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of Environmental Chemical Engineering 5 (2017) 5381–5388 Contents lists available at ScienceDirect Journal of

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

journal homepage: www.elsevier.com/locate/jece Adsorption of distillery spent wash on activated bagasse

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

Jemal Fito a , , Nurelegne Tefera b , Stijn W.H. Van Hulle c

a Ethiopian Institute of Water Resources, Addis Ababa University, P.O. Box 150461, Addis Ababa, Ethiopia

b Addis Ababa Science and Technology University, Ethiopia

c Department of Industrial Biological Sciences, Ghent University, Graaf Karel de Goedelaan 5, B-8500, Kortrijk, Belgium

T
T

ARTICLE INFO

Keywords:

Adsorption Bagasse y ash COD removal Kinetics Spent wash Thermodynamics

ABSTRACT

This study aimed to characterize distillery spent wash and COD removal from it using bagasse y ash (BFA). The results of the analyses showed that the average value of BOD 5 and COD were 35,990 mgL 1 and 13,9671 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 di erent 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 (q e ) from 6 to 92.40 mg g 1 and resulted in an increase in removal eciency from 24 to 61.6%. Adsorptive capacity (116.30 mg g 1 ) calculated by the pseudo-second order model (R 2 = 0.98) indicated that pseudo-second order kinetic model tted better with the experimental data. Moreover, the Gibbs free energy change ( Δ G) (5.61 to 11.84 kJ mol 1 )) showed that adsorption process was spontaneous whereas the po- sitive value of the Δ 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 ( Δ S = 0.17 kJ (Kmol) 1 ). In general, thermodynamic study 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.

1. Introduction

The rapid advancement of industrialization and progress of civili- zation 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 a ecting the water consumed, the air inhaled and the soil lived on [3] . Industrial waste management is one of the most important environ- mental problems faced by today s world because industrial processes create a variety of wastewater pollutants that are di cult 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 e uent with very limited space for treatment and disposal [5] . Alcohol distilleries are extensively growing because of the varia- bility 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 ad- justment of pH for fermentation broth is made by sulphuric acid [6] . These supplements are the major contributor to spent wash pollution. 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 (C 17 18 H 26 27 O 10 N)

Corresponding author. E-mail address: tojemal120@gmail.com (J. Fito).

Received 12 August 2017; Received in revised form 30 September 2017; Accepted 2 October 2017

Available online 07 October 2017 2213-3437/ © 2017 Elsevier Ltd. All rights reserved.

J. Fito et al.

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 dis- persed 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 pre- sence of these recalcitrant components in the spent wash makes it hardly degradable in the di erent (biological) wastewater treatment stages and results in the discharge into the environment [6] . As dis- tillery spent wash is an eco-toxic e uent that is unsafe to dispose into agricultural and aquatic ecosystem [13] , ethanol distilleries are con- sidered 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 euent into the water bodies might be lead to eutrophication [15] . Cost-e ective and e cient treatment methods for distillery spent wash are still under investigation but the pollution controlling gov- ernment policies are more and more stringent. Conventional waste- water 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 coagula- tion occulation, ltration and di erent combinations of these methods have also been tested for the treatment of distillery spent wash, but were not e ective. Furthermore, the conventional biological treatments such as trickling lter and activated sludge are better but ine cient 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 e uents such as distillery spent wash [17] . However, the color causing pigments of spent wash are not e ectively 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. 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 simulta- neously removing of other inorganic pollutants such as nutrients, salts and metals. Adsorption is more popular among many treatment methods be- cause of its simple design, easy operation and the possibility of ad- sorbent re-use or recycling. This technology is commonly employing in wastewater treatment because of its economic viability, technical fea- sibility and socially acceptability [19] . Today, special attention is given for agro-based inexpensive adsorbents such as sugarcane bagasse, wood sawdust, bagasse y ash, wood ash and rice husk because of their minimum environmental polluting e ect [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 e cient, available and does not require any ex- pensive pretreatment process. The development of adsorbent from industrial by-products like ba- gasse y ash (BFA) is a potential research area because of the com- mercially 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 e ective and attractive process. For instance, 78% removal e ciency 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 )

