Professional Documents
Culture Documents
Organic Mateer Removal
Organic Mateer Removal
y
Dida Gudeta1,2, Dawit Derese1, Fekadu Fufa1, Bart Van der Bruggen2,3
nl
1
Faculty of Civil and Environmental Engineering, Jimma University, Ethiopia; 2Department of
Chemical Engineering, KU Leuven, Belgium;3Faculty of Engineering and the Built Environment,
Tshwane University of Technology, Private Bag X680, Pretoria 0001, South Africa
O
ABSTRACT
The presence of natural organic matter (NOM) in source water has *Correspondence to Author:
posed many challenges for conventional water treatment facilities. Dida Gudeta
Small organic acids, such as humic acid, present in NOM, have a Faculty of Civil and Environmen-
of
high potential to influence the performance of water treatment pro-
tal Engineering, Jimma University,
cesses. Uncontrolled application of agricultural chemicals leads to
Ethiopia; Department of Chemical
the simultaneous presence of toxic substances. In this work, batch
Engineering, KU Leuven, Belgium
adsorption experiments were conducted to examine the biosorp-
o
tion of HA onto chemically activated coffee husk. The biosorption
process was studied as a function of operating conditions, such as
contact time, pH of the solution, HA concentration, adsorbent dose
Pr
AJCR: https://escipub.com/american-journal-of-chemical-research/ 1
Dida Gudeta et al., AJCR, 2019; 3:14
y
Humic substances (HS) are among the major
promising method for the removal of HS from
components of NOM and account for 30–80%
water due to its universal nature, ease of
of the dissolved organic matter in natural water;
nl
regeneration, inexpensiveness and ease of
they are well known as precursors for
operation (Ali, 2011, Dabrowski, 1999).
potentially harmful disinfection by-products
(Yang et al., 2004). The major fractions of HS A variety of adsorbents such as amino-
O
are humic acid (HA), fulvic acid (FA), and functionalized magnetic mesoporous silica,
humin (Matilainen et al., 2011). The presence cationic surfactant-modified bentonite and
of these species in raw water facilitates the activated carbon have been reported as being
reproduction of microorganisms in drinking effective for the removal of NOM from drinking
water (Dabrowski, 1999). Yet it is important to
of
water distribution systems. They also induce
the utilization of a high chlorine dose and act as explore low cost and locally available
the precursor for the formation of harmful adsorbents with a high adsorption efficiency to
disinfection by-products (DBP), such as remove NOM from water and wastewater.
ro
trihalomethanes (THMs), which are classified Activated carbon (AC) is a widely used
as potentially carcinogenic chlorine organic adsorbent in water and wastewater treatment
compounds (Lee et al., 2009). They can cause processes. For years, many biosorbent
a reducing in the efficiency of water treatment materials made from agricultural byproducts
rP
facilities by interfering with various oxidants, have been utilized to remove pollutants from
increasing the solubility of heavy metals due to water and wastewater. These include coconut
complexation with metals and adsorbed organic husk and shell, sea weeds (Amuda et al.,
pollutants (Yang et al. 2007). 2007), maize leaf, coffee beans (Kaikake et al.,
Particularly, small organic acids such as HA 2006 and Haftu G. et al., 2014) and rice husk
facilitate the regrowth of bacterial activities in ash (Imyim and Prapalimrungsi., 2010). By
Fo
the distribution system and biofilm formation in optimizing the preparation conditions or/and
pipelines. Microbial regrowth can deteriorate adsorption process, it is possible to increase
the taste and odour of the drinking water and it the removal efficiency of pollutants onto
can even lead to potential health hazards (Anke activated carbon. The maximum adsorption
Grefte, 2013). capacities, ease of regeneration and low-cost of
adsorbents demonstrated that the adsorbents
Many technologies have been introduced to
obtained from agricultural waste have a wide
remove NOM from drinking water sources.
range of applications for organic pollutants
Among these coagulation, flocculation, granular
removal (Zhou et al., 2015).
activation carbon (GAC), reverse osmosis, ion
exchange, electro-dialysis, electrolysis, This study addresses the utilization of
advanced oxidation and adsorption processes chemically activated coffee husk (CACH) for
biosorption of HA from water.
