbent [29, 30]. Because of its
greater surface area and pore development, the coat-derived
activated carbon adsorbs pollutants significantly. All the five
images show the surface structure and porosity of the pre-
pared adsorbents. Even though there are some bulk areas in
the adsorbents, wide distribution of pores can be seen from
the images. The pores need not be of circular shape but pores
with deep extensions are possible. The porous structure of
the adsorbents substantiated that there is a maximum uptake
of the adsorbate from the aqueous solution when treated.
3.2 Adsorption experiments
Adsorption experiments were done in 250-mL Erlenmeyer
conical flasks by taking 50 mL of 100 ppm stock solution.
13

Fig. 1  a–e Surface morphology
of goat and sheep dung biomass
(goat + ­ZnCl2 activated, sheep
+ ­ZnCl2 activated, goat +
KOH activated, sheep + KOH
activated, goat (hydrothermally
activated))
The conical flasks were loaded with varying amounts of
adsorbent, made to sit for varied contact times and pH.
The samples were shaken in a rotary shaker at 120 rpm and
they were withdrawn at predetermined interval of time.
They were analyzed for methylene blue dye removal spec-
trophotometrically using UV spectrophotometer at 664
nm. The pH in the flasks is adjusted using HCl and NaOH
by a pH meter. Furthermore, to make the experiments eas-
ier, Response Surface Methodology was used [6].
3.3 Response Surface Methodology (RSM)
RSM is an economical experimental design methodology
that helps us determine the optimum value of required
design parameters by significant reduction of experimen-
tal time even though complex information is extracted to
the maximum. This statistical method has been used widely
for the development of adsorption process variables. It
also provides the correct number of reliable responses of
measurement and the optimal value of the design variables
that produce maximum/minimum values [7]. In the present
13
Biomass Conversion and Biorefinery
study, Box-Behnken Design has been used where the num-
ber of experiments is comparatively less than any other RSM
design models. This type of design uses quadratic model
fitting and it is a powerful design where it can be used as an
alternative to the other time-consuming designs. In order
to connect the response and the independent variables, a
second-order polynomial equation is used.
∑n ∑n ∑n ∑n
Y = a0 + ap + a p2+ a p p (1)
i=1 i i i=1 ii i j>1 i=1 ij i j
Here, Y indicates the response, pi and pj constitute the
coded values of the independent variables i and j respec-
tively. a0 is a constant, the variable influence on the response
(regression coefficient for direct effect) is represented by ai,
aii is the parameter which represents the curve shape (regres-
sion coefficient for the quadratic effect) and finally aij is the
effect of interaction between i and j (regression coefficient
for interplay effect) [8].
Box-Behnken Design (BBD) requires only minimum runs
to predict the responses of higher order. As a result, it allows
building of design as a sequence by the use of blocks, and
Biomass Conversion and Biorefinery

