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WANG XIAOYI
2014/15
EFFICIENCY OF ACTIVATED CARBON
ADSORPTION IN REMOVAL OF SELECTED
PHAMACEUTICALS FROM WATER
Submitted by
Wang Xiaoyi
2014/15
ABSTRACT
This study presents adsorption performance for caffeine and salicylic acid using Granular
activated carbon (GAC) and various Powdered Activated Carbons (PAC) namely Hydrodarco
C, NRS EA 0.5-1.5, SAE 2 and SAE Super. It was found that for caffeine SAE Super
outperformed the rest with much higher removal efficiencies. The data were well fit to
Langmuir isotherm model. As for salicylic acid, desorption occurred when using GAC and SAE
2, resulting in a less efficient adsorption performance. Either Langmuir or Freundlich model
could be fitted. However, Freundlich gave a slightly better fit. With regard to adsorption
kinetics, it was better explained by the second-order kinetic model for all the activated carbons.
Although the activated carbons behaved somewhat differently toward the two pharmaceuticals,
SAE Super can be recommended for its better overall performance compared to the others.
ii
ACKNOWLEDGEMENTS
The author would like to express her sincere gratitude to Assoc. Prof. Tan Soon Keat for giving
his continuous support throughout the whole project. The author appreciates the many learning
opportunities provided and the invaluable experience gained in the accomplishment of this
project.
The author would like to extend her thankfulness to Ms. Zhang Dongqing and Dr. Antoine
Trzcinski for their guidance and help on preparing the resources, conducting the experiments
and analyzing the results. The experiments could not be successful without their kind advice
and selfless efforts.
Last but not least, the author is grateful for the support provided by the staffs of the AEBC
Laboratory. They displayed professionalism and always helped to ensure the availability of the
equipment required for the experiments.
iii
TABLE OF CONTENTS
ABSTRACT ..................................................................................................................... ii
ACKNOWLEDGEMENTS .......................................................................................... iii
LIST OF FIGURES ........................................................................................................ v
LIST OF TABLES ......................................................................................................... vi
CHAPTER 1 INTRODUCTION ................................................................................... 1
1.1 Background ....................................................................................................................... 1
1.1.1 Pharmaceuticals and Personal Care Products (PPCPs) ............................................... 1
1.1.2 Activated Carbon Adsorption ...................................................................................... 1
1.2 Objectives and Scope ........................................................................................................ 3
CHAPTER 2 LITERATURE REVIEW ....................................................................... 5
2.1 Mechanisms for PPCP Removal by Activated Carbon Adsorption ............................. 5
2.1.1 Mathematical Models applied ..................................................................................... 5
2.2 Effectiveness of Activated Carbon for PPCP Removal ................................................. 8
CHAPTER 3 MATERIALS AND METHODOLOGY ............................................. 10
3.1 Materials .......................................................................................................................... 10
3.1.1 Activated Carbons ..................................................................................................... 10
3.1.2 Pharmaceuticals ......................................................................................................... 10
3.2 Methodology .................................................................................................................... 11
3.2.1 Calibration Curve ...................................................................................................... 11
3.2.2 Adsorption Test ......................................................................................................... 12
CHAPTER 4 RESULTS AND DISCUSSIONS ......................................................... 14
4.1. Caffeine ........................................................................................................................... 14
4.1.1 Evolution with Time of Caffeine Concentration ....................................................... 14
4.1.2 Effect of Adsorbent on Removal Rate of 50 mg/L Pharmaceutical Solution............ 17
4.1.3 Langmuir and Freundlich Isotherm Model................................................................ 18
4.1.4 First- and Second-order Kinetic Model ..................................................................... 20
4.2 Salicylic Acid ................................................................................................................... 21
4.2.1 Evolution with Time of Salicylic Acid Concentration .............................................. 21
4.2.2 Effect of Adsorbent on Removal Rate of 50 mg/L Pharmaceutical Solution............ 24
4.2.3 Langmuir and Freundlich Isotherm Model................................................................ 25