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[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 di erent size of adsorbates in the treatment process [24] . Moreover, BFA has good porous structure and adsorption capacity, in addition to, easily mod- i ed 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 acti- vated carbons commercial were 336.6 m 2 g 1 , 599.32 kgm 3 and 18.81 MJkg 1 whereas these properties for BFA were 168.39 m 2 g 1 , 185.51 kgm 3 and 19.23 MJkg 1 , respectively [23] . Hence, BFA has a potential to substitute commercially available carbon due to its com- parable e ciency and a signi cantly 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] . Si- milarly, the treatment of synthetic dairy wastewater by means of ad- sorption 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 e ciency [27] . Practically, some adsorbents are disposed of without the re- generation because of their low cost and unlimited availability. Re- generation 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, H 2 SO 4 , HNO 3 , CH 3 COOH, C 2 H 5 OH, acetone NaOH and distilled water are very e ective 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 e - ciency 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 y 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 °C for 24 h. Then it was washed with de-ionized water repeatedly until all hydrogen peroxide on the surface was re- moved. This activated bagasse y ash (BFA) was placed 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 15 kV (JEOL JSM-7600F FEG-SEM, JEOL, USA). The sample was ap- plied on carbon tape, and measured at a working distance of 8 mm. 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 1000× magni cations [19] .

J. Fito et al.

2.2. The e ect 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 re ux method which is suitable for a wide range of wastes such as distillery spent wash. A wastewater sample was re uxed in strongly acid solution with a known excess of potassium dichromate (K 2 Cr 2 O 7 ). After digestion, the remaining un- reduced K 2 Cr 2 O 7 is titrated with ferrous ammonium sulphate to de- termine the amount of K 2 Cr 2 O 7 consumed and the oxidizeable matter was calculated in terms of oxygen equivalent. Due to it is higher oxi- dizing ability dichromate re ux method was preferred over other pro- cedures using other oxidants. Hence, the COD concentration of waste- water was determined by open reux method (APHA 5220 B) and dilution process was performed by distilled water at laboratory scale [30] . The e ect of initial COD concentration on treatment e ciency 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 e ect of pH on adsorption

The e ect of pH on removal e ciency of organic matter on bagasse y ash form distillery spent was tested at screening stage of the treat- ment. The pH range of 3 8 was selected and its e ects 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 25°C.

2.4. Adsorption kinetics

Batch adsorption kinetics tests were carried out using di erent contact time under xed experiment condition ( Table 1). Wastewater samples were taken and placed into 250 mL conical asks; and agitated at 160 rpm using water bath shaker at the xed temperature of 25 °C. Afterwards, the solution was centrifuged at 3500 rpm for 30 min. Fi- nally, the solution was ltered using Whatman lter paper 42 and the COD analysis was performed as per standard methods for the ex- amination of water and wastewater [30] . The amounts of organic matter adsorbed onto activated carbon was determined according to Eq. (1) .

c

t

v

c

0

m

q t =

(1)

where c o is initial concentration of COD and c t 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, q e can be calculated as the amount of organic matter adsorbed onto activated carbon at equili- brium.

2.5. Adsorption thermodynamics

Batch experimental adsorption thermodynamics was performed in

Table 1 Adsorption kinetics conditions and adsorbent (BFA) particle size.

Contact time(h)

COD mgL 1

pH

Adsorbent (g)

Temp. (°C)

APS

1

6000

8

4

25

< 162 μ m

2

3

4

5

6

where APS is adsorbent (BFA) particle size.

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250 mL conical asks. Wastewater samples were agitated at 160 rpm using water bath shaker which was operated at the predetermined di erent temperatures indicated in Table 2 . Then the agitated samples were centrifuged and ltered through Whatman lter paper 42. Finally, the ltrate samples were tested for a change in COD concentration and the amount of organic matter adsorbed was calculated according to Eq. (1) .

