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Accepted Manuscript

Title: Adsorption of distillery spent wash on activated bagasse


fly ash: Kinetics and thermodynamics

Authors: Jemal Fito, Nurelegne Tefera, Stijn W.H. Van Hulle

PII: S2213-3437(17)30506-7
DOI: https://doi.org/10.1016/j.jece.2017.10.009
Reference: JECE 1919

To appear in:

Received date: 12-8-2017


Revised date: 30-9-2017
Accepted date: 2-10-2017

Please cite this article as: Jemal Fito, Nurelegne Tefera, Stijn W.H.Van
Hulle, Adsorption of distillery spent wash on activated bagasse fly
ash: Kinetics and thermodynamics, Journal of Environmental Chemical
Engineering https://doi.org/10.1016/j.jece.2017.10.009

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Adsorption of distillery spent wash on activated bagasse fly ash: Kinetics and
thermodynamics

Jemal Fito1, Nurelegne Tefera 2 and Stijn W.H. Van Hulle 3

1 Ethiopian Institute of Water Resources, Addis Ababa University, Ethiopia. P.O. Box 150461
Addis Ababa; Email: fitojemal120@gmail.com, +251 912083842

2
Addis Ababa Science and Technology University, Ethiopia. Cell phone: - +2519-12-50-29-95

3
Department of Industrial Biological Sciences, Ghent University, Belgium, address: Graaf Karel
de Goedelaan 5, B-8500, Kortrijk, Tel.: +32 56 241251

Abstract

This study aimed to characterize distillery spent wash and COD removal from it using bagasse fly
ash (BFA). The results of the analyses showed that the average value of BOD5 and COD were
35990 mgL-1 and 139671 mgL-1, respectively. High amount of total nitrogen (1217 mgL-1), total
phosphorous (45 mgL-1), total solids (156 mgL-1) and low acidity (pH 4) were recorded.
Adsorption of this spent wash on BFA was investigated at different temperatures, contact times,
initial COD concentrations, pH solutions and adsorbent (BFA) doses. Raising temperature from
15 to 328 K resulted in increasing the uptake of the organic matter from 29.5 to 75.5 %. Varying
the initial COD concentration from 1000 mgL-1 to 6000 mgL-1 increased the adsorptivity capacity
(qe) from 6 to 92.40 mg g-1 and resulted in an increase in removal efficiency from 24 to 61.6 %.
Adsorptive capacity (116.30 mg g-1) calculated by the pseudo-second order model (R2 = 0.98)
indicated that pseudo-second order kinetic model fitted better with the experimental data.
Moreover, the Gibbs free energy change (G) (-5.61 to -11.84 kJ mol-1)) showed that adsorption
process was spontaneous whereas the positive value of the H (42.29 kJ mol-1) indicates an
endothermic process. Similarly, increasing the degree of disorder at the liquid-solids interfaces
was observed from entropy change (S = 0.17 kJ (Kmol)-1). In general, thermodynamic study

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revealed that adsorption process was feasible, spontaneous and endothermic; and the application
of BFA is the promising option for removal of organic matter (COD) from molasses spent wash.

Keywords: Adsorption; Bagasse Fly Ash; COD removal; Kinetics; Spent wash; Thermodynamics

1. Introduction

The rapid advancement of industrialization and progress of civilization has drawn special attention
to the improper handling of waste materials that resulted in environmental degradation [1]. Today,
our environment is continuously degrading due to the disposal of industrial wastes into the ambient
environment [2]. Hence, industrial pollution is a major factor that causes the degradation of the
environment which is affecting the water consumed, the air inhaled and the soil lived on [3].
Industrial waste management is one of the most important environmental problems faced by
today’s world because industrial processes create a variety of wastewater pollutants that are
difficult to handle and expensive to treat [4]. Furthermore, the demand for water and the generation
of wastewater is increasing at an alarming rate while the disposal of wastewater is still a major
problem faced by many industries due to the complexity and huge volume of effluent with very
limited space for treatment and disposal [5].

Alcohol distilleries are extensively growing because of the variability of oil prices and the
consumption of ethanol as the energy source and raw material for many industries [6]. The unique
nature of alcohol distilleries is the consumption of high volume of raw water. However, the
majority of the input materials end up in the form of wastes [7]. The distillery wastes account 88%
to 95% of total volume whereas the ethanol contains only 5% to 12% of the raw materials [8]. In
line with this, for every liter of ethanol production, about 12 to 15 L of distillery spent wash is
generated [9]. Indeed, ethanol distillery is one of the major agro-based industries which generate
spent wash as the residue of fermented mash. Usually, the term vinasse or molasses spent wash is
commonly used for distillery wastewater. During ethanol production in the fermentation process,
diluted molasses is used with supplements such as yeast, ammonium sulphate, urea and phosphate
while the adjustment of pH for fermentation broth is made by sulphuric acid [6]. These
supplements are the major contributor to spent wash pollution.