also the parameters of the model are evaluated using the Table 2  Coded values as BBD Run order p1 p2 p3
design as well as the lack of fit of the model is determined matrix
[7]. Here, the second-order polynomial gives the relation 1 0 0 0
between response and independent variables. In this study, 2 1 −1 0
the level of independent variables were chosen up to p1, p2 3 −1 −1 0
and p3 and these were described up to three coded levels of 4 0 0 0
−1, 0 and 1 for lower, middle and upper limits respectively, 5 0 1 −1
as shown in Table 1. In the current study, three independent 6 −1 0 1
variables with three levels of BBD have been used for the 7 0 1 1
experiments. 8 0 0 0
The equation used to determine the number of experi- 9 0 0 −1
mental runs is, 10 0 0 0
11 1 0 −1
N = 2n(n − 1) + Nc (2) 12 1 0 1
13 0 0 0
Here, the number of factors is represented by n and Nc
14 −1 1 0
indicates the number of central points. In the present study,
15 1 1 0
n = 3 and Nc = 4 and as a result, a total of 17 experimental
16 0 −1 1
runs are to be performed for 60 ppm concentration of meth-
17 −1 0 −1
ylene blue dye solution. From Table 2 of BBD matrix for
coded values, we can see that the experimental parameters
are shuffled to minimize the possibility of bias in the experi-
ments as well as this method saves our time and energy in which indicated that the present experimental study is good
turn giving a well-established result [8]. with high reliability. Next, the adequate precision factor
Table 3 represents the variation between the predicted (AP) gives the signal to noise ratio and its value above
and experimental values for the % dye removal. In the pre- 4 is advantageous. In our experiment, the value of AP is
sent study, BBD modelling correlated the % dye removal 43.99 which indicated our experiment is adequate as well
with the operating variables, namely, pH, adsorbent weight as advantageous. The results of ANOVA for 60 ppm dye
and contact time. ANOVA (analysis of variance) is used concentration are shown in Table 4 and model statistics for
for the determination of accuracy of the experiment and 60 ppm dye concentration is represented in Table 5.
it consists of the degree of freedom (DF), sum of squares,
F-value, P-value and the model statistics. The value of R2
for methylene blue dye removal is determined to be 0.9961
for 60 ppm concentration. The value of adjusted R2 will be Table 3  Experimental and predicted values of % dye removal
always less than the R2 value as it is calculated by omit- Run order % removal - actual % removal
ting the non-significant terms in the model. The Adj. R2 - predicted
value for the experiment is 0.9911. The predicted R2 value 1 93.64 93.71
says how good the regression model predicts the responses 2 83.16 83.669
for the experiments. For the determination of the degree 3 71.39 70.951
of accuracy with which the experiments are compared, the 4 84.1 84.1
coefficient of variation (CV) is used. Therefore, if the CV 5 84.1 84.1
produced is higher, then the reliability of the experimental 6 84.1 84.1
procedure is low [18]. So, a value less than 10% obtained 7 82.6 82.091
from the experiments is considered adequate or reproduc- 8 84.1 84.1
ible. The present study has produced a CV value of 1.1% 9 94.92 93.859
10 62.24 63.301
11 92.27 92.823
Table 1  Coded and experimental values of independent variables 12 64.8 64.73
13 80.56 79.569
Independent variables Units Coded values −1 0 1
14 92.08 92.519
pH p1 2 4 6 15 85.99 86.981
Adsorbent weight g p2 0.5 1 1.5 16 70.23 69.677
Contact time min p3 15 37 60 17 84.1 84.1

13
 Biomass Conversion and Biorefinery

Table 4  ANOVA table for Source Sum of squares df Mean square F-value P-value (Prob> F)
60ppm dye concentration
Model 1482.898081 9 164.7664534 200.9128229 < 0.0001
A-pH 1358.507813 1 1358.507813 1656.536473 < 0.0001
B-adsorbent dosage 17.0236125 1 17.0236125 20.75824279 0.0026
C-contact time 40.41005 1 40.41005 49.27518345 0.0002
AB 4.1209 1 4.1209 5.024940664 0.0599
AC 9.954025 1 9.954025 12.13773326 0.0102
BC 0.156025 1 0.156025 0.190253674 0.6758
A^2 48.45918421 1 48.45918421 59.09013208 0.0001
B^2 0.940026316 1 0.940026316 1.146248747 0.3199
C^2 1.273684211 1 1.273684211 1.553104318 0.2528
Residual 5.740625 7 0.820089286
Lack of fit 5.740625 3 1.913541667
Pure error 0 4 0
Cor total 1488.638706 16