4.2.4 First- and Second-order Kinetic Model ..................................................................... 27
CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS .............................. 29
5.1 Conclusions...................................................................................................................... 29
5.2 Recommendations in Future Works ............................................................................. 29
REFERENCES.............................................................................................................. 31
iv
LIST OF FIGURES
v
LIST OF TABLES
Table 1. Specifications and characteristics of activated carbons ............................................. 10
Table 2. Properties of pharmaceuticals .................................................................................... 11
Table 3. Removal efficiencies according to different initial caffeine concentrations .............. 17
Table 4. Isotherm constants of Langmuir and Freundlich models for adsorption onto the five
activated carbons ............................................................................................................. 20
Table 5. Kinetic constants for first- and second-order model for caffeine concentration of 50
mg/L ................................................................................................................................ 21
Table 6. Removal efficiencies according to different initial salicylic acid concentrations ...... 24
Table 7. Isotherm constants of Langmuir and Freundlich models for adsorption onto the five
activated carbons ............................................................................................................. 27
Table 8. Kinetic constants for first- and second-order model for salicylic acid concentration of
50 mg/L ........................................................................................................................... 27
vi
CHAPTER 1 INTRODUCTION
1.1 Background
Although the exact effects of these chemicals on humans and the environment are not yet
known, pharmaceuticals have been detected throughout the environment where at least in some
cases, they have been shown to have a detrimental effect (Alfred et al., 2011). Because PPCPs
can be active at extremely low concentrations, they are of concern for potential ecological and
environmental impacts, and they may concentrate in the food chain and especially affect aquatic
organisms (Weil, 2009). There also exists unpredictable biochemical interactions between
different PPCPs when mixed, and the full effects of the mixtures of low concentrations of
PPCPs are also unknown.
Contemporarily, there is no drinking water standard for PPCP compounds and most drinking
water treatment plants cannot or do not treat for these compounds. The technology needed to
remove PPCPs from wastewater is lagging behind science’s ability to detect them. From recent
studies, caffeine, trimethoprim, sulfamethoxazole, carbamazepine, diclofenac and salicylic acid
were found to be the dominant compounds in wastewater treatment plants (Kosma et al., 2014).
1
processes, can be a more effective and powerful approach for PPCP removal.
The activation process of activated carbons produces it with extensive internal porosity, which
will create large amount of surface area to which contaminants can adsorb. Nowadays, the
application of the activated carbon adsorption method is very broad, with an emphasis on the
micropollutants removal of an aqueous solution.
2
1.2 Objectives and Scope
The primary objective of this experiment is to determine the removal efficiency of
pharmaceuticals using granular and powdered activated carbons and to select the activated
carbon with the best adsorption performance for each pharmaceutical. Five activated carbons
and two pharmaceuticals, Caffeine and Salicylic Acid, were chosen. The introduction and
detailed properties of each adsorbent and pharmaceutical will be shown in Chapter 3.
Before conducting the experiment, a study of the activated carbon adsorption process will be
discussed. Furthermore, in order to analyze the performance of the absorbents in terms of the
surface adsorption mechanisms, the adsorption process and the removal efficiency, some
mathematical models are applied, including Langmuir and Freundlich isotherm models, first-
3
and second-order kinetic models. A review on these models will also be elaborated in the
following chapter.
4
CHAPTER 2 LITERATURE REVIEW
One activated carbon may be very effective in removing a specific compound, but if its
adsorption is highly reversible, it will cause further environmental problems (Cecen & Aktas,
2009). Nevertheless, desorption of activated carbons does not occur often in an aqueous phase
according to many studies before.
5
Igbokwe, 2008). The performance and the adsorption capacity of the activated carbon can then
be predicted from the equilibrium adsorption isotherm (Kumar et al., 2008). Many researchers
including Potgieter (1991) and Ochonogor et al. (2005) have suggested that adsorption isotherm
is very useful in selecting the best activated carbon for adsorption of compounds of interests.
Langmuir and Freundlich isotherm equations are widely used for modeling adsorption data
(Jeppu & Clement, 2012).
𝐾𝐿 𝐶𝑒
𝑞𝑒 =
1 + 𝑎𝐿 𝐶𝑒
where qe is the amount of solute adsorbed onto the activated carbon in equilibrium, Ce is the
solute concentration in water phase at equilibrium, KL and aLare Langmuir equilibrium constant.