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Distillery spent wash properties described in terms of a recalcitrant, complex, high organic matters
of COD (80,000 to 160,000 mgL-1), low acidity (pH 3.7 to 4.5) with high content of dissolved
inorganic salts [10]. The dark brown color of the spent wash is due to the presence of the color
causing pigment known as melanoidins (C17–18H26–27O10N) which is formed under non-enzymatic
(Maillard) reaction between sugar and amino compounds at high temperature[11].The peculiar
feature of melanoidins are very acidic, long polymeric and highly dispersed colloidal particles with
the negatively charged surface due to the dissociation of carboxylic acids and phenolic groups
[12]. Phenols, melanin and caramels are others color causing compounds. The presence of these
recalcitrant components in the spent wash makes it hardly degradable in the different (biological)
wastewater treatment stages and results in the discharge into the environment [6]. As distillery
spent wash is an eco-toxic effluent that is unsafe to dispose into agricultural and aquatic ecosystem
[13], ethanol distilleries are considered as a major polluting industry. In India, for example,
distilleries are grouped under the “Red Category” by the Central Pollution Control Board due to
the severity of the pollution caused by the spent wash [10].The acidity of the spent wash enhances
the dissolution of metals in the water bodies whereas the dark brown color of spent wash hinders
photosynthesis activities by blocking sunlight [14]. Additionally, direct discharging of untreated
effluent into the water bodies might be lead to eutrophication [15].

Cost-effective and efficient treatment methods for distillery spent wash are still under investigation
but the pollution controlling government policies are more and more stringent. Conventional
wastewater treatment systems usually consist of primary treatment to remove solids, oils and fats;
secondary biological treatment to remove organic matter and nutrients and tertiary treatment such
as polishing stage [16]. Various conventional physicochemical methods such as coagulation–
flocculation, filtration and different combinations of these methods have also been tested for the
treatment of distillery spent wash, but were not effective. Furthermore, the conventional biological
treatments such as trickling filter and activated sludge are better but inefficient in the removal of
the color causing pigments, the dark brown color. Among the current treatment technologies, high
rate anaerobic treatment is the most suitable and attractive primary treatment option for high
strength organic effluents such as distillery spent wash [17]. However, the color causing pigments
of spent wash are not effectively degraded by primary biological treatment because only about 6 -
7% of pollutants are removed by conventional biological methods [18]. This showed that anaerobic
treatment alone cannot remove organic and inorganic pollutants to permissible discharging limits.

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Hence, other treatment methods like adsorption can be coupled with the biological method in
removing color causing pigment and organic matter (COD) by low-cost adsorbents which have
also the advantage of simultaneously removing of other inorganic pollutants such as nutrients, salts
and metals.

Adsorption is more popular among many treatment methods because of its simple design, easy
operation and the possibility of adsorbent re-use or recycling. This technology is commonly
employing in wastewater treatment because of its economic viability, technical feasibility and
socially acceptability [19]. Today, special attention is given for agro-based inexpensive adsorbents
such as sugarcane bagasse, wood sawdust, bagasse fly ash, wood ash and rice husk because of
their minimum environmental polluting effect [20]. The application of such adsorbents for the
treatment of wastewater is increasing rapidly due to the growth of awareness of public and
environmental protections [21]. Usually, adsorption technique is attractive if the adsorbent
material used is cheap, more efficient, available and does not require any expensive pretreatment
process.

The development of adsorbent from industrial by-products like bagasse fly ash (BFA) is a potential
research area because of the commercially activated carbon is expensive. BFA is by-product from
the powerhouse of the sugar factory. The application of this adsorbent for the wastewater treatment
is proved to be an effective and attractive process. For instance, 78% removal efficiency was
achieved through adsorption of acrylonitrile on BFA from the aqueous solution of 100 mgL-1 [22].
BFA adsorptive capacity of 101.5 mg g-1 was also reported for the treatment of dairy wastewater
(COD 3900 mgL-1) [23]. In another study, in the removal of malachite green dye from aqueous
solution with BFA, commercially graded and laboratory made activated carbons, BFA showed a
wide pore size distribution with the good surface area which helps to interact with the different
size of adsorbates in the treatment process [24]. Moreover, BFA has good porous structure and
adsorption capacity, in addition to, easily modified nature by chemical treatment to increase its
adsorptive properties. In sorption behaviors comparison of BFA with commercially activated
carbon, the BET surface area, bulk density and heating value of activated carbons commercial
were 336.6 m2g-1, 599.32 kgm-3 and 18.81 MJkg-1 whereas these properties for BFA were 168.39
m2g-1, 185.51 kgm-3 and 19.23 MJkg-1, respectively [23]. Hence, BFA has a potential to substitute

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commercially available carbon due to its comparable efficiency and a significantly low-cost [25].
The application of BFA for the treatment of industrial dye wastewater resulted in removal of COD
(51%), color (70%), turbidity (71%) and TSS (96%) [26]. Similarly, the treatment of synthetic
dairy wastewater by means of adsorption onto the activated carbon-commercial and BFA resulted
in a maximum COD removal of 68.7% and 26%, respectively [23].