2.6. Spent wash collection

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 fac- tory in plastic bottles that were pre-cleaned with acid. After the sam- pling, the e uent 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 la- boratory and grab sampling techniques were used for physical para- meters 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 103 105 ° C), am- monia (APHA 4500, MgO Distillation methods), nitrate (APHA 4500- NO 3 B, Ultraviolet spectrophotometric screening methods), total ni- trogen (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 re ex 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 95°C 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 di erent concentrations.

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 re- corded in raw spent wash which are out of the Ethiopian distillery ef- uent discharging limits 40 °C and 6 to 9, respectively. The increase in

J. Fito et al.

Table 2 Thermodynamic conditions for adsorption process.

Journal of Environmental Chemical Engineering 5 (2017) 5381–5388

Temperature (°C)

COD mgL 1

pH

Adsorbent dose

Contact time

Centrifugation

15

6000

8

4 g

4 h

350 rpm (30 min)

25

35

45

55

e uent temperature has a great impact on the environment by accel- erating chemical reactions and rate of biological process in water body and soil that received the e uent. In such conditions, it would be a great threat to the survival of various biological communities. The acidic nature of distillery e uent may be attributed to the amount of sulphuric acid that is consumed for pH adjustment in broth fermenta- tion. Moreover, acidity is one of the essential biotic factors that can serve as pollution index and also inuence the rate of biological reac- tion which determines the survival of various microorganisms [3] . The distillery spent wash organic matter COD and BOD found to be 139671 mgL 1 and 35989 mgL 1 , respectively. These values are ex- tremely exceeding the recommended level set by Ethiopian distillery e uent discharging limits which are COD 250 mgL 1 and BOD 5 60 mgL 1 . The disposal of e uent 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 1 and 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 e uent 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 (NH 2 ) 2 ) is used as a nitrogen-release fertilizer and source of nutrient for yeast (saccharomyces cerevisiae) for bioethanol production. Furthermore, diammonium phosphate (DAP) ((NH 4 ) 2 HPO 4 ) 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 condi- tions 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 e uent. High amount of total solids 156 gL 1 was recorded which also

Table 3 Physico-chemical characteristics of distillery spent wash.

extremely exceeded the discharging limits (50 mgL 1 ). This high amount of total solid might be due to the insoluble organic and in- organic matter present in the e uent. When the e uent discharged into a stream or any water bodies, the enormous total solid particulates a ect 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 an- other pollutants that can cause water and soil pollution with adverse e ects towards the environment.

3.2. The ratio of BOD 5 to COD in distillery spent wash

The ratio of BOD 5 to COD is a good indicator for the degree of de- gradability of organic matter by the microbial community and the nature of biochemical reaction in wastewater treatment plant. Thus, the correlation between BOD 5 and COD in distillery spent wash was in- vestigated and the results were presented in Table 3 . This relation be- tween BOD 5 to COD was positive and linear with a well-de ned 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 e ective 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 di cult 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 conrmed that very poor bio- degradability of euent [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 di cult. 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 e ective treatment option for distillery spent wash still under

Parameters

M 1

M 2

M 3

M 4

Average

ES

pH EC (mS/cm) Temp ((°C) TS (g/L) BOD(mgL 1 ) COD (mgL 1 ) BOD/COD NeNO 3 (mgL 1 ) NeNH 3 (mgL 1 ) TN (mgL 1 ) TP (mgL 1 ) PO 4 3 (mgL 1 ) Cl (mgL 1 ) SO 4 2 (mgL 1 )

3.94 + 0.02 40.3 + 0.42 46.7 + 0.71 143.1 + 4.13 37661 + 53.74 126684 + 24.25

3.96 ± 0.02 42.8 ± 0.6 47.3 ± 0.25 157.6 ± 3.71 42880 ± 40.5

3.96 ± 0.09 40.7 ± 1.56 49.6 ± 0.78 155.7 ± 3.89 35751 ± 55.15 167479 ± 77.78

4.17 ± 0.057 50.5 ± 1.02 47.2 ± 0.50 169.4 ± 0.85 27661 ± 86.97 126316 ± 446.2

4.01

69

43.6

47.7

40

156.4

50

35990

60

138207

± 207

139671

250

0.29

0.31

0.21

0.22

0.26

2.40 + 0.28 12.7 + 0.85 1151 + 71.82 32.2 + 0.87 18.97 + 0.62 5968 + 62.15 4443 + 18.29