This equation can be linearized by plotting Ce/qe against Ce, yielding a straight line with a slope
of aL /KL and an interception point of 1/KL. The Linearized isotherm equation is represented as
𝐶𝑒 𝑎𝐿 𝐶𝑒 1
= +
𝑞𝑒 𝐾𝐿 𝐾𝐿
The Freundlich isotherm is an alternative model to the Langmuir isotherm model. It assumes
heterogeneity of adsorption sites (Desta, 2013). It can be expressed as
𝑞𝑒 = 𝐾𝐹 𝐶𝑒 1⁄𝑛
where qe and Ce mean the same as in the equation of Langmuir model, KF represents the
quantity of adsorbate adsorbed onto activated carbon for a unit equilibrium concentration and
1/n is a Freundlich constant.
Although the constants are specific to test conditions and adsorption type, they are very useful
in the assessment of the performance of different activated carbon adsorbents (Okeola &
Odebunmi, 2010). The degree of nonlinearity between solution concentration and adsorption is
represented by the coefficient n: If n = 1, then adsorption is linear; if n < 1, then adsorption is a
6
chemical process; if n > 1, then adsorption is a physical process (Desta, 2013). The most
common situation is n >1, and the n values within the range of 1–10 represent good adsorption
(Özer & Pirinççi, 2006).
When the Freundlich equation is linearized into logarithmic form for data fitting and parameter
evaluation, the equation becomes:
1
𝑙𝑜𝑔𝑞𝑒 = 𝑙𝑜𝑔𝐾𝐹 + 𝑙𝑜𝑔𝐶𝑒
𝑛
where KF and n are correspond to the adsorption capacity and adsorption intensity, respectively.
Based on the linear plot, Langmuir and Freundlich adsorption constants and correlation
coefficients R2 can be evaluated to determine the most suitable model for the activated carbon
adsorption of each selected pharmaceutical.
𝑑𝑞𝑡
= 𝑘𝑓 (𝑞𝑒 − 𝑞𝑡 )
𝑑𝑡
where qt (mg/g) is the amount of adsorbate absorbed at time t, qe is the adsorption capacity in
equilibrium, and kf is the rate constant for pseudo-first-order model. By integration and applying
the initial conditions qt = 0 at t = 0 and qt = qt at t = t, the following form of the equation is
obtained (Abdullah et al., 2009):
𝑘𝑓 𝑡
log(𝑞𝑒 − 𝑞𝑡 ) = 𝑙𝑜𝑔𝑞𝑒 − ( )
2.303
The adsorption rate constant, kf, and equilibrium adsorption capacity, qe, of the first-order
model can be calculated from the slope and intercept of the plots of log(qe –qt ) against t.
7
𝑑𝑞𝑡
= 𝑘𝑠 (𝑞𝑒 − 𝑞𝑡 )2
𝑑𝑡
where ks is the rate constant of pseudo-second-order model (in g/mg min). After integration of
this equation for the same boundary conditions as above, the equation becomes:
𝑡 1 1
= 2
+ ( )𝑡
𝑞𝑡 (𝑘𝑠 𝑞𝑒 ) 𝑞𝑒
The initial sorption rate, h, at t = 0 can be defined as h=ksqe2. This rate, along with the
equilibrium adsorption capacity, qe, and the second-order rate constants, ks, can be obtained
from the slope and intercept of the plots of t/qt against t.
Lee et al. (2009) indicated that the compounds which are more nonpolar, more hydrophobic,
and have lower solubility should be removed efficiently by carbon adsorption. Moreover,
compounds with lower molecular weight are more efficiently removed by activated carbon
because of increased accessibility to inner pores of the carbon. Besides, the pH of the solution
will also affects adsorption for ionic solutes. Referring to Crittenden et al. (2005), activated
carbon has a nonpolar surface at a neutral pH. Given that water is a polar liquid, nonpolar
organics are more hydrophobic and have lower aqueous solubility. As a result, neutral
hydrophobic compounds will have the strongest affinity to carbon surface, and organic
compounds that are polar, hydrophilic, or charged will not be adsorbed as strongly due to strong
water-adsorbate forces (Crittenden et al., 2005).