Table 5  Model statistics for 60 ppm dye concentration
Std. Dev. 0.905587812 R-squared 0.996143708
Mean 82.02235294 Adj. R-squared 0.991185619
C.V. % 1.104074414 Pred. R-squared 0.938299334
PRESS 91.85 Adeq precision 43.99584994
In the present experiment, % dye removal was determined
using the operating variables pH, adsorbent weight and con-
tact time. To pictorially represent the % dye removal, 2D
contour plot and 3D response surface plots have been gener-
ated and is shown in Fig. 2. The plots give the relationship
between the % dye removal and the operating variables. The
plot shows the effect of two independent operating variables
while keeping the other one as constant [9].
3.4 Influence of different variables on methylene
blue dye adsorption
From the literature, it is observed that in the process of
adsorption, pH of dye solution is an important factor that
influences the surface properties of animal manure–derived
adsorbents. The experimental results reveal that adsorption
of dye solution varies with pH and therefore, dye adsorp-
tion on animal dung–derived activated carbon significantly
varies with pH. The dye adsorption percentage on animal
waste–derived activated carbon increased when pH increases
and obtained a highest value approximately at pH value of 6.
From Fig. 2a, it is evident that the adsorption process onto
the adsorbent is a pH-base done and the colour red in the
graph indicates higher rate of adsorption at pH= 6. Along
with the pH indication, it also shows the effect of adsorbent
dosage for the dye removal working hand in hand with pH.
Also, from Fig. 3a, the effect of contact time for dye removal
which acts along with pH shows that increased contact time
gives maximum dye removal percentage. The effect of con-
tact time along with adsorbent dosage can be seen in Fig. 4a.
This figure conveys that both contact time and adsorbent
dosage play significant roles in dye removal by the adsor-
bent. From the experimental results, it is observed that when
the adsorbent dosage increased, the removal rate of dye also
increased and then it reaches to constant value, whereas the
quantity of methylene blue adsorbed per unit mass of both
adsorbents decreased when the adsorbent dosage increased.
This may be the fact that in limited adsorbate, the increase
of dosage may lead to an excess of adsorbents, which in turn
ensuing in reduction of MB dye adsorption per unit mass
of adsorbents. The same results are obtained in literature
studies also [26].
The adsorption efficiency of animal dung under vari-
ous initial concentrations of MB dye was studied and
is shown in Table 6. The experimental results indicated
that when the initial concentration of MB dye increased
from 20 to 100 ppm, the equilibrium adsorption quantity
of MB increased from 3.22 to 14.12 mg/g, whereas the
subsequent removal percentage showed a decrease trend.
These results imply that when initial concentration of MB
dye increased, the MB molecules spread around the adsor-
bent got enhanced respectively. The MB dye concentration
gradient among the adsorbent and dye solution increased
which makes increase of mass-transfer force; in turn, more
MB dye molecules might be adsorbed by adsorbents. How-
ever, with the increase in initial concentration of MB dye,
the residual unadsorbed MB molecules in the dye solu-
tion increased, which was causing the reduction in MB dye
removal efficiency. The same trends are observed in litera-
ture [26]. Some of the experimental results of adsorption

13
Biomass Conversion and Biorefinery

Fig. 2  Effect of adsorbent Design-Expert® Software

Factor Coding: Actual Dye Removal
weight and pH for the % dye Dye Removal
Design Points
1.50

removal: a 2D contour plot; b 92.98

3D response surface plot 63.25

1.30
X1 = A: pH
X2 = B: Adsorbent dosage

B: Adsorbent dosage
Actual Factor
C: Contact time = 60.00 1.10

75 80 85 90

0.90

70
0.70

0.50
2.00 3.00 4.00 5.00 6.00

A: pH

(a)

Design-Expert® Software
Factor Coding: Actual
Dye Removal
Design points above predicted value
Design points below predicted value
92.98

63.25
95
X1 = A: pH
X2 = B: Adsorbent dosage 90
Actual Factor
C: Contact time = 60.00
85
Dye Removal