4.03 ± 0.22 14.21 ± 0.29 1355 ± 25.56 41.3 ± 1.09 23.35 ± 0.95 4862 ± 65.18 4561 ± 7.55

5.72 ± 0.820 17.62 ± 0.57 1208 ± 42.61 36.5 ± 1.15 25.515 ± 2.14 7475 ± 120.21 4917 ± 37.47

4.11 ± 0.23 11.62 ± 0.59 1154 ± 55.85 70.8 ± 3.59 16.12 ± 1.39 76001 ± 34.14 6012 ± 38.53

4.06

14.04

20

1217

40

45

5

21.99

6476

4983

J. Fito et al.

Journal of Environmental Chemical Engineering 5 (2017) 5381–5388

of Environmental Chemical Engineering 5 (2017) 5381–5388 Fig. 1. SEM surface of BFA before (left) and

Fig. 1. SEM surface of BFA before (left) and after (right) the treatment with wastewater.

investigation.

3.3. Bagasse y 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 ( Fig. 1 ) 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 signi cant adsorbent surface change and with diminishing in porosity was observed due to the interactions between adsorbate and adsorbent.

3.4. The e ect 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 di erent initial COD con- centrations 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 xed temperature of 25 °C. Adsorption e - ciency 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 (q e ) was increased from 6 to 92.4 mg g 1 as the removal e ciency 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 in- crease in driving force of concentration gradient which increases the mass transfer rate [34] . In another study, the application of bagasse y 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 y ash (85.5 mg g 1 ),

activated carbon (40.5 mg g 1 ) and bagasse y

reported [36] . Furthermore, 90% removal of cadmium 14 mgL 1 and

nickel 12 mgL 1 of wastewater was also achieved using BFA [29] .

ash (7.3 mg g 1 ) were

3.5. The e ect of pH on adsorption

A screening experiment was conducted to understand the e ect of the pH variations on COD removal e ciency. However, an insigni cant change was observed as the pH values changed from acid media to alkaline. For instance, the removal percentage of COD was increased by

5385

only 9.2% when pH value shifted from 3 to 8 under the experimental condition of an adsorbent dose of 4 g in 100 mL, contact time 4 h and initial COD concentration 6 000 mgL 1 . This might be attributed to the e ect 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 inuenced 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 ef- fect of contact time on adsorption process at various time 60, 120, 180, 240 and 300 min, while initial COD concentration (600 mgL 1 ), ad- sorbent 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 hap- pened due to the reason that the adsorbate can get su cient 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- rst-order and pseudo-second order were employed to determine adsorption kinetics phenomena which indicated in Eq. (2) [37] . The pseudo- rst-order equation was given as follows:

log(

(2)

where the parameters q t and q e are the amount of organic matter ad- sorbed onto activated carbon of BFA (mg g 1 ) at time t and equili- brium, respectively. The adsorption rate constant (k 1 = 0.008 min 1 ) was observed whereas the calculated adsorptive capacity (q e ) was 76 mg g 1 (R 2 = 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:

)

qq−=

et

k 1 t

2.303

log

q

e

t

1

t

t

kq

2

2

q

=

+

q

(3)

where k 2 (g mg 1 min 1 ) is the rate constant of a pseudo second order adsorption model. The plot of t t vs t is shown in Fig. 2 below. The

ee

q

J. Fito et al.

J. Fito et al. Journal of Environmental Chemical Engineering 5 (2017) 5381–5388 Fig. 2. The rate

Journal of Environmental Chemical Engineering 5 (2017) 5381–5388

Fig. 2. The rate of pseudo-second-order adsorption against time.

estimated values of the pseudo second order rate constant (k 2 ) and the adsorption capacity were 0.0002 g mg 1 min 1 and 116.3 mg g 1 (R 2 = 0.98), respectively. To select the best model for adsorption kinetics, the R 2 value and calculated value of adsorption capacity (q ecal ) of the pseudo- rst-order and pseudo-second order were compared. The experimental value of maximum adsorptive capacity (q eexp ) was determined to be 124.80 mg g 1 . This clearly showed that the second order model is performing better as the R 2 is very high and q ecal is nearly the same as the experimental value (q eexp ).