However, adsorption technology using activated carbon like BFA has some restrictions such as
the cost of the activated carbon, the need for regeneration after exhausting and the loss of
adsorption efficiency [27]. Practically, some adsorbents are disposed of without the regeneration
because of their low cost and unlimited availability. Regeneration of BFA usually carried out many
times throughout the treatment process either by thermal or solvent desorption. For instance,
solvents such as aqueous solution (usually about 0.1 N) of HCl, H2SO4, HNO3, CH3COOH,
C2H5OH, acetone NaOH and distilled water are very effective and commonly used in regeneration
processes [28].

Disposal of BFA as solid waste to the environment causes a huge problem in sugar industries
particularly at Metahara sugar factory. The attempt of employing of this by- product as an
adsorbent for wastewater treatment is the good solution for the environment and wonderful
practice of waste to resources conversion. Many kinds of research conducted so far on adsorption
treatment of organic matter removal from wastewater have been focused on either to investigate
the efficiency of the treatment or the equilibrium isotherms. However, in this study, adsorption
kinetics and thermodynamics are investigated during removal of organic matter from distillery
spent wash. Therefore, the intention of this study is to assess the physicochemical properties of the
distillery spent wash and its treatment with activated BFA.

2. Materials and Methods


2.1. Adsorbent
2.1.1. Adsorbent development

Bagasse fly ash was collected from the dumping site of the Metahara sugar factory in the regional
state of Oromiya (Ethiopia). It was taken to laboratory and sun-dried for two days. For organic
matter removal from the surface of adsorbent, it was soaked in hydrogen peroxide (30% by
concentration) at 60℃ for 24h. Then it was washed with de-ionized water repeatedly until all
hydrogen peroxide on the surface was removed. This activated bagasse fly ash (BFA) was placed
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into an oven at 100°C until it was dried completely. Finally, it was powdered, sieved and stored in
a vacuum desiccator until it was used for the treatment [29].

2.1.2. Adsorbent characterization


A surface morphology of adsorbent (BFA) was determined using the scanning electron microscope
and SEI resolution 1.0 nm guaranteed at 15kV (JEOL JSM-7600F FEG-SEM, JEOL, USA). The
sample was applied on carbon tape, and measured at a working distance of 8mm. The sample
preparation and analysis was done as per the standard operating procedure of JEOL JSM 7600F
SEM which was operated at 15 kV and current of 10 A under 1000X magnifications (Hegazy et
al. 2014).
2.2.The effect of initial COD concentration on adsorption

Wastewater samples were taken in bottles with glass-stoppered and tests were performed without
delay on the same day. The most popular current testing method for COD is open reflux method
which is suitable for a wide range of wastes such as distillery spent wash. A wastewater sample
was refluxed in strongly acid solution with a known excess of potassium dichromate (K2Cr2O7).
After digestion, the remaining unreduced K2Cr2O7 is titrated with ferrous ammonium sulfate to
determine the amount of K2Cr2O7 consumed and the oxidizeable matter was calculated in terms of
oxygen equivalent. Due to it is higher oxidizing ability dichromate reflux method was preferred
over other procedures using other oxidants. Hence, the COD concentration of wastewater was
determined by open reflux method (APHA 5220 B) and dilution process was performed by
distilled water at laboratory scale [30]. The effect of initial COD concentration on treatment
efficiency was investigated at a constant adsorbent dose (4 g in 100 mL solution), pH (8), and the
contact time of the treatment (4 h) under various initial COD concentrations such as 1000, 2000,
3000, 4000, 5000 and 6000 mgL-1.

2.3.The effect of pH on adsorption

The effect of pH on removal efficiency of organic matter on bagasse fly ash form distillery spent
was tested at screening stage of the treatment. The pH range of 3 – 8 was selected and its effects

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on adsorption were recorded under the experimental condition of COD concentration 6000 mgL-
1
, adsorbent dose 4 g in 100 mL solution, contact time 4 h and temperature of 25̊C.

2.4. Adsorption kinetics

Batch adsorption kinetics tests were carried out using different contact time under fixed experiment
condition (Table1). Wastewater samples were taken and placed into 250 mL conical flasks; and
agitated at 160 rpm using water bath shaker at the fixed temperature of 25 ̊C. Afterwards, the
solution was centrifuged at 3500 rpm for 30 minutes. Finally, the solution was filtered using
Whatman filter paper 42 and the COD analysis was performed as per standard methods for the
examination of water and wastewater [30].

The amounts of organic matter adsorbed onto activated carbon was determined according to
Equation1.
𝑐0− 𝑐𝑡
𝑞𝑡 = 𝑣 (1)
𝑚

where co is initial concentration of COD and ct is concentration of COD at contact time of t whereas
v is the volume of the adsorbate and m is the mass of the adsorbent in g. Similarly, qe can be
calculated as the amount of organic matter adsorbed onto activated carbon at equilibrium.

