Tez
-
Upload
ayse-celik -
Category
Engineering
-
view
354 -
download
5
description
Transcript of Tez
GRADUATION THESIS
REMOVAL OF IBUPROFEN FROM AQUEOUS SOLUTIONS BY ADSORPTION ON LENTIL AND RICE HUSK
Supervisor: Prof. Dr. Belma KIN ÖZBEK
10051042 Esra ALTUN11051803 Ayşe ÇELİK
CONTENTS
Materials and Methods
Conclusions
Results and Discussions
Adsorption
Industrial Wastewater Treatment
Pharmaceuticals
PHARMACEUTICALS
These excreted wastes can easily metabolise by microorganisms in sewage treatment plants.
Many human and veterinary pharmaceuticals aren’t completely metabolized and excreted unchanged via urine
and feces.
Pharmaceuticals are organic compounds that are signing anthropogenic origin, consumed, produced and/or excreted
by humans and animals, or used in household products.
Consume of Pharmaceutical in Public
Years0
20
40
60
80
100
120
140
160
180
30%
153%
1994-2002 2002-2012
% C
hang
e
IBUPROFEN
Acidic drugs are ionic in neutral pH, which makes them an interesting compound to study.
Ibuprofen is a non-steroidal acidic anti-inflammatory drug which is largely used throughout the world (Lischman et al.,
2006).
Melting Point; 77-78 °C
Boiling Point ;157 °C (4 mmHg)
Storage T ;-20°C Freezer
Water Solubulity; Insoluble
UV Spectrum;
220nm
Colourless, Crystalline
Steam Pressure;
1.86.10-4(mm Hg)
pKa; 4.9
Henry Laws Constant 1.50.10-7
(atm.m3/mole)
INDUSTRIAL WASTEWATER TREATMENT
Industrial wastewater treatment includes the mechanisms and processes used to treat waters which have been contaminated in some way by anthropogenic industrial or commercial activities prior to its release into the environment.
In the developed world, recent trends have been to minimize or recycle waste inside the production process.
Sources of Industrial Wastewater;Iron and steel industryMines and quarriesFood industryComplex organic chemicals industry
Solid remo
val
• Most solids can be removed by using simple sedimentation techniques with the solids recovered as sludge or slurry.
Oil and
grease
removal
• Skimming devices can recover many oils from open water surfaces.
Removal of biodegrada
ble organ
ics
• Biodegradable organic materials can be removed using extended usual wastewater treatment processes such as trickling filter or activated sludge.
Activated
sludge
process
• Activated sludge is a biochemical process for treating sewage and industrial wastewater by air (or oxygen) and microorganisms.
Treatment of acids and
alkalies
• Alkalis and acids can usually be neutralized under controlled conditions. Neutralization frequently produces sediment that will require treatment as a solid residue that may also be toxic.
Treatment of toxic
materials
• Toxic materials (many organic materials, metals, acids, alkalis and non-metallic elements) are generally resistant to biological processes unless very dilute. Metals can often be precipitated out by changing the pH or by treatment with other chemicals.
Trickling filter
process
• A trickling filter consists of a bed of rocks, slag, gravel, plastic media or peat moss. The process involves adsorption of organic compounds in the wastewater by the microbial slime layer covering the bed media. Aerobic conditions are continued by forced air flowing through the bed.
ADSORPTION
Adsorption is the adhesion of molecules, atoms or ions from a dissolved solid, liquid or gas to a surface.
Adsorption is the binding of molecules or particles to a surface. It must be distinguished from absorption by the filling of pores in a solid. The surface binding is generally weak and reversible.
Types of Adsorption;Physical adsorption or physisorptionChemical adsorption or chemisorption
Physisorption
Low heat of adsorption
Van der Waal's forces
Takes place at low temperature
Its reversible
Related to the ease of liquefaction of the gas
Not very specific
It forms multi-molecular layers
No requirement of activation energy
Chemisorption
High heat of adsorption
Chemical bond forces
Takes place at high temperature
It is irreversible
Extent of adsorption is generally not related to liquefaction of the gas
Highly specific
Forms monomolecular layers
Requires activation energy
• Schematic representation of the adsorption and possible subsequent reaction of carbon monoxide on various solid surfaces
Most Important Adsorbents
Adsorbents are usually used in the form of rods, spherical pellets, monoliths or moldings, with hydrodynamic diameters between 10 and 0.5 mm.