AJCR: https://escipub.com/american-journal-of-chemical-research/ 2
Dida Gudeta et al., AJCR, 2019; 3:14
2. Materials and Methods amount of adsorbent in 250 mL Erlenmeyer
2.1. Adsorbent Collection and Preparation flask. The effects of different operating
parameters such as adsorbate concentration,
The adsorbent, coffee husk was obtained from
adsorbent dose, contact time, agitation speed
a local coffee processing factory in Jimma,
and pH of the solution were investigated. The
Ethiopia. It was washed with distilled water,
working solution was agitated on a horizontal
dried at 110℃ for 24 h in a laboratory oven to
shaker at 200 rpm for adsorption equilibrium to
remove moisture, then crushed and sieved to
be achieved. Then each sample was filtered
obtain a particle size < 0.3 mm. Then it was
through 0.45 µm filter paper and prepared for
treated with H3PO4, 85% (w/w) solution in a 1:1
further analysis of dissolved organic matter.
mass proportion, and activated at 550°C for 2 h
Finally, the concentration of HA in the solution
in a muffle furnace (Nabertherm Muffle Furnace
y
was determined using a DR-5000
LT 15/11). After the activation, excess H3PO4
spectrophotometer at a wavelength of 254 nm
was washed with hot distilled water until a pH ≈
nl
(Joseph et al., 2012).
6 was reached (Oliveira et al., 2009 and
Lamine et al., 2014). Chemical activation of the Beside the adsorption experiments, control
biosorbent could increase the anion adsorption experiments with HA using blanks with no
adsorbent material were performed periodically
O
efficiency by creating an external surface of the
adsorbent to be positively charged (Wang et al., and ensured that no HA losses occurred during
2016). the experiments.
2.2. Preparation of Adsorbate Solution The percentage and the amount of HA
adsorbed per unit mass of adsorbent, q t (mg/g),
of
A stock solution of l000 mg/L of HA was
at any time t (min) were computed employing
prepared by dissolving 1 g HA powder in
Eqs. (1) and (2) respectively.
distilled water. The pH of the stock solution
was raised to pH ≈ 11 with 0.1 M NaOH and (1)
ro
solution was adjusted back to pH ≈ 6 with 0.1 M concentration of HA in aqueous phase at time t
or N HCl and filtered through a 0.45 µm filter to (mg/L), qt = the amount of HA adsorbed per unit
remove the undissolved HA powder. The mass of the adsorbent (mg/g), M = dry mass of
concentration of the HA in the clear solution the adsorbent (g), V = initial volume of the
was calculated by a gravimetric method. The adsorption test (L).
stock solution was stored in refrigerator at 4 -
Fo
Where ks is the rate constant for sorption where b (L/mg) is the Langmuir isotherm
kinetics (g mg-1 min-1). The straight-line plot of constant and Co (mg /L) is the initial
t/qt vs t was used to calculate the rate constant, concentration of HA. The shapes of the
ks (Hameed et al., 2007; Oliveira et al., 2007; isotherm are expressed by RL. There are four
Ahmad and Rahman, 2011). probabilities for the RL values: For favorable
y
adsorption (0<RL<1), for unfavorable adsorption
(5) (RL>1), for linear adsorption (RL = 1) and
nl
Where qt is the amount of HA absorbed (mg/g) irreversible adsorption (RL =0) (Haftu et al.,
at a given time (min); kp (mg/ (g. min0.5)) is the 2014).
intra-particle diffusion rate constant; C (mg/g) is 2.9. Freundlich isotherm
the intercept of the intra-particle diffusion
Freundlich’s equation is an empirical model
O
model. The plot of qt versus t0.5 was used to
based on heterogeneous adsorption over
determine the adsorption mechanism.