2.5. Adsorption thermodynamics

Batch experimental adsorption thermodynamics was performed in 250 mL conical flasks.


Wastewater samples were agitated at 160 rpm using water bath shaker which was operated at the
predetermined different temperatures indicated in Table 2. Then the agitated samples were
centrifuged and filtered through Whatman filter paper 42. Finally, the filtrate samples were tested
for a change in COD concentration and the amount of organic matter adsorbed was calculated
according to Equation 1.

2.6. Spent wash collection

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Ethanol distillery spent wash samples were collected from Metahara sugar and distillery factory
located in Oromiya regional state, Ethiopia. The wastewater samples were taken at the discharge
point of the factory in plastic bottles that were pre-cleaned with acid. After the sampling, the
effluent samples were immediately taken to the laboratory and stored in the refrigerator at 4°C
until they were used for analyses. The frequency of sampling was done on the monthly based
interval, four times throughout the study period. Composite sampling techniques were applied for
physicochemical analyses which measured in the laboratory and grab sampling techniques were
used for physical parameters that analyzed onsite at sampling points.

2.7. Physicochemical analyses


Temperature, pH and electrical conductivity (EC) were measured immediately on sites while other
the physico-chemical parameters such as total solids (APHA 2540 B, Total solid dried at 103-
1050C), ammonia (APHA 4500, MgO Distillation methods), nitrate (APHA 4500-NO3- B,
Ultraviolet spectrophotometric screening methods), total nitrogen (APHA 4500B, B- Kjldahal
Test), phosphate (APHA 4500-P-C,Vandomolybdophosphoric acid), total phosphorus (APHA
3030F and APHA 4500-P), chemical oxygen demand (APHA 5220 B, Open reflex method),
biochemical oxygen demand (APHA 5210 B, 5-days BOD test), chloride (APHA 4500-Cl-B,
argentometric) and sulphate (APHA 3030E, turbidmetric method) were measured in the laboratory
as per standard methods for the examination of water and wastewater [30].

2.8. Preparation of synthetic Wastewater

Melanoidins is a constituent of distillery spent wash. To minimize the interferences from distillery
spent wash with adsorption treatment, melanoidins containing distillery wastewater was prepared
by mixing 4.5 g of glucose (G8270 D-(+), Sigma-Aldrich), 1.88 g of glycine (G7126, Sigma-
Aldrich) and 0.42 g of sodium bicarbonate in 100 mL of distilled water which was heated for 7 h
at 95̊C until dried. Then 100 mL of distilled water was added to form a melanoidins solution [31].
Finally, dilution of wastewater solution was made accordingly and the pH adjustment was
performed using 0.1 M NaOH and 0.1 M HCl solutions. The COD of the synthetic wastewater was
determined as per the standard methods for the examination of water and wastewater [30] and its
treatment was performed with activated carbon (BFA) at different concentrations.

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3. Results and Discussion
3.1. Physicochemical properties of distillery spent wash

The physicochemical properties of spent wash were investigated and the results of analyses were
described in terms of total solids (TS), temperature, pH, electrical conductivity (EC), chloride,
BOD, COD, ammonia, nitrate, total nitrogen, phosphate, total phosphorus and sulphates. These
analyses were carried out for four solid months and the results are presented in Table 3.

The average values of temperature 47.66 ̊C and pH 4.01 were recorded in raw spent wash which
are out of the Ethiopian distillery effluent discharging limits 40 ̊C and 6 to 9, respectively. The
increase in effluent temperature has a great impact on the environment by accelerating chemical
reactions and rate of biological process in water body and soil that received the effluent. In such
conditions, it would be a great threat to the survival of various biological communities. The acidic
nature of distillery effluent may be attributed to the amount of sulphuric acid that is consumed for
pH adjustment in broth fermentation. Moreover, acidity is one of the essential biotic factors that
can serve as pollution index and also influence the rate of biological reaction which determines the
survival of various microorganisms [3].

The distillery spent wash organic matter COD and BOD found to be 139671 mgL-1and 35989 mgL-
1
, respectively. These values are extremely exceeding the recommended level set by Ethiopian
distillery effluent discharging limits which are COD 250 mgL-1and BOD5 60 mgL-1. The disposal
of effluent with such high loads of BOD and COD into the stream and land can create toxic
conditions by immediate depletion of oxygen which disturbs the water chemistry and biological
communities. Both total nitrogen (1217 mgL-1) and total phosphorous (45 mgL-1) contents were
exceeding the discharging limits which are 40 mgL-1and 5 mgL-1, respectively. Probably, the
presence of these pollutants is caused by the nitrogen and phosphorous sources that are added
during the fermentation process. The unique thing about this distillery effluent analysis is the value
of ammonia (14.04 mgL-1) which was within the range of recommended level (20 mgL-1).
Additionally, the nitrate (4.06 mgL-1) and phosphate (20.99 mgL-1) were also obtained. Urea (CO
(NH2)2) is used as a nitrogen-release fertilizer and source of nutrient for yeast (saccharomyces

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cerevisiae) for bioethanol production. Furthermore, diammonium phosphate (DAP) ((NH4)2HPO4)
fertilizer is an excellent source of P and nitrogen (N) which is commonly used in distillery
fermentation. Metahara ethanol distillery data indicated that urea and DAP fertilizers are applied
at the rate of 1.81 and 0.63 kg(kL)-1 of ethanol, respectively. These conditions might be attributed
to high concentrations of nitrogen and phosphorus sources of distillery spent wash. Thus, the
pollutants are potential contributors for eutrophication of lakes, rivers and another water bodies
which received the effluent.