3.7. The e ect of temperature on adsorption

The e ect of temperature on adsorption e ciency was highly pro- nounced and presented in Fig. 3 . This is clearly shown that adsorption process was endothermic. Increasing adsorption e ciency with tem- perature is attributed to the increasing di usion rate of organic mole- cules 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. Ad- ditionally, increasing adsorption with temperature indicated the che- misorption nature of the adsorption phenomena [39] which is con- sistent 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 (K d ) can be de- termined in three ways. The rst 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 K d values as shown in Eq. (4) .

K = q

d

e

c e

(4)

where c e is the equilibrium concentration of solution (mgL 1 ), q e (mg g 1 ) is the amount of organic matters adsorbed on the surface of the adsorbent (BFA) and K d is the adsorption equilibrium constant. The K d value of this experiment was calculated at the adsorption equili- brium of di erent temperatures (15, 25, 35, 45 and 55 °C). To determine the correct value of the thermodynamic parameters, this K d was calculated to become dimensionless by multiplying 1000 which is almost the same as the density of solution ( ρ 1000 gL 1 ) [40] . This density concept was used in [41] in order to calculate the K d 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 (K d ) by Equation (5) . The equilibrium constant K d increased with increasing temperature from 15 to 55 °C which indicated that the adsorption of organic matters favored at higher temperature 55 °C.

(5)

ΔG = −RTln K d

The errors aroused when the values of Δ G is calculated using Eq. (5) was adjusted since K d is multiplied by correction factor and become dimensionless parameter otherwise the values of Gibbs free energy

parameter otherwise the values of Gibbs free energy Fig. 3. Removal e ffi ciency of COD

Fig. 3. Removal eciency of COD against temperature.

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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 con rmed 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 speci c condition. The degree of negativity for Δ G increases with increasing temperature which con- rmed that the degree of spontaneity and feasibility of the adsorption process are increased with increasing temperature. This process might be associated with the increase in the mobility of the adsorbate parti- cles. Change in enthalpy and entropy were calculated according to the Van t Ho equation (Eq. (6) ). Moreover, the Van t Ho concept can give some information on the sorption mechanism for studied adsorbent which shows the relationship between the adsorption coe cient K d and other thermodynamic parameters at di erent temperature that ex- pressed as Equation (6) .

ln K =−

d

Δ

H

RT

+

Δ S

R

(6)

where the Δ H is the enthalpy change (kJ mol 1 ), Δ 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 coe cient was associated with tem- perature in linear plot of lnK d versus T which was shown in Fig. 4 . From this linear relationship, the values of enthalpy and entropy changes were determined from the slope and intercept of the equation, respec- tively. The Coecient of determination (R 2 ) 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 con rmed that the process was endothermic and increased the removal of organic pollutants on the surface of the BFA with increasing temperature. The idea of physi- sorption or chemisorption process can be identi ed according to the magnitude of Δ H. 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 tem- perature 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 in- teractions, chemisorption [43] . The value of ΔH assigned to judge

1

Table 4 Adsorption thermodynamic results of organic matters on BFA.