However, another parameter that will give obvious negative effect on the adsorption efficiency
is the natural organic matter (NOM), which is usually measured as DOC in the water. The
presence of NOM can reduce the removal efficiency of microconstituents by activated carbon
due to the competition for adsorption sites. To be more specific, the NOM can block the pores
8
within the activated carbon structure, leaving less opportunity for the microconstituents to be
adsorbed (Lee et al., 2009). Westerhoff et al. (2005) also stated that the quantity and
characteristics of DOC in the water is an important parameter that can influence the removal
efficiency for activated carbon.
This adverse impact on the effectiveness of activated carbon can be attributed to the fact that
molecules of both the solute and the solvent have the possibility to be adsorbed onto the
adsorbent and compete for the available surface area of the activated carbon (Lee et al., 2009).
Any presence of other compounds especially the NOM can significantly reduce the removal
efficiency. Therefore, adsorption studies of single solutes in distilled water provide an upper
limit to the adsorbability of a compound.
In real life situation, the concentration of absorbable natural organic matter in wastewater may
be orders of magnitude higher than the concentration of the target PPCPs. The adsorption
capacity and operating life can be dramatically reduced by competitive adsorption between
compounds. As a result, a pretreatment of the wastewater prior to the use of activated carbon
adsorption will be very advantageous. Many studies have found that combined use of activated
carbon with other wastewater treatment processes is highly effective at removing
microconstituents. For example, Verliefde et al. (2007) reported that the combination
application of membrane process with activated carbon adsorption appeared to be very
effective. He also pointed out that nanofiltration (NF) membrane and activated carbon used
together can provide a robust dual barrier for the removal of organic microconstituents, because
the NF membrane is able to effectively remove high- molecular weight polar solutes, while
activated carbon is more effective at removing non-polar solutes.
Overall, the use of activated carbon will yield significant benefits in wastewater effluent quality
(Oulton et al., 2010). Activated carbon can provide an additional barrier in a treatment
procedure that, when combined with other effective processes, should offer a multi-barrier and a
more effective approach for PPCP removal (Lee et al., 2009). Therefore, the selection of
activated carbon with the best performance is very important in the design and operational
strategies to maximize PPCP removal.
9
CHAPTER 3 MATERIALS AND METHODOLOGY
3.1 Materials
d99=150 μm
3.1.2 Pharmaceuticals
The pharmaceuticals selected in this experiment are caffeine and salicylic acid, which were both
purchased from Sigma-Aldrich. A summary of their properties is shown in Table 2.
10
Pharmaceutical Formula Use Mol. Weight log Kow Solubility
(g/mol) (g/L)
Caffeine C8H10N4O2 Stimulant 194.19 -0.07 20
Salicylic Acid C7H6O3 Analgesic 138.12 2.26 2
Table 2. Properties of pharmaceuticals
The octanol water partition-coefficient (Kow) is the ratio of a chemical’s concentration in the
octanol phase to its concentration in the aqueous phase. It can be used in measuring how
hydrophilic or hydrophobic a chemical substance is. When comparing the Kow values of two
solutes, the compound with higher Kow number could be considered more hydrophobic (Mitra,
2004). The polar character of a compound can also be described by this constant, although there
is not a direct relation between Kow and the charge distribution in the molecule (Moldoveanu &
David, 2014). Frequently, molecules with low values of Kow are indicated as polar. Moreover,
caffeine is moderately soluble in water at room temperature, while salicylic acid is poorly
soluble.
3.2 Methodology
Their nearly one correlation coefficient R2 value indicates an almost perfect positive linear
relationship between the chemical concentration and the machine absorbance. It is, thus,
acceptable to be further used to determine the samples’ concentration.