independent sites and is given by non-linear
2.7. Adsorption Isotherms equation (Eq. 8):
Adsorption isotherm models were used to
of
(8)
evaluate the capacity of CACH to adsorb HA,
the relationship between the amounts of HA where Kf (L/g) related with the total adsorption
adsorbed at equilibrium per unit mass of the capacity and 1/n is dimensionless number
adsorbent and the concentration of HA in the related to the intensity of adsorption
ro
aqueous phase at equilibrium. In thus study, incorporating all the factors affecting adsorption
Langmuir and Freundlich models were tested capacity and intensity.
for equilibrium description. 2.10. Desorption
rP
y
the contact time increased from 20 to 120 min.
The fast adsorption at the initial stage could be 3.4. Effect of HA concentration
because of the presence of a large number of The effect of the HA concentration was
nl
surface sites for adsorption. With increasing investigated by varying from 0.5 to 20 mg/L at
initial contact time in a given mass of equilibrium conditions. At this concentration
adsorbent, the adsorption rate increased and intervals, the amount of HA per unit mass of
O
then gradually reached equilibrium after 60 min. adsorbent was increased from 0.0487 to 1.394
However, in previous studies using similar mg/g, in 100 ml solution. This is in agreement
adsorbents for the removal of 25 - 50 mg/L of with the finding that a more concentrated
Remazol Brilliant Orange 3R dye from water, solution adsorbs better (Mohammed and Firas,
the equilibrium was reached after 5 h (Ahmad 2013). On the contrary, as shown in Fig. 5, the
of
and Rahman, 2011). percentage of adsorption was significantly
3.2. Effect of pH decreased from 97.3 to 69.7% as the
concentration of the HA increased from 0.5 to
The removal efficiency of the adsorbent
20 mg/L. This could be because the sites with
ro
R2 0.998 R2 0.968
y
SSE 0.006 SSE 0.058
nl
Table . 2. The kinetics parameters for adsorption of HA onto CACH
Pseudo-first order Pseudo-second order Intra-particle diffusion
O
Parameter Value Parameter Value Parameter Value
R2 0.961 R2 0.997
ro
rP
Fo
Fig. 1. HA removal efficiency versus contact time of CACH (Co: 10 mg/L, adsorbent dose: 10
g/L, pH: 6, agitation speed: 200rpm)
AJCR: https://escipub.com/american-journal-of-chemical-research/ 6
Dida Gudeta et al., AJCR, 2019;3:14
y
Fig. 2. HA removal efficiency versus pH (Co: 10 mg/L, adsorbent dose: 10 g/L, contact time: 60
nl
min, agitation speed: 200rpm)
O
of
ro
Fig. 3. HA Removal efficiency versus agitation speed versus (C o: 10 mg/L, adsorbent dose: 10g/L,
rP
Fig. 4. HA removal efficiency versus adsorbent dose (C o: 10 mg/L, pH: 6, contact time: 60 min,
agitation speed: 200rpm)
AJCR: https://escipub.com/american-journal-of-chemical-research/ 7
Dida Gudeta et al., AJCR, 2019; 3:14
y
Fig. 5. Adsorption capacity versus initial concentration (pH: 6, contact time: 60 min, agitation
nl
speed: 200 rpm, adsorbent dose: 10 g/ L)
O
of
ro
rP
AJCR: https://escipub.com/american-journal-of-chemical-research/ 8
Dida Gudeta et al., AJCR, 2019; 3:14
to 0.570. This range of RL values indicates that results were reported in other studies (Garcia,
the adsorption process is favorable. 2011; Bouras et al., 2015; Liu et al., 2015;
3.6. Adsorption kinetics Wang et al., 2016; An et al., 2016).
The linear plots of pseudo-first order and 3.7. Desorption
pseudo-second order sorption kinetics constant The adsorption process was significantly
values of Kf, Ks, qe,cal and qe,exp are given in Fig. decreased at high pH values. This indicates
8, Fig. 9 and table 2. The linear plot of pseudo- that HA desorption from the spent CACH can
first order vs has coefficient of take place in alkaline medium. Series of batch
2
determination R > 0.96 and the modeled desorption processes were carried out using
equilibrium capacity is qe,cal (0.941). 100 mL of 0.1, 0.2 and 0.3 M NaOH solution.