High amount of total solids 156 gL-1 was recorded which also extremely exceeded the discharging
limits (50 mgL-1). This high amount of total solid might be due to the insoluble organic and
inorganic matter present in the effluent. When the effluent discharged into a stream or any water
bodies, the enormous total solid particulates affect the light intensity of water bodies that interfere
the natural aquatic ecosystem. Additionally, the result of other parameters such as electrical
conductivity (43.6 mScm-1), chloride (6476 mgL-1) and sulphates (4983 mgL-1) were recorded but
there are no standards for these parameters to monitor the distillery spent wash. These are another
pollutants that can cause water and soil pollution with adverse effects towards the environment.
3.2. The ratio of BOD5 to COD in distillery spent wash

The ratio of BOD5 to COD is a good indicator for the degree of degradability of organic matter by
the microbial community and the nature of biochemical reaction in wastewater treatment plant.
Thus, the correlation between BOD5 and COD in distillery spent wash was investigated and the
results were presented in Table 3. This relation between BOD5 to COD was positive and linear
with a well-defined pattern was observed. The concept of bio-degradability capacity which is
commonly termed as biodegradability index (BI), is used to provide basic information for selection
of appropriate treatment technology and treatment plant design. Usually, for fairly degradable and
effective biological treatment, the BOD/ COD > 0.6 is expected and for the value of BI in between
0.3 and 0.6, seeding of acclimatized microorganisms is required. For BOD/COD < 0.3 biologically
treatment becomes difficult since biodegradation will not proceed [32]. Because of recalcitrant and
refractory compounds in distillery spent wash, sometimes very low BOD/COD (0.049) was
reported which confirmed that very poor biodegradability of effluent [33]. In this study, the
calculated value of BI in distillery spent wash was about 0.3 which indicated that biological
treatment is possible but could become difficult. However, the actual value of BI from the
experimental value is 0.26. This is clearly indicated that another treatment technology has to seek
for and the reason why effective treatment option for distillery spent wash still under investigation.

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3.3. Bagasse fly ash characterization using Scanning electron microscopy

The adsorbent (BFA) surface morphology was investigated using scanning electron microscopy
(SEM) before and after the adsorption treatment with wastewater. The SEM images of the
adsorbent (Figure1) shows that a large number of various size of pores with irregular and
heterogeneous shapes were observed which contributed to the surface area of adsorbent. This
remarkably rough and pores containing surface revealed that the material is providing the binding
sites for adsorbates. Moreover, the adsorbent morphology after treatment indicated that significant
adsorbent surface change and with diminishing in porosity was observed due to the interactions
between adsorbate and adsorbent.

3.4.The effect of initial COD concentration on adsorption

In this analysis, adsorbent dose (4 g in 100 mL solution), pH (8), and contact time (4 h) were kept
constant but different initial COD concentrations such as 1000, 2000, 3000, 4000, 5000 and 6000
mgL-1 were taken. The temperature of the treatment system was monitored in water bath shaker at
the fixed temperature of 25 ℃. Adsorption efficiency increases with increasing initial COD
concentration due to the fact that resistant to the uptake of the adsorbate was minimized in such
conditions. The adsorptive capacity (qe) was increased from 6 to 92.4 mg g-1 as the removal
efficiency was raised from 24 to 61.6 % for 1000 mgL-1 and 6000 mgL-1 initial COD concentration,
respectively. The increase in an initial concentration of adsorbate is due to an increase in driving
force of concentration gradient which increases the mass transfer rate [34]. In another study, the
application of bagasse fly ash as an adsorbent for the removal of brilliant green dye from aqueous
solution resulted in the adsorptive capacity of 65.8 mg g-1 [35]. The color removal from ink
wastewater by sawdust fly ash (85.5 mg g−1), activated carbon (40.5 mg g−1) and bagasse fly ash
(7.3 mg g−1) were reported [36]. Furthermore, 90% removal of cadmium 14 mgL-1 and nickel 12
mgL-1 of wastewater was also achieved using BFA [29].