80

75

70

65

1.50 6.00
1.30 5.00
1.10
4.00
0.90
3.00
B: Adsorbent dosage 0.70 A: pH
0.50 2.00

(b)

of methylene blue dye by zinc chloride–activated goat 3.5 Adsorption isotherms

dung as adsorbent various initial concentration of dye and
contact time are represented in Tables 6 and 7. Finally, To analyze the experimental data of adsorption isotherms, a
Fig. 5 represents the relationship between the actual experi- variety of mathematical models have been used. These iso-
mental values and the predicted values where a very close therm studies using different mathematical models will help us
uniformity can be seen from the graph. The adsorption of to explain about the process of distribution of adsorbate in both
methylene blue dye by goat and sheep gung–derived acti- solid and liquid phases and they also show when the process
vated carbon was activated by different chemicals like zinc of adsorption reaches the equilibrium [6, 10–12]. Adsorption
chloride, potassium hydroxide and hydrothermally acti- isotherms also play an important role in the optimization of
vated carbon. From the experimental results, it is observed the adsorbent usage. In the present study, the equilibrium char-
that methylene blue dye removal percentage of potassium acteristics of methylene blue dye removal by G + ­ZnCl2, S +
hydroxide–activated goat dung was high (99.6%) compared ­ZnCl2, G + KOH, S + KOH and G(H) were studied through
to the dye removal percentage of goat dung activated by the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich
­ZnCl2 was 97.7%, sheep dung activated by KOH was 96.4% equilibrium isotherms. In recent times, the Langmuir isotherm
and sheep activated by Z ­ nCl2 and goat dung activated by model is the most extensively employed isotherm for adsorption
hydrothermal process was 65.4%. studies and it explains the single-layer adsorption on adsorbent’s

13
 Biomass Conversion and Biorefinery

Fig. 3  Effect of contact time (a)

and pH for % dye removal: a
Design-Expert® Software
2D contour plot; b 3D response Factor Coding: Actual
60.00
Dye Removal
Dye Removal
surface plot Design Points
92.98

63.25
51.00
X1 = A: pH
X2 = C: Contact time

Actual Factor

C: Contact time
B: Adsorbent dosage = 1.50 42.00

80
90

33.00

70

24.00

15.00
2.00 3.00 4.00 5.00 6.00

A: pH

(b)
Design-Expert® Software
Factor Coding: Actual
Dye Removal
Design points above predicted value
Design points below predicted value
92.98

63.25

X1 = A: pH 100
X2 = C: Contact time

Actual Factor 90
B: Adsorbent dosage = 1.50
Dye Removal

80

70

60

60.00 6.00
51.00
5.00
42.00
4.00
33.00
3.00
C: Contact time 24.00
A: pH
15.00 2.00

surface with fixed number of indistinguishable sites. The equi-
librium isotherm studies have given the results (Figs. 6, 7 and
8) where the coefficient of determination (R2) indicated the
Freundlich isotherm fitted best for G + Z ­ nCl2 and S + Z ­ nCl2
whereas the Langmuir isotherm fitted best for G + KOH and S
+ KOH. In contrary to these results, G (H) was best followed by
the Dubinin–Radushkevich isotherm. All the adsorption equilib-
rium isotherm parameters are presented in Table 8.
The main and one of the assumptions in the Freundlich
isotherm is a monolayer adsorption along with a heterogene-
ous energetic allocation of active sites, attached by relations
between the adsorbed molecules.
The linearized equation for the Freundlich isotherm is given as
1
( )
Log qe = Log KF + Log Ce (3)
n
where qe (mg/g) is the adsorption capacity of the adsor-
bent at equilibrium and Ce (mg/L) is the final equilibrium
concentration of the dye. Finally, KF (mg/g) and n are the
constants that are obtained from the intercept and slope of the
isotherm plotted. For this isotherm, a plot between Log qe vs
Log Ce gave a straight line for both the adsorbents. From the
intercept and slope, KF and n were calculated (Table 8). From
the table, the value of n was found to be greater than 1 and
comes between 1 and 10 which indicated a favourable process
of adsorption by both the adsorbents [6]. Besides, Table 6
represents the coefficient of determination and the maximum
adsorption capacity of activated carbon derived from animal
wastes using various precursors. These experimental results
reveal that adsorption capacity changes and depends on the
properties of adsorbent, characteristics of activation agent,
the degree of surface alteration, temperatures, etc. Besides, it
is observed that KOH solution–activated goat adsorbent has
significant adsorption capacity. Due to the availability and
cheapness of goat manure, it is also a good quality material
for adsorbent preparation.