Fig. 8 shows the percentage removal of HA
y
Furthermore, in the linear plot of pseudo-
second order kinetics, the plot of t/qt vs t is a desorbed by different concentration of NaOH
straight line with coefficient of determination, R 2 solution. The result showed that desorption
nl
> 0.99. In addition, the modeled equilibrium increased from 70.4 to 90.7%, where the
capacity, qe,cal is 0.972, which is comparable concentration of NAOH increased from 0.1 to
with the experimental equilibrium capacity, 0.3 M. To test the adsorption potential of the
O
qe,exp (0.958) obtained from pseudo-second regenerated adsorbent, three more cycles of
order kinetics. Thus, the kinetics of HA adsorption-desorption were conducted by
adsorption on CACH are well described by a maintaining the previous experimental
pseudo-second order equation, which assumes conditions. The experimental study indicated
that chemisorptions process takes place. that the regenerated material has an average
of
Consequently, the overall rate of removal of HA adsorption capacity of 84.10% and shows the
is controlled by chemical adsorption reactions, reusability of the adsorbent material.
and not by mass transfer limitations. Similar
ro
rP
Fo
Fig.8 . Percentage of HA desorbed from CACH (Co: 10 mg/L, dose: 10 g/L, shaking speed: 200
rpm, pH > 11)
AJCR: https://escipub.com/american-journal-of-chemical-research/ 9
Dida Gudeta et al., AJCR, 2019; 3:14
increased from 1 to 25 g/L, the concentration of 7. Banerjee, S., Chattopadhyaya, MC. (2016)
HA in the aqueous solution was observed to Adsorption characteristics for the removal of a
toxic dye, tartrazine from aqueous solutions by a
reduce from 10 to 1.67 mg/L, which is below
low cost agricultural by-product. Arab. J. Chem.
the WHO guideline value of 2 mg/L for (in press)
dissolved organic matter in drinking water to http://dx.doi.org/10.1016/j.arabjc.2013.1006.1005
prevent formation of disinfection byproducts. .
The adsorption isotherm was most satisfactorily 8. Berhe, S., Ayele, D., Tadesse A, Mulu A (2015)
Adsorption Efficiency of Coffee Husk for
described by a Langmuir isotherm (R2 > 0.99 Removal of Lead(II) from Industrial Effluents:
and SSE = 0.006) and Freundlich models. A Equilibrium and Kinetic Study. International
pseudo-second order kinetic model Journal of scientific and Research Publication,
successfully explains the kinetic data with R2 > 15: 9, ISSN 2250-3153.
y
0.99, which suggests the dominance of 9. Bouras HD, Benturki O, Bouras N, Attou M,
Donnot A, Merlin A, Addoun F, Holtz MD (2015)
chemisorptions process. Desorption processes The use of an agricultural waste material from
nl
was carried out in alkaline medium by using Ziziphus jujuba as a novel adsorbent for humic
NaOH. The study indicated that as the acid removal from aqueous solution. Journal of
concentration of NaOH is increased from 0.1 Molecular Liquids, 211:1039-1046.