Adsorbents are mostly microporous and high specific surface materials (200 - 2000 m2/g)
The adsorbent is the separating agent which is used to express the difference between molecules in a mixture: adsorption equilibrium or kinetics.
Activated carbon
Silica gel
Alumina
Alumino silicates
ZeoliteMordenite
Clays
Carbon nanotubes
Red mud
Adsorbents
Factors Affecting Adsorption
• Surface area of adsorbent• Particle size of adsorbent• Contact time or residence time• Solubility of solute (adsorbate) in liquid (wastewater)• Affinity of the solute for the adsorbent (carbon)• Number of carbon atoms• Size of the molecule with respect to size of the pores• Degree of ionization of the adsorbate molecule• pH
Adsorption IsotermsNAME ISOTHERM EQUATION APPLICABILITY
Langmuir Chemisorption and physical adsorption
Freundlich Chemisorption and physical adsorption at low coverages
Temkin Chemisorption
Langmuir isotherm vs. Freundlich isotherm
Theoretical justification
Assumes reversible adsorbtion
and desorption
Represents well data for
single components
Represents an empirical model
No assumption
Used also for mixtures of compounds
LANGMUIR FREUNDLICH
Temkin Isotherm
Temkin isotherm comprises a factor that explicitly taking into the account of adsorbent–adsorbate interactions.
The model assumes that heat of adsorption of all molecules in the layer would decrease linearly rather than logarithmic with coverage by ignoring the extremely low and large value of concentrations (Tempkin et al., 1940; Aharoni et al., 1977).
As denoted in the equation, its derivation is characterized by a uniform distribution of binding energies.
Adsorption Kinetics
Pseudo-first order rate model
Pseudo-second order rate model
Intraparticle diffusion model
Elovich kinetic model
MATERIALS and METHODS
MATERİALSIbuprofen• The chosen pharmaceutical ibuprofen was supplied from a
pharmaceutical factory and used as the single component adsorbate in the present study. The concentration of ibuprofen was used as 30 mg/L
Rice Husk• Rice husk was supplied from Güven Rice Factory in Osmancık
Çorum. Rice husk’s outer surface area is around 4000 m2/ m3. The moisture of rice husk was obtained 7% in the present study.
Lentil Husk• Lentil husk was supplied from Arpacioglu lentil production
factory in Şehitkamil in Gaziantep. The moisture of lentil husk was obtained 1%.
APARATUS
IKA KS 4000 IC Shaker
Scale
SHIMADZU UV-1800
spectrofotometer
Eutech pH meter
Syringe Filter
Experimental MethodsSeveral amounts of adsorbent were poured to 100 mL water and taken to the shaker for a good mixing for an hour.
3 mg of ibuprofen was dissolved in 5 mL methanol and it was added into the solution.
pH of the solutions were adjusted before the adsorption experiments.
When the adsorption started, samples were taken in defined time intervals.
Experimental MethodsDuring the adsorption experiments, the residual of the ibuprofen amounts were examined for a time interval.
For determination ibuprofen amounts, the adsorbent solution was filtrated by using the syringe filter and absorbance values were measured.
By using the calibration curve, the concentration values were calculated from absorbance values.
In the meantime, adsorbent solution without ibuprofen was used as blank solution at defined pH and temperature values.
The absorbance values of the blank solution were measured.
Calibration curve of ibuprofen
σ=0.00384
RESULTS and
DISCUSSIONS
pH Effect on Ibuprofen Adsorption Concentrations (mg/L)
Time (h) pH 3 pH 4 pH 5
0 30.00 30.00 30.00
1 21.92 24.59 29.19
2 16.55 22.38 25.36
3 16.36 20.95 22.76
4 15.84 20.95 21.89
5 15.52 20.63 21.27
6 15.00 18.98 21.09
• The ibuprofen adsorption was examined at various pH values such as 3, 4 and 5, respectively.