SN Temperature (K)

Δ G (kJ (mol) 1 )

K d

Δ H(kJ (mol) 1 )

Δ

S(kJ

(K

mol) 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

whether the physisorption or chemisorption is a controversy in litera- ture but the magnitude of the Δ 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] . 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 anity between the ad- sorbate 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 treat- ment option like adsorption. Adsorptive capacity of activated carbon produced from bagasse y ash was increased with increasing contact time, initial COD concentration and temperature. The adsorptive ca- pacity (q e ) 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 °C). Adsorption kinetics study follows pseudo-second order model with k 2 = 0.0002 g mg 1 min 1 . The q e 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 re- vealed that the process is endothermic. The positive value in entropy change conrmed that the increasing of randomness at the solid-liquid

rmed that the increasing of randomness at the solid-liquid Fig. 4. The thermodynamics analysis plotting curve

Fig. 4. The thermodynamics analysis plotting curve of lnK d versus 1/T.

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interface. Finally, activated BFA is the promising option for removal of organic matter removal (COD) from molasses spent wash under the study condition.

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 nancial 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 oering us complete laboratory facilities and Ethiopian Sugar Corporation Research and Development Center for providing us bagasse y ash and all other ne- cessary supports.

References

[1] K. Narain, T. Yazdani, Eect on physico-chemical and structural properties of soil amended with distillery euent and ameliorated by cropping two cereal plant spp, Env. Earth Sci. 66 (2012) 977 984, http://dx.doi.org/10.1007/s12665-011-1344-x . [2] K. Nath, D. Singh, Y.K. Sharma, Combinatorial eects of distillery and sugar factory euents in crop plants, J. Environ. Biol. 28 (2007) 577 582 . [3] P. Saranraj, D. Stella, Eect of bacterial isolates on reduction of physico chemical characteristics in sugar mill euent, Int. J. Pharm. Biol. Arch. 3 (2012) 1121 1128 . [4] A. Kadam, K. Upadhyay, Wastewater treatment of alcohol distillery, Jr. Ind. Pollut. Control. 28 (2012) 14 . [5] K.V.A. Chopra, Fertigation eect of distillery euent on agronomical practices of Trigonella foenum-graecum L. (Fenugreek), Environ. Monit. Assess. (2012) 1207 1219, http://dx.doi.org/10.1007/s10661-011-2033-7 . [6] S. Mohana, B.K. Acharya, D. Madamwar, Distillery spent wash: treatment tech- nologies and potential applications, J. Hazard. Mater. 163 (2009) 12 25, http://dx. doi.org/10.1016/j.jhazmat.2008.06.079 . [7] A.K. Jain, A. Ross, S. Prabhakar, An introduction to biometric recognition, IEEE trans. circuits syst, Video Technol. 14 (2004) 4 20, http://dx.doi.org/10.1109/ TCSVT.2003.818349 . [8] D. Pant, A. Adholeya, Biological approaches for treatment of distillery wastewater:

a review, Bioresour. Technol. 98 (2007) 2321 2334, http://dx.doi.org/10.1016/j. biortech.2006.09.027 . [9] A.K. Biswas, M. Mohanty, K.M. Hati, A.K. Misra, Distillery euents eect on soil organic carbon and aggregate stability of a Vertisol in India, Soil Tillage Res. 104 (2009) 241 246, http://dx.doi.org/10.1016/j.still.2009.02.012 . [10] S. Basu, S. Mukherjee, A. Kaushik, V.S. Batra, Integrated treatment of molasses distillery wastewater using micro ltration (MF), J. Environ. Manage. 158 (2015) 55 60, http://dx.doi.org/10.1016/j.jenvman.2015.04.037 . [11] H. Wang, H. Qian, W. Yao, Melanoidins produced by the Maillard reaction: struc- ture and biological activity, Food Chem. 128 (2011) 573 584, http://dx.doi.org/ 10.1016/j.foodchem.2011.03.075 . [12] R.K. Prasad, S.N. Srivastava, Sorption of distillery spent wash onto y ash: kinetics and mass transfer studies, Chem. Eng. J. 146 (2009) 90 97, http://dx.doi.org/10. 1016/j.cej.2008.05.021 . [13] M. Chandrakant, R. Kedar, Physico-chemical analysis and microbial degradation of spent wash from sugar industries, Res. J. Chem. Sci. 3 (2013) 53 56 . [14] R.P. De Souza, F. Girardi, V.S. Santana, N.R.C. Fernandes-Machado, M.L. Gimenes, Vinasse treatment using a vegetable-tannin coagulant and photocatalysis, Acta Sci. Technol. 35 (2013) 89 95, http://dx.doi.org/10.4025/actascitechnol.v35i1.11011 . [15] L.T. Valderrama, C.M. Del Campo, C.M. Rodriguez, L.E. De- Bashan, Y. Bashan, Treatment of recalcitrant wastewater from ethanol and citric acid production using the microalga Chlorella vulgaris and the macrophyte Lemna minuscula, Water Res.