13
Biomass Conversion and Biorefinery

Fig. 4  Effect of contact time Design-Expert® Software

Factor Coding: Actual Dye Removal
and adsorbent dosage for % dye Dye Removal
Design Points
60.00

removal: a 2D contour plot; b 92.98

3D response surface plot 63.25

51.00
X1 = B: Adsorbent dosage
X2 = C: Contact time

Actual Factor

C: Contact time
A: pH = 6.00 42.00

92.5
33.00

92

24.00

91 91.5
91
90.5
15.00
0.50 0.70 0.90 1.10 1.30 1.50

B: Adsorbent dosage

(a)

Design-Expert® Software
Factor Coding: Actual
Dye Removal
Design points above predicted value
Design points below predicted value
92.98

63.25

X1 = B: Adsorbent dosage
X2 = C: Contact time
100
Actual Factor
A: pH = 6.00
90
Dye Removal

80

70

60

1.50
60.00
1.30
51.00

42.00 1.10

33.00 0.90

C: Contact time 24.00 0.70 B: Adsorbent dosage

15.00 0.50

(b)

Table 6  Adsorption of MB dye for various initial concentration of Table 7  Adsorption of MB dye using various contact time by zinc
dye by zinc chloride–activated goat dung adsorbent chloride–activated goat dung
S. No. Adsorbent Contact Ci (initial) Ce (final) qe (mg/g) S. No. Adsorbent Contact Ci (Initial) Ce (final) qt (mg/g)
dosage (g) time (min.) (mg/L) (mg/L) dosage (g) time (min.) (mg/L) (mg/L)

1 1 60 20 3.9 3.22 1 1 0 60 - -
2 1 60 40 10.8 5.84 2 1 5 60 19.3 8.14
3 1 60 60 17.1 8.58 3 1 10 60 18.5 8.3
4 1 60 80 21.9 11.62 4 1 15 60 17.9 8.42
5 1 60 100 29.4 14.12 5 1 20 60 17.5 8.5
6 1 25 60 17.3 8.54
7 1 30 60 17.2 8.56
8 1 40 60 17.2 8.56
Apart from ­ZnCl2-activated adsorbents, KOH-activated
9 1 50 60 17.2 8.56
adsorbents followed the Langmuir equilibrium isotherm model.
10 1 60 60 17.2 8.56
The linearized equation for the Langmuir isotherm is given as,

which is in the form of y = mx + c, indicating the value of

( )
1
(4)
( ) ( )
1∕qe = ∗ 1∕CE + 1∕qmax
KL qmax KL can be obtained from the slope and qmax (mg/g)—this

13
 Biomass Conversion and Biorefinery

Fig. 5  Plot between actual and Design-Expert® Software

Dye Removal Predicted vs. Actual
predicted experimental values Color points by value of
for % dye removal Dye Removal:
100.00
92.98

63.25

90.00

Predicted
80.00

70.00

60.00

60.00 70.00 80.00 90.00 100.00

Actual

Fig. 6  Freundlich isotherm 1.4

for methylene blue adsorption
(adsorbent dosage = 1 g, pH =
6, contact time = 60 min) 1.2
y = 0.6912x + 0.1001
R² = 0.9723
1

0.8 G + ZnCl2
Log qe

S + ZnCl2
0.6
y = 0.7402x + 0.0457 Linear (G + ZnCl2)
R² = 0.9838
0.4 Linear (S + ZnCl2)

0.2

0
0 0.5 1 1.5 2
Log Ce

Fig. 7  Langmuir isotherm for

0.7
methylene blue adsorption
(adsorbent dosage = 1g, pH =
6, contact time = 60 min) 0.6
y = 2.9089x + 0.0577
0.5 R² = 0.9877