3.5.The effect of pH on adsorption


A screening experiment was conducted to understand the effect of the pH variations on COD
removal efficiency. However, an insignificant change was observed as the pH values changed from
acid media to alkaline. For instance, the removal percentage of COD was increased by only 9.2%
when pH value shifted from 3 to 8 under the experimental condition of an adsorbent dose of 4 g

11
in 100 mL, contact time 4 h and initial COD concentration 6 000 mgL-1. This might be attributed
to the effect of the activating agent (hydrogen peroxide) of adsorbent which enhance the positive
valence on the surface on the adsorbent and favors adsorption phenomena at acidic media for
negatively charged spent wash. Moreover, the adsorptive capacity of BFA was influenced mainly
by the interaction between the adsorbent (BFA), spent wash and the solution media either the H +
or OH- .

3.6. Adsorption of kinetics study

Batch adsorption experiment was carried out to investigate the effect of contact time on adsorption
process at various time 60, 120, 180, 240 and 300 minutes, while initial COD concentration (600
mgL-1), adsorbent dose (4 g per 100 mL), pH (8) and at room temperature were kept constant.
Increasing the contact time increased the uptake of the organic matter on the surface of the
adsorbent. This is might be happened due to the reason that the adsorbate can get sufficient time
to interact with the surface of adsorbent which increases the chance of attachment. This indicates
that equilibrium was not yet achieved. Hence, the longer time needed to achieve the equilibrium
might be attributed to the fact that the concentration of the initial solution is so high.

Additionally, pseudo-first-order and pseudo-second order were employed to determine adsorption


kinetics phenomena which indicated in Equation 2 [37]. The pseudo-first-order equation was given
as follows:

𝑘1 𝑡
log( 𝑞𝑒 − 𝑞𝑡 ) = 𝑙𝑜𝑔 𝑞𝑒 − (2)
2.303

where the parameters qt and qe are the amount of organic matter adsorbed onto activated carbon of
BFA (mg g-1) at time t and equilibrium, respectively. The adsorption rate constant (k1 = 0.008 min-
1
) was observed whereas the calculated adsorptive capacity (qe) was 76 mg g-1 (R2= 0.88).

Also a pseudo second order rate equation was employed to evaluate the adsorption process. The
pseudo second order rate equation is given by:

𝑡 1 𝑡
= 2
+ (3)
𝑞𝑡 𝑘2 𝑞𝑒 𝑞𝑒

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where k2 (g mg−1 min−1) is the rate constant of a pseudo second order adsorption model. The plot
𝑡
of 𝑞 vs t is shown in Figure 2 below. The estimated values of the pseudo second order rate constant
𝑡

(k2) and the adsorption capacity were 0.0002 g mg−1 min−1 and 116.3 mg g-1(R² = 0.98),
respectively.

To select the best model for adsorption kinetics, the R² value and calculated value of adsorption
capacity (qe cal) of the pseudo-first-order and pseudo-second order were compared. The
experimental value of maximum adsorptive capacity (qe exp) was determined to be 124.80 mg g-1.
This clearly showed that the second order model is performing better as the R2 is very high and qe
cal is nearly the same as the experimental value (qe exp).

3.7. The effect of temperature on adsorption

The effect of temperature on adsorption efficiency was highly pronounced and presented in Figure
3. This is clearly shown that adsorption process was endothermic. Increasing adsorption efficiency
with temperature is attributed to the increasing diffusion rate of organic molecules which will
create many contact opportunities with a number of active sites on the surface the adsorbent.
Hence, increasing mobility of the adsorbate at high temperature can result in increasing the uptake
of organic matter on BFA. Raising adsorptive capacity of the adsorbent with temperature might be
associated with an increasing kinetic energy of the adsorbate which enhances its availability at the
active sites of the adsorbent [38]. The uptake of the organic matter on BFA was increased from
29.5 to 75.5 % as temperature raised from 15 to 55 ̊C. Additionally, increasing adsorption with
temperature indicated the chemisorption nature of the adsorption phenomena [39] which is
consistent with the results of this study. Even though increasing temperature favors the adsorption
process of this study, sometimes adsorptive capacity can be decreased with increasing temperature.
At elevated temperatures, the earlier adsorbed molecules on a surface of adsorbent tend to desorb
because the adsorptive forces between the active sites of adsorbent and adsorbate species are
weakened.

3.8. Adsorption thermodynamics

The study of adsorption thermodynamics phenomena was carried out over the range of
temperatures 15 to 55 ̊C. At each equilibrium point of adsorption processes, the equilibrium
adsorption distribution constant sometimes also called equilibrium constant (Kd) can be

13
determined in three ways. The first two ways were based on Freundlich and Langmuir constants.
The third method was based on adsorption thermodynamics equilibrium. For this study, the third
method was employed to determine 𝐾𝑑 values as shown in Equation 4.

𝑞𝑒
𝐾𝑑 = (4)
𝑐𝑒

where ce is the equilibrium concentration of solution (mgL-1), qe (mg g-1) is the amount of organic
matters adsorbed on the surface of the adsorbent (BFA) and Kd is the adsorption equilibrium
constant. The Kd value of this experiment was calculated at the adsorption equilibrium of different
temperatures (15, 25, 35, 45 and 55 ̊C).