L.H. Andrade, F.D.S. Mendes, J.C. Espindola, M.C.S. Amaral, Nano ltration as tertiary treatment for the reuse of dairy wastewater treated by membrane bior- eactor, Sep. Purif. Technol. 126 (2014) 21 29, http://dx.doi.org/10.1016/j.seppur.

2014.01.056 . [17] M. Rajeshwari, A. Balakrishnan, K. Lata Kansal, V.V.N. Kishore, State-of-the-art of anaerobic digestion technology for industrial wastewater treatment, Renew. Sustain. Energy Rev. 4 (2000) 135 156, http://dx.doi.org/10.1016/S1364- 0321(99)00014-3 . [18] C. David, M. Arivazhagan, F. Tuvakara, Ecotoxicology and environmental safety decolorization of distillery spent wash e uent by electro oxidation (EC and EF) and Fenton processes: a comparative study, Ecotoxicol. Environ. Saf. 121 (2015)

[16]

5388

Journal of Environmental Chemical Engineering 5 (2017) 5381–5388

[19] A.K. Hegazy, N.T. Abdel-Ghani, G.A. El-Chaghaby, Adsorption of phenol onto ac- tivated carbon from seaweed: determination of the optimal experimental para- meters using factorial design, Appl. Water Sci. 42 (2014) 952 956, http://dx.doi. org/10.1016/j.jtice.2011.04.003 . [20] Y. Satyawali, M. Balakrishnan, Removal of color from biomethanated distillery spentwash by treatment with activated carbons, Bioresour. Technol. 98 (2007)

[21] K.Z. Elwakeel, A.M. Elgarahy, S.H. Mohammad, Use of beach bivalve shells located

at Port Said coast (Egypt) as a green approach for methylene blue removal, J.

Environ. Chem. Eng. 5 (2017) 578 587, http://dx.doi.org/10.1016/j.jece.2016.12.

[22] A. Kumar, B. Prasad, I.M. Mishra, Adsorption of acrylonitrile from aqueous solution using bagasse y ash, J. Water Process Eng. 2 (2014) 129 133, http://dx.doi.org/ 10.1016/j.jwpe.2014.05.003 . [23] J.P. Kushwaha, V.C. Srivastava, I.D. Mall, Treatment of dairy wastewater by com- mercial activated carbon and bagasse y ash: parametric, kinetic and equilibrium modelling, disposal studies, Bioresour. Technol. 101 (2010) 3474 3483, http://dx. doi.org/10.1016/j.biortech.2010.01.002 . [24] I.D. Mall, V.C. Srivastava, N.K. Agarwal, I.M. Mishra, Adsorptive removal of ma- lachite green dye from aqueous solution by bagasse y ash and activated carbon- kinetic study and equilibrium isotherm analyses, Colloids Surfaces A Physicochem, Eng. Asp. 264 (2005) 1728, http://dx.doi.org/10.1016/j.colsurfa.2005.03.027 .

I. Ali, M. Asim, T.A. Khan, Low cost adsorbents for the removal of organic pollutants

[25]

Rev. J. Eng. Technol. Util. 2 (2013) 110. [27] K.A. Adegoke, O. Solomon, Dye sequestration using agricultural wastes as ad- sorbents, Water Resour. Ind. 12 (2015) 824, http://dx.doi.org/10.1016/j.wri.