11
Caffeine Calibration Curve
1.6
1.4 R² = 0.9983
Absorbance 1.2
1
0.8
Caffeine
0.6
0.4 Linear (Caffeine)
0.2
0
0 10 20 30
Conc. (mg/L)
1
0.8 Salicylic Acid
0.6
0.4 Linear (Salicylic
Acid)
0.2
0
0 10 20 30
Conc. (mg/L)
12
were performed with the help of a magnetic stirrer at speed of 350 rpm, ensuring adequacy
contact between the activated carbon and the solution. Due to the fact that the pharmaceutical
solution was prepared using DI water and the objective of this experiment was to test the
adsorbability of activated carbons under different pharmaceutical concentrations, the pH value
was not controlled. The experiment was conducted at room temperature around 25◦C. Figure 3
below shows the experiment setup for the adsorption test.
The adsorption tests were carried out for 24 hours to ensure that the adsorption equilibrium had
been attained. Parafilm was used to cover and seal the beakers to prevent evaporation during the
experiment. Samples were collected from the beakers at 0 min, 10 min, 30 min, 45 min, 1 hour,
2 hour, 3 hour, 6 hour and 24 hour, respectively. They were then filtered through a 0.45 microns
filter using a syringe into a 2ml Eppendorf tube. The concentration of all the samples was
measured using UV spectrophotometry eventually. In order to calculate the coefficient of
variance (COV) to determine the human error range, ten identical samples were taken from the
beaker with 50 mg/L pharmaceutical concentration at 24 hour.
13
CHAPTER 4 RESULTS AND DISCUSSION
4.1. Caffeine
30
40 mg/L
25
25 mg/L
20
15 10 mg/L
10 5 mg/L
5 1 mg/L
0
0 5 10 15 20 25 30
Time (hr)
Figure 4. Evolution with time of caffeine concentration using 100 mg/L GAC
14
Hydrodarco C (Caffeine)
50
45
40
35
50 mg/L
Conc. (mg/L)
30
40 mg/L
25
25 mg/L
20
10 mg/L
15
5 mg/L
10
1 mg/L
5
0
0 5 10 15 20 25 30
Time (hr)
Figure 5. Evolution with time of caffeine concentration using 100 mg/L Hydrodarco C
30
40 mg/L
25
25 mg/L
20
10 mg/L
15
5 mg/L
10
1 mg/L
5
0
0 5 10 15 20 25 30
Time (hr)
Figure 6. Evolution with time of caffeine concentration using 100 mg/L NRS EA 0.5-1.5
15
SAE 2 (Caffeine)
50
40
50 mg/L
Conc. (mg/L)
30
40 mg/L
25 mg/L
20
10 mg/L
10 5 mg/L
1 mg/L
0
0 5 10 15 20 25 30
Time (hr)
Figure 7. Evolution with time of caffeine concentration using 100 mg/L SAE 2
30
40 mg/L
25
25 mg/L
20
15 10 mg/L
10 5 mg/L
5 1 mg/L
0
0 5 10 15 20 25 30
Time (hr)
Figure 8. Evolution with time of caffeine concentration using 100 mg/L SAE Super
It was observed that almost all activated carbons, except for NRS carbon, reached equilibrium
within half an hour. For NRS carbon, the caffeine concentration gradually decreased from the
beginning until 24 hour. Another observation was that SAE Super had the sharpest drop and
performed the most of its adsorption within 10 minutes. Also, it was seen that the
pharmaceutical concentration went up a bit using Hydrodarco C and SAE Super after 6 hour
and 3 hour, respectively. However, the increase was so small that it can be negligible.
16
Moreover, the concentration in the control sample remained the same at the beginning and the
end, indicating that the change in the concentration of pharmaceutical was due to the presence
of the activated carbons.
With regard to the removal efficiency at equilibrium, a summary was made in Table 3. At
concentration lower than 10 mg/L, most of the removal efficiencies were nearly 100%.
However, the values at equilibrium were so small that the UV spectrophotometer was not
efficient enough to determine the concentration. Therefore, it was more reasonable to analyze
their removal efficiency at higher concentrations. It was found that SAE Super outperformed the
others with the highest efficiency achieved in each of the concentration. It was in line with the
literature that higher removals are obtained with increasing total surface area of the activated
carbons.