0.4 G + KOH
1/qe

0.3 S + KOH
y = 2.7491x + 0.0403
R² = 0.9958 Linear (G + KOH)
0.2
Linear (S + KOH)
0.1

0
0 0.05 0.1 0.15 0.2 0.25
1/Ce

13
Biomass Conversion and Biorefinery

Fig. 8  Dubinin–Radushkevich 1
isotherm for methylene blue
adsorption by hydrothermally
0.8
carbonized adsorbent (adsorbent
dosage = 1 g, pH = 6, contact
0.6
time = 60 min)
y = -1E-05x + 0.8601
0.4 R² = 0.9506

ln (qe)
ln (qe)
0.2 Linear (ln (qe))

0
0 20000 40000 60000 80000 100000
-0.2

-0.4
ε2

is the maximum adsorption capacity being obtained from

the intercept. For the adsorbents G + KOH and S + KOH,
Table 8  Adsorption isotherm studies for the removal of methylene
blue dye by adsorption on G + Z ­ nCl2, S + Z
­ nCl2, G + KOH, S +
the plot between 1/qe vs 1/Ce has given straight line with
KOH and G (H) 1/qmax as the intercept. In the Langmuir isotherm, a special
dimensionless constant called the separation factor plays an
Parameters G + Z
­ nCl2 S + ­ZnCl2 G + KOH S + KOH G (H)
important role where its equation is
Langmuir
(5)
( )
Slope 1.046 0.9131 2.7491 2.9089 7.378
RL = 1∕ 1 + KL Ci
Inter- 0.0491 0.0587 0.0403 0.0577 0.2393
cept
where Ci is the initial dye concentration and, in this case, it is
R2 0.9726 0.955 0.9958 0.9877 0.9129
20 mg/L. The value of RL represents the type of the isotherm
qmax 20.367 17.036 24.81 17.331 4.179
to be either unfavourable when RL is greater 1, linear if RL
(mg/g) = 1 or favourable if 0 < RL < 1 or RL = 0. The calculated RL
RL 0.262 0.205 0.773 0.7159 0.6065 value was 0.826, indicating that the adsorption of the lead
KL 0.0469 0.064 0.0146 0.0198 0.032 was a favourable process. The adsorbents G + KOH and S
Freundlich + KOH gave the RL value as 0.773 and 0.7159 respectively
Slope 0.7402 0.6912 0.8993 0.6928 0.4646 and it indicates that methylene blue adsorption is a favour-
Inter- 0.0457 0.1001 −0.4085 −0.2399 −0.4091 able process and forms a monolayer over the surface of the
cept adsorbents. The hydrothermally carbonized adsorbent G (H)
KF 1.1109 1.2592 0.3904 0.5756 0.3898 followed the Dubinin–Radushkevich equilibrium model in
R2 0.9839 0.9723 0.9926 0.9207 0.7407 contrary to the other four adsorbents. Its linearized form is
N 1.3509 1.4467 1.1112 1.4434 2.152 given as
Temkin
Slope 5.2456 4.8827 3.2545 2.3401 0.6899 ln qe = ln qm − 𝛽𝜖 2 (6)
Inter- −5.0119 −4.1126 −3.8591 −2.1421 −0.3535
cept Using this isotherm, the pore energy distribution can be
BT (J/ 5.2456 4.8827 3.2545 2.3401 0.6899 obtained where the constant β helps to find out the adsorp-
mol) tion potential (E (kJ/mol)) required for sufficient adsorp-
R2 0.899 0.8774 0.9061 0.9542 0.7498 tion. Furthermore, Dubinin–Radushkevich isotherms are
0.4037 0.3055 0.4003 0.5991 extensively used in the characterization of several industrial
D–R adsorbents. The constant β which is directly related to the
Slope −4E−06 −3E−06 −5E−06 −6E−06 −1E−05 porous structure of the adsorbent helps in the qualitative
Inter- 2.3517 2.3245 1.7585 1.6998 0.8601 measurement of the average pore size of the adsorbent. Since
cept G(H) follows the Dubinin–Radushkevich isotherm, it can
β 4E−06 3E−06 5E−06 6E−06 1E−05 be proved that hydrothermal carbonization is a significant
R2 0.7795 0.7504 0.8407 0.9232 0.9506 method for preparing adsorbents with potential adsorption
E (kJ/ 353.55 408.248 316.228 288.675 223.61 capacity.
mol)