[28] D. Rameshraja, V. Chandra, J. Prakash, I. Deo, Quinoline adsorption onto granular activated carbon and bagasse y ash, Chem. Eng. J. 181182 (2012) 343 351, http://dx.doi.org/10.1016/j.cej.2011.11.090 .

V.K. Gupta, C.K. Jain, I. Ali, M. Sharma, V.K. Saini, Removal of cadmium and nickel from wastewater using bagasse y asha sugar industry waste, Water Res. 37

2006.07.037 . [34] H. Lata, V.K. Garg, R.K. Gupta, Adsorptive removal of basic dye by chemically activated Parthenium biomass: equilibrium and kinetic modeling, Desalination 219 (2008) 250 261, http://dx.doi.org/10.1016/j.desal.2007.05.018 .

[29]

[35] V.S. Mane, I.D. Mall, V.C. Srivastava, Use of bagasse y ash as an adsorbent for the removal of brilliant green dye from aqueous solution, Dye. Pigment. 73 (2007) 269 278, http://dx.doi.org/10.1016/j.dyepig.2005.12.006 . [36] S. Noonpui, P. Thiravetyan, W. Nakbanpote, S. Netpradit, Color removal from water-based ink wastewater by bagasse y ash, sawdust y ash and activated carbon, Chem. Eng. J. 162 (2010) 503 508, http://dx.doi.org/10.1016/j.cej.2010.

05.051 . Y.A. Aydin, N.D. Aksoy, Adsorption of chromium on chitosan: optimization, kinetics

[37]

and thermodynamics, Chem. Eng. J. 151 (2009) 188 194, http://dx.doi.org/10. 1016/j.cej.2009.02.010 . [38] S. Agarwal, I. Tyagi, V. Kumar, N. Ghasemi, Kinetics, equilibrium studies and thermodynamics of methylene blue adsorption on Ephedra strobilacea saw dust and modi ed using phosphoric acid and zinc chloride, J. Mol. Liq. 218 (2016) 208 218, http://dx.doi.org/10.1016/j.molliq.2016.02.073 .

[39] A. Simaratanamongkol, P. Thiravetyan, Decolorization of melanoidin by activated carbon obtained from bagasse bottom ash, J. Food Eng. 96 (2010) 14 17, http://dx. doi.org/10.1016/j.jfoodeng.2009.06.033 . [40] S.K. Milonji ć, A consideration of the correct calculation of thermodynamic para- meters of adsorption, J. Serb. Chem. Soc. 72 (2007) 1363 1367, http://dx.doi.org/ 10.2298/JSC0712363M . [41] Y. Hu, H. Wang, G. Cao, C. Meng, W. Yuan, The adsorption of toluenediamine from the wastewater by activated carbon in batch and xed bed systems, Desalination

[42] A.A. Taha, M.A. Shreadah, A.M. Ahmed, H. Fathy, Multi-component adsorption of Pb (II), Cd (II), and Ni (II) onto Egyptian Na-activated bentonite; equilibrium, ki- netics, thermodynamics, and application for seawater desalination, Biochem. Pharmacol. 4 (2016) 1166 1180, http://dx.doi.org/10.1016/j.jece.2016.01.025 . [43] R.S. Pohndorf, T.R.S. Cadaval Jr., L.A.A. Pinto, Kinetics and thermodynamics ad- sorption of carotenoids and chlorophylls in rice bran oil bleaching, J. Food Eng. 185 (2016) 9 16, http://dx.doi.org/10.1016/j.jfoodeng.2016.03.028 . [44] O. Abdelwahab, N.K. Amin, Adsorption of phenol from aqueous solutions by Lu a cylindrica bers: kinetics, isotherm and thermodynamic studies, Egypt. J. Aquat. Res. 39 (2013) 215 223, http://dx.doi.org/10.1016/j.ejar.2013.12.011 . [45] C. Chen, M. Zhang, Q. Guan, W. Li, Kinetic and thermodynamic studies on the adsorption of xylenol orange onto MIL-101(Cr), Chem. Eng. J. 183 (2012) 60 67, http://dx.doi.org/10.1016/j.cej.2011.12.021 .