17
Caffeine 50 mg/L
50
45
40
35
Conc. (mg/L)
30 Granular
25 Hydrodarco C
20 NRS Carbon
15
SAE 2
10
SAE Super
5
0
0 5 10 15 20 25 30
Time (hr)
Figure 9. Evolution with time of initial caffeine concentration of 50 mg/L for the total five activated
carbons
18
Langmuir (Caffeine)
600
500
400
Granular
Ce/qe
300 Hydrodarco
NRS
200
SAE Super
100 SAE 2
0
0 10 20 30 40 50
Ce
Freundlich (Caffeine)
0
-2 -1.5 -1 -0.5 0 0.5 1 1.5 2
-0.5
-1 Granular
Hydrodarco
log qe
-1.5
NRS
SAE 2
-2
SAE Super
-2.5
-3
log Ce
Figure 11. Freundlich isotherm model for caffeine
19
Model GAC Hydrodarco NRS SAE 2 SAE Super
Langmuir
KL -0.772 -0.323 0.042 0.250 0.297
aL -6.396 -3.936 0.212 1.613 1.347
qe(mg/g) 145 92 186 168 214
R2 0.994 0.991 0.879 0.994 0.991
Freundlich
KF 0.060 0.048 0.044 0.062 0.079
n 3.541 4.871 2.334 3.050 2.229
R2 0.727 0.633 0.528 0.581 0.622
Table 4. Isotherm constants of Langmuir and Freundlich models for adsorption onto the five
activated carbons
20
R2 0.999 0.999 0.994 1 1
Table 5. Kinetic constants for first- and second-order model for caffeine concentration of 50 mg/L
25 mg/L
30
25 10 mg/L
20 5 mg/L
15
1 mg/L
10
5
0
0 5 10 15 20 25 30
Time (hr)
Figure 12. Evolution with time of salicylic acid concentration using 100 mg/L GAC
21
Hydrodarco C (Salicylic Acid)
60
50
40 50 mg/L
Conc. (mg/L)
40 mg/L
30
25 mg/L
20 10 mg/L
5 mg/L
10 1 mg/L
0
0 5 10 15 20 25 30
Time (hr)
Figure 13. Evolution with time of salicylic acid concentration using 100 mg/L Hydrodarco C
25 40 mg/L
20 25 mg/L
15 10 mg/L
10 5 mg/L
5 1 mg/L
0
0 5 10 15 20 25 30
Time (hr)
Figure 14. Evolution with time of salicylic acid concentration using 100 mg/L NRS EA 0.5-1.5
22
SAE 2 (Salicylic Acid)
50
45
40
35
50 mg/L
Conc. (mg/L)
30
40 mg/L
25
25 mg/L
20
10 mg/L
15
5 mg/L
10
1 mg/L
5
0
0 5 10 15 20 25 30
Time (hr)
Figure 15. Evolution with time of salicylic acid concentration using 100 mg/L SAE 2
25 40 mg/L
20 25 mg/L
15 10 mg/L
10 5 mg/L
5 1 mg/L
0
-5 0 5 10 15 20 25 30
Time (hr)
Figure 16. Evolution with time of salicylic acid concentration using 100 mg/L SAE Super
A summary of the removal efficiency is shown in Table 6. From the table, it was found that
GAC and SAE 2 had a better adsorption performance. However, they experienced desorption
after 3 hours with a desorption percentage of about 50%, meaning that they did not reach an
equilibrium and actually had a much lower removal efficiency considering the desorption. Even
though it was stated in the literature that desorption of activated carbons does not occur often in
23
an aqueous phase, if it occurred, it could affect the overall removal efficiency to some extent.
Thus, in this case, it was shown that a slightly larger surface area of an activated carbon can
result in a higher pharmaceutical removal; the removal efficiency will also depend on several
other factors; desorption can have a significant impact on the overall adsorption performance.