13
 Biomass Conversion and Biorefinery

3.6 Adsorption kinetics 0.9937 to 0.9998. Similarly, the value of correlation coef-

Modelling of adsorption kinetics is of supreme importance
to illustrate the investigational data and to develop the
experimental results for situations further than those treated
experimentally. In the present study, the kinetic analysis
of adsorbate uptake by the adsorbents that determine the
rate of the adsorption process was done by various kinetic
models like pseudo-1st order, pseudo-2nd order, Elovich
kinetic model and intra-particle diffusion kinetic model and
the results are tabulated in Table 9. The adsorption of sol-
ute rate in kinetic analysis, which calculates the residence
time needed for the end of the adsorption process, may be
established.
The linearized forms of their equations are:
(7)
( ) ( )
Pseudo − 1st order ∶ ln qe − qt = ln qe − k1 t
Pseudo − 2nd order ∶ t∕qt = 1∕ k2 qe 2 + t∕qe
( ) ( ) ( )
(8)
1 1
( ) ( )
Elovich model ∶ qt = ln (𝛼𝛽) + ln(t) (9)
𝛼 𝛼
( )
Intra − particle diffusion model ∶ ln Ce ∕qe = B ln Ce − ln(A)
(10)
The pseudo-second-order model assumes that the occu-
pying rate of adsorption sites is proportional to the square
of the number of unoccupied sites. The kinetic parameters
of the different adsorbents for methylene blue adsorption
process kinetic parameters are given in Table 7. The coef-
ficient of determination (R2) for the pseudo-first order was
varied from 0.80 to 0.926, demonstrating that it may per-
haps not be used to explain the complete adsorption process
appreciably. Conversely, the value of correlation coefficient
(R2) of the pseudo-second-order kinetic model ranges from
ficient (R2) varies from 0.5093 to 0.8323 and 0.67 to 0.95 for
intra-particle diffusion and Elovich equation, respectively.
As a result, among the four kinetic models studied, it is
observed that the best model which was followed by all the
five adsorbents was pseudo-2nd-order kinetic model. Here,
the plot between t/qt vs time (Temkin) gave a straight line
for all the five adsorbents resulting in a coefficient of deter-
mination of 0.9937–0.9998, which indicate the adsorption
of dye followed a pseudo-second-order reaction compared
to the other kinetic models. This means that if the experi-
mental data fits well to pseudo-second-order model, then it
indicates an inclination towards chemisorption. Besides, the
pseudo-second-order kinetic model was more appropriate to
illustrate the adsorption of methylene blue dye, demonstrat-
ing that the adsorption process was dominated by chem-
isorption. This chemisorption implicated electron sharing or
electron transport among the adsorbate and the adsorbent.
From the literature, it is observed that approximately all the
experimental research studies utilizing the empirical models
found that the pseudo-second-order model provides the best
fit to the experimental data. The slope and intercept of the
plot (Fig. 9) are used to calculate the values of qe and k2 [6].
3.7 Regeneration studies
It is well known that regeneration of goat and
sheep–derived activated carbon after the completion of
adsorption process to be utilized for numerous cycles
which minimizes the operational and running expenses
of the industrial effluent treatment method quite consider-
ably. The utilized adsorbent was collected and washed it
numerous times by distilled water. The washed adsorbent
dried in a hot air oven about 60 min at the temperature of
50 °C. The dried adsorbent was used for the next cycle