To determine the correct value of the thermodynamic parameters, this Kd was calculated to become
dimensionless by multiplying 1000 which is almost the same as the density of solution ( ≈ 1000
gL–1) [40]. This density concept was used in [41] in order to calculate the Kd value which was
missed in many literature and sources of errors in determining the values of other thermodynamic
parameters. The value of the Gibbs free energy change during the adsorption process is related to
the equilibrium constant (Kd) by Equation 5. The equilibrium constant Kd increased with
increasing temperature from 15 to 55 ̊C which indicated that the adsorption of organic matters
favored at higher temperature 55 ̊C.

𝐺 = −RTln 𝐾𝑑 (5)

The errors aroused when the values of G is calculated using Equation 5 was adjusted since 𝐾𝑑 is
multiplied by correction factor and become dimensionless parameter otherwise the values of Gibbs
free energy were incorrect. Thermodynamic analysis showed that all values of Gibbs free energy
change were ranged from -5.61 to -11.84 kJ mol-1 which showed that high driving force is required
for adsorption process. These negative values were confirmed that the adsorption of organic matter
onto BFA adsorbent was spontaneous and thermodynamically favored. However, The positive
values of Gibbs free energy change indicated the small amount of energy is needed from external
to carry out adsorption which declared the increases of free energy change with temperature [42].
Hence, it can be concluded the increase in non-spontaneity nature is in parallel with the increase
of adsorption temperature under this specific condition. The degree of negativity for G increases
with increasing temperature which confirmed that the degree of spontaneity and feasibility of the

14
adsorption process are increased with increasing temperature. This process might be associated
with the increase in the mobility of the adsorbate particles.

Change in enthalpy and entropy were calculated according to the Van’t Hoff equation (Equation
6). Moreover, the Van’t Hoff concept can give some information on the sorption mechanism for
studied adsorbent which shows the relationship between the adsorption coefficient Kd and other
thermodynamic parameters at different temperature that expressed as Equation 6.

𝐻 𝑆
𝑙𝑛 𝐾𝑑 = − + (6)
𝑅𝑇 𝑅

where the H is the enthalpy change (kJ mol-1), 𝑆 is the entropy change (kJ mol-1 K-1), R is
universal gas constant (8.314 J mol-1 K-1) and T is the absolute temperature (K).

The equilibrium distribution coefficient was associated with temperature in linear plot of 𝑙𝑛 𝐾𝑑
1
versus 𝑇 which was shown in Figure 4. From this linear relationship, the values of enthalpy and

entropy changes were determined from the slope and intercept of the equation, respectively. The
Coefficient of determination (R2) of the equation was 0.98.

Overall the adsorption thermodynamics analyses help to predict the nature of adsorption
phenomena. The calculated values of enthalpy and entropy change with the Gibbs free energy
change were shown in Table 4. From the adsorption process, the values of the enthalpy change
were positive (42.29 kJmol-1) which confirmed that the process was endothermic and increased
the removal of organic pollutants on the surface of the BFA with increasing temperature. The idea
of physisorption or chemisorption process can be identified according to the magnitude of ΔH.
Endothermic nature of adsorption system most likely indicates physical adsorption since
adsorption increases with increasing the temperature of the system. Even though the level of the
interactions between adsorbate and adsorbent was determined by physisorption or chemisorption,
sometime adsorption increases with increasing temperature which might be indicative of
chemisorption and vice versa for physisorption. For those change in enthalpy values greater than
20 kJ mol−1, the process is predominantly governed by chemical interactions, chemisorption [43].
The value of H assigned to judge whether the physisorption or chemisorption is a controversy
in literature but the magnitude of the H that lie in the range of 2.1 to 20.9 and 80 to 200 kJ
mol−1 are considered as physical and chemical adsorption, respectively [44].

15
Another thermodynamics parameter is the entropy change which normally shows whether the
adsorption mechanism is an associative or dissociative based on its magnitude and sign. Usually,
the negative value of entropy change involves association mechanism. The value of the entropy
change in this study was 0.17 kJ (Kmol) −1 and positive. The positive value of the entropy change
involves the dissociation process which indicates some structural changes in the adsorbates and
adsorbents in the process [42]. On the other hand, the positive entropy change also indicated that
there was a good affinity between the adsorbate and adsorbent [45]. Generally, thermodynamics
study showed that the adsorption process was a feasible, spontaneously, endothermic and
physicochemisorption process.