to0.3 N, the percentage of desorption was 10. Dabrowski A (1999) Adsorption—its development
O
and application for practical purposes. In:
increased from 70.44 to 90.72%, which Da˛browski A (ed) Studies in surface science and
indicates the regenerability of the adsorbent catalysis. Elsevier, pp 3–68
material. The experimental data demonstrated 11. García, I (2011) Removal of Natural Organic
that CACH could be a potential candidate to be Matter to reduce the presence of
of
used to remove NOM from aqueous solution. Trihalomethanes in drinking water. Doctoral
thesis. School of Chemical Science and
REFERENCES Engineering Royal Institute of Technology,
1. Ahmad, MA. And Rahman, NK. (2011) Stockholm, Sweden.
Equilibrium, kinetics and thermodynamic of 12. Haftu G. Alemayehu, Abiyu K.Burkute and
ro
Remazol Brilliant Orange 3R dye adsorption on Asnake G.Ede (2014) Adsorptive Removal of
coffee husk-based activated carbon. Chemical Pb(II) and Cr(VI) from Wastewater using Acid
Engineering Journal, 170:154–161. Untreated Coffee Husk. Interlink Continental J.
2. Alexandrina Rodrigues, Anto´nio Brito, Peter Environ. Sci. Toxicol. ,1(2), 009-016.
Janknecht, Maria Fernanda Proenc¸and Regina 13. Hameed, BH.,Din, AT., and Ahmad, AL (2007)
rP
Nogueira (2009) Quantification of humic acids in Adsorption of methylene blue onto bamboo-
surface water: effects of divalent cations, pH, and based activated carbon: Kinetics and equilibrium
filtration. J. Environ. Monit.,11:377–382. studies. J.Hazard. Mater., 141:819–825.
3. Ali, I. (2011) The quest for active carbon 14. Heijman, S. G. J., Verliefde, A. R. D.,
adsorbent substitutes, inexpensive adsorbents Cornelissen, E. R., Amy, G., and van Dijk, J. C
for toxic metal ions removal from wastewater. (2007) Influence of natural organic matter (NOM)
Fo
y
Total Environ, 407(6):1990–1997 385.
20. Lin J and Zhan Y (2012) Adsorption of humic 31. Wang L, Han, C., Nadagouda, M., Dionysios D
acid from aqueous solution onto unmodified and (2016) An innovative zinc oxide-coated zeolite
nl
surfactant-modified chitosan/zeolite composites. adsorbent for removal of humic acid. Journal of
Chem Eng J., 200–202:202–213. Hazardous Materials,
21. Liu J, Jingjing Cao, Huan Chen, Dongmei Zhou. //dx.doi.org/10.1016/j.jhazmat.2016.03.07
Adsorptive removal of humic acid from aqueous 32. Wang, J., Lijuan, B., Yanfen, J, Hongrui M,
O
solution by micro and mesoporous covalent xiaolong Y (2014) Removal of Humic acid from
triazine-based framework. Colloid and Surface A: aqueous solution by magnetically separable
Physicochem. Eng. Aspects, 2015, 481:276-282. Polyaniline: Adsorption behavior and
22. Matilainen A, Gjessing ET, Lahtinen T, Hed L, mechanism. Journal of Colloid and Interface
Bhatnagar A, Sillanpa¨a¨M (2011) An overview Science, 430:140-146.
of
of the methods used in the characterization of 33. Yang J, Jia J, Liao J, Wang Y (2004) Removal of
natural organic matter (NOM) in relation to fulvic acid from water electrochemically using
drinking water treatment. Chemosphere, active carbon fiber electrode. Water Res.,
83(11):1431–1442 38(20):4353–4360
23. Matilainen, A., Vepsäläinen, M. and Sillanpää, M 34. Yang X, Shang C, Westerhoff P (2007) Factors
ro
removal from drinking water by membrane Removal of organic pollutants from aqueous
technology. Sep. Purif. Rev., 43:1–61. solution using agricultural wastes: A review.
25. Mohammed Nsaif and Firas Saeed (2013) The Journal of Molecular Liquids, 212:739–762.
Predisposition of Iraqi Rice Husk to Remove 36. Zulfikar, MA., Afrita, S., Wahyuningrum, D.,
Heavy Metals from Aqueous Solutions and Ledyastuti, M (2016) Preparation of Fe3O4-
Capitalized from Waste Residue. Res. J. Appl. chiston hybrid nano-particles used for humic acid
Fo
AJCR: https://escipub.com/american-journal-of-chemical-research/ 11