Table 9  Kinetic analysis of the Parameters G + ­ZnCl2 S + ­ZnCl2 G + KOH S + KOH G (H)
adsorbents for methylene blue
adsorption Pseudo-1st order
K1 −0.0011 −0.00089 −0.00146 −0.0016 −0.0014
R2 0.8074 08113 0.8657 0.9267 0.9178
Pseudo-2nd order
K2 0.5751 0.5162 0.2173 0.2151 0.1249
R2 0.9998 0.9995 0.9964 0.9963 0.9937
Intra-particle diffusion
Kdiff 0.8175 0.8095 0.5119 0.5252 0.2916
R2 0.5093 0.5099 0.786 0.7876 0.8323
Elovich model
α 0.5623 0.5682 0.9575 0.9316 1.6986
β 0.7876 0.7199 1.9386 1.8878 0.8667
R2 0.6753 0.6751 0.9165 0.9215 0.9502

13
Biomass Conversion and Biorefinery
Fig. 9  Pseudo-2nd-order kinetic
model for Methylene Blue
adsorption
as regenerated adsorbent. Using the regenerated adsor-
bents, the adsorption process was conducted four times
repeatedly and it was observed that the dye removal effi-
ciency decreased with increase in number of cycles. For
KOH-activated goat dung, the removal percentage was
decreased as 99.6>85.6>79.4>63.2. Since goat and sheep
dung–derived activated carbon adsorbents are waste mate-
rials, they are actually very cheap and easily or abundantly
available materials. However, the literature studies enlight-
ened that animal waste–derived adsorbents are nutrient-
enriched biochar and are environmentally friendly manure
which may be a replacement for chemical fertilizers [23].
4 Conclusion
In the present study, the potential of goat and sheep
dung–derived carbon, activated with different chemicals,
as adsorbents for the removal of methylene blue dye from
aqueous solution in a batch system was investigated. The
surface morphological studies were done using Field
Emission Scanning Electron Microscope. Batch adsorp-
tion studies were done by Response Surface Methodology
and the adsorption showed a pH-dependent profile and pH
was found out to be 6 as the optimum value. The percent-
age of methylene blue dye removal was analyzed to be
99.6% and the maximum adsorption capacity was found
to be 24.81 mg/g for the adsorbent of goat dung activated
with potassium hydroxide. The models developed using
RSM have given a successful interpretation of the experi-
mental values in accordance with the operating variables.
The present study has produced a CV value of 1.1% which
indicated that the experimental study is good with high
reliability. The equilibrium adsorption isotherm modelling
has shown that the equilibrium data fitted best for the Fre-
undlich model for Z ­ nCl2-activated adsorbents, Langmuir
model for KOH-activated adsorbents and Dubinin–Radu-
shkevich model for hydrothermally carbonized adsorbent.
Kinetic data perfectly fitted with the pseudo-2 nd-order
kinetic model for all the five adsorbents and demonstrating
that the adsorption process was dominated by chemisorp-
tion. Using the regenerated adsorbents, the adsorption
process was conducted and observed that the dye removal
efficiency decreased with increase in number of cycles.
For instance, in KOH-activated goat dung, the removal
percentage was decreased as 99.6>85.6>79.4>63.2.
Acknowledgements The authors wish to thank Kongu Engineering
College, Erode, Tamil Nadu, India, for their constant support, encour-
agement and providing facilities to carry out this research work.
Author contribution Senthilkumar Kandasamy: conception and design,
data analysis and interpretation, manuscript correcting, final approval.
Neeraja Madhusoodanan: collection and assembly of data, data analy-
sis and interpretation, manuscript writing. Prathap Senthilkumar: col-
lection and assembly of data, data analysis and interpretation. Vasant
Muneeswaran: collection and assembly of data, data analysis and inter-
pretation. Naveenkumar Manickam: collection and assembly of data,
data analysis and interpretation, manuscript writing, final approval.
Venkata Ratnam Myneni: collection and assembly of data, data analysis
and interpretation, manuscript writing, final approval.
Funding The authors thankfully acknowledge the financial support
provided by Indian Institute of Chemical Engineers (IIChE), Kolka-
tta (Ref. No. AG/R&D/2022/519, dt 3.2.2022) for carrying out this
research work.
Data availability All the experimental data and relevant materials are
included in the manuscript.
Declarations
Ethical approval This declaration is not applicable.
13
 Biomass Conversion and Biorefinery

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