4. Conclusions

Investigation of physicochemical properties of distillery spent wash showed that high amount of
organic matter which expressed in terms of COD and BOD; and total solids were obtained with
high acidic property. Moreover, the ratio of BOD/COD of distillery spent wash was very low
(0.03) which indicated that treatment of the spent wash by biological method would be a big
challenge and need to look for another treatment option like adsorption. Adsorptive capacity of
activated carbon produced from bagasse fly ash was increased with increasing contact time, initial
COD concentration and temperature. The adsorptive capacity (qe) was also increased from 6 to
92.4 mg g-1 as the initial COD concentration was increased from 1000 mgL-1 and 6000 mgL-1. The
uptake of the organic matter on the adsorbent surface was increased from 29.5 to 75.5 % with the
temperature (from 15 to 55℃). Adsorption kinetics study follows pseudo-second order model with
k2 = 0.0002 g mg−1 min−1. The qe value was in good agreement with the observation data. Based
on adsorption thermodynamic, the change in Gibbs free energy showed that the adsorption process
was feasible and spontaneous whereas the enthalpy change was positive which revealed that the
process is endothermic. The positive value in entropy change confirmed that the increasing of
randomness at the solid-liquid interface. Finally, activated BFA is the promising option for
removal of organic matter removal (COD) from molasses spent wash under the study condition.

16
Funding Sources

This work was supported by United States Agency for International Development (USAID) under
the USAID/HED funded grant in the Africa-US Higher Education Initiative – HED 052-9740-
ETH-11-01.

Acknowledgments

We would like to thank Ethiopian Institute of Water Resources, Addis Ababa University for
supervising financial support given by the United States Agency for International Development
(USAID) under the USAID/HED funded grant in the Africa-US Higher Education Initiative –
HED 052-9740-ETH-11-01. We would also like to thank Ghent University, Faculty of Bioscience
Engineering for offering us complete laboratory facilities and Ethiopian Sugar Corporation
Research and Development Center for providing us bagasse fly ash and all other necessary
supports.

17
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21
Figure1 SEM surface of BFA before (left) and after (right) the treatment with wastewater

22
3.5
3
2.5
2
t/qt

1.5
1
0.5
0
0 50 100 150 200 250 300 350
Time (min.)

Figure 2 The rate of pseudo-second-order adsorption against time

90
80
70
Removal COD %

60
50
40
30
20
10
0
280 290 300 310 320 330
Temperature (K)

Figure 3 Removal efficiency of COD against temperature

23
5
4.5
4
3.5
3
LnKd

2.5
2
1.5
1
0.5
0
0.003 0.0031 0.0032 0.0033 0.0034 0.0035
1/T (K)

Figure 4. The thermodynamics analysis plotting curve of lnKd versus 1/T

24
Table 1 Adsorption kinetics conditions and adsorbent (BFA) particle size
Contact time(h) COD mgL-1 pH Adsorbent (g) Temp. (̊C) APS
1
2 6000 8 4 25 <162 μm
3
4
5
6
where APS is adsorbent (BFA) particle size

Table 2 Thermodynamic conditions for adsorption process


Temperature (℃) COD mgL-1 pH Adsorbent dose Contact time Centrifugation
15
25 6000 8 4g 4h 350 rpm (30 min)
35
45
55

25
Table 3 Physico-chemical characteristics of distillery spent wash
Parameters M1 M2 M3 M4 Average ES

pH 3.94+0.02 3.96±0.02 3.96±0.09 4.17±0.057 4.01 6-9

EC (mS/cm) 40.3+0.42 42.8± 0.6 40.7±1.56 50.5±1.02 43.6 -

Temp ((̊C) 46.7+0.71 47.3± 0.25 49.6±0.78 47.2±0.50 47.7 40

TS (g/L) 143.1+4.13 157.6±3.71 155.7±3.89 169.4±0.85 156.4 50

BOD(mgL-1) 37661+53.74 42880±40.5 35751±55.15 27661±86.97 35990 60

COD (mgL-1) 126684+24.25 138207±207 167479±77.78 126316± 446.2 139671 250

BOD/COD 0.29 0.31 0.21 0.22 0.26 -

N-NO3- (mgL-1) 2.40+0.28 4.03±0.22 5.72±0.820 4.11±0.23 4.06 -

N-NH3 (mgL-1) 12.7+0.85 14.21±0.29 17.62±0.57 11.62±0.59 14.04 20

TN (mgL-1) 1151+71.82 1355±25.56 1208±42.61 1154±55.85 1217 40

TP (mgL-1) 32.2+0.87 41.3±1.09 36.5±1.15 70.8±3.59 45 5

PO43- (mgL-1) 18.97+0.62 23.35± 0.95 25.515±2.14 16.12±1.39 21.99 -

Cl- (mgL-1) 5968+62.15 4862±65.18 7475±120.21 76001±34.14 6476 -

SO4-2 (mgL-1) 4443+18.29 4561±7.55 4917±37.47 6012±38.53 4983 -

where M1, M2, M3 and M4 are first, second, third and fourth month of sampling, respectively. But ES refers Ethiopian
standard for the maximum permissible limit of distillery spent wash to be discharged. Each value of the parameter
described as mean value± standard deviation at n = 3.

26
Table 4 Adsorption thermodynamic results of organic matters on BFA
SN Temperature (K) G (kJ(mol)-1) Kd H(kJ(mol)-1) S(kJ(Kmol)-1)

1 288 -5.61 10.4 42.29 0.17

2 298 -6.98 16.7

3 308 -8.97 33.2

4 318 -11.06 65.6

5 328 -11.84 76.9

27

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