24
Salicylic Acid 50 mg/L
60
50
40
Conc. (mg/L)
Granular
30 Hydrodarco C
NRS Carbon
20
SAE 2
10 SAE Super
0
0 5 10 15 20 25 30
Time (hr)
Figure 17. Evolution with time of initial salicylic acid concentration of 50 mg/L for the total five
activated carbons
25
Langmuir (Salicylic Acid)
250
200
150 Granular
Ce/qe
Hydrodarco
100 NRS
SAE 2
50 SAE Super
0
0 10 20 30 40 50
Ce
-0.5
Granular
-1
Hydrodarco
log qe
NRS
-1.5
SAE 2
SAE Super
-2
-2.5
log Ce
26
Model Granular Hydrodarco NRS SAE 2 SAE Super
Langmuir
KL 0.026 0.482 0.015 0.046 0.023
aL 0.070 3.070 0.071 0.124 0.118
qe (mg/g) 225 178 164 265 150
R2 0.913 0.922 0.900 0.877 0.933
Freundlich
KF 0.025 0.049 0.017 0.041 0.022
n 1.335 3.484 1.437 1.523 1.615
R2 0.988 0.939 0.910 0.936 0.934
Table 7. Isotherm constants of Langmuir and Freundlich models for adsorption onto the five
activated carbons
27
Overall, the activated carbons performed differently toward the two pharmaceuticals. This may
be probably due to the characteristics of the pharmaceuticals. According to the literatures,
compounds with lower molecular weight and lower solubility and which are more nonpolar and
more hydrophobic should be removed efficiently by carbon adsorption. The molecular weight
of caffeine and salicylic acid can be deemed as similar and salicylic acid is less soluble in water.
Also, based on the value of Kow, salicylic acid is less polar and more hydrophobic compared to
caffeine. It was observed that especially at higher pharmaceutical concentrations salicylic acid
was adsorbed more by most of the activated carbons, which in line with the literatures.
However, desorption occurred significantly for salicylic acid especially using GAC and SAE 2,
because the adsorption was a more physical process and hence not very stable. It was also found
that SAE Super seemed to be more efficient in adsorbing caffeine. Hence, there is no simple
relationship between the characteristic of pharmaceuticals such as hydrophobicity, solubility
and polarity and the adsorption affinity toward the adsorbent.
28
CHAPTER 5 CONCLUSIONS AND
RECOMMENDATIONS
5.1 Conclusions
Results from the experiment showed that activated carbons are able to greatly reduce the
pharmaceutical concentrations in water. Analysis of the five activated carbons for a specific
pharmaceutical adsorption provided evidences that the total surface area of the activated carbon
was a very essential characteristic in determining the adsorption efficiency. SAE Super was
found to be the most efficient activated carbon in removing caffeine. Salicylic acid was
removed more by GAC and SAE 2, but desorption affected their final removals dramatically,
leading to a better selection of NRS carbon and SAE Super to treat salicylic acid.
In addition, Langmuir isotherm model was the best fit for caffeine, while Freundlich model was
better for salicylic acid. This suggested that the adsorption of caffeine was a monolayer
chemisorption process and with n value greater than 1 in Freundlich model, a multilayer
physical process was indicated for the adsorption of salicylic acid. In combination with the
observation that more desorption appeared when treating salicylic acid, it is evident that the
physical adsorption process was usually unstable and reversible.
Through analysis of the adsorption kinetics, it can be concluded that for all of the activated
carbons and the pharmaceuticals the second-order kinetic model was the perfect fit.
Furthermore, SAE Super had the fastest initial sorption rate with the highest h value.
In conclusion, based on the results and analysis, SAE Super was considered as the best activated
carbon in removing caffeine and salicylic acid in water. Although no simple relationship
between the properties of the activated carbon and the pharmaceutical and the removal
efficiency can be stated in judging the best adsorbent, their properties still have important
influences on their adsorption performances. Typically, the activated carbon with larger total
surface area will perform better.
29
other compounds. However, in reality, the wastewater contains many different contaminants,
which will affect the activated carbons’ performance in several aspects. Because this activated
carbon adsorption method can be further applied to a membrane bioreactor (MBR) to enhance
the overall performance of the treatment process, conducting this experiment with MBR
effluent instead of DI water will be worth doing in next experiment. Specifically, it is known
that some natural organic matter (NOM) or soluble microbial products (SMP) in the effluent
may affect the activated carbon’s performance. Hence, in future work, an experiment can be
designed to determine whether there is any competition between SMP and the pharmaceuticals
as well as to analyze the adsorption efficiency with the presence of other compounds.
30
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