• The adsorbent concentration was 10 g/L and ibuprofen concentration was 30 mg/L at temperature of 25 0C.
• The adsorption percentages for pH 3, 4 and 5 were obtained as 50.0 %, 36.7% and 29.7%, respectively.
pH Effects on Ibuprofen Adsorption
0 1 2 3 4 5 6 70
5
10
15
20
25
30
35
pH 3 pH 4 pH 5
Time (h)
Conc
entr
ation
(mg/
L)
Rice Husk Concentration Effect on Ibuprofen Adsorption
• The ibuprofen adsorption was examined at various adsorbent concentration values such as 5, 10, 20 and 40g/L, respectively.
• The pH value was 3 and ibuprofen concentration was 30 mg/L at temperature of 25 0C.
• The adsorption percentages for adsorbent concentrations 5, 10, 20 and 40g/L were obtained as 10.17 %, 50.00 %, 53.73 % and 51.99 %, respectively.
Concentrations (mg/L)
Time (h) 5 g/L 10 g/L 20 g/L 40 g/L
0 30.00 30.00 30.00 30.00
1 27.97 21.92 19.28 16.51
2 27.46 16.55 16.51 15.95
3 27.27 16.36 14.41 15.32
4 27.27 15.84 14.21 14.96
5 26.95 15.52 13.88 14.82
6 26.95 15.00 13.88 14.40
Rice Husk Concentration Effect on Ibuprofen Adsorption
0 1 2 3 4 5 6 70
5
10
15
20
25
30
35
5 g/L 10 g/L 20 g/L 40 g/L
Time (h)
Conc
entr
ation
(mg/
L)
Temperature Effect on Ibuprofen Adsorption
Concentrations (mg/L)
Time (h) 25 ºC 30 ºC 40 ºC
0 30.00 30.00 30.00
1 19.28 18.96 19.49
2 16.51 16.83 17.36
3 14.41 14.70 15.23
4 14.21 14.17 14.90
5 13.88 13.84 14.70
6 13.88 13.84 14.57
• Ibuprofen adsorption was examined for various temperatures such as 25, 30 and 40 ºC, respectively.
• At pH 3, ibuprofen concentration was 30 mg/L and rice husk concentration was 20 g/L.
• The adsorption percentages for temperatures 25, 30 and 40 ºC were obtained as 53.73%, 53.88% and 51.44%, respectively.
Temperature Effect on Ibuprofen Adsorption
0 1 2 3 4 5 6 70.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
25 C 30 C 40 C
Time (h)
Conc
entr
ation
(mg/
L)
Ibuprofen Adsorption onto Lentil Husk for Optimum Conditions
• The optimum conditions were 20 g/ L adsorbent, 30 mg/ L ibuprofen, pH 3 and room temperature.
• The removal percentage of ibuprofen was 26.43%.
Time (h) Concentration (mg/ L)
0 30.00
1 26.45
2 24.85
3 23.67
4 22.84
5 22.49
6 22.07
0 1 2 3 4 5 6 70.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
Time (h)
Conc
entr
ation
(mg/
L)
Optimum data of adsorption onto rice husk
• From 6 hours’ experiments, optimum conditions were; pH 3, room temperature (25 ± 2 ºC), 180 rpm shaking velocity and 20 g/L adsorbent concentration.
Time (h) Adsorbed Concentration (mg/L) qt (mg/g)
0 0.00 0.00
1 10.72 0.54
2 13.49 0.67
3 15.59 0.78
4 15.79 0.79
5 16.12 0.81
6 16.12 0.81
Adsorption capacities (qe) of 20 g/L rice husk against time
0 1 2 3 4 5 6 70.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
Time (h)
qt (m
g/g)
Adsorption Isotherms
Langmuir Isotherm• Ce was adsorbed ibuprofen concentration and qe was removed ibuprofen
per unit mass of adsorbent.
Time (h) Ce = C1-C2 (mg /L) Ce/ qe (g/L)
1 10.72 13.31
2 13.49 16.73
3 15.59 19.35
4 15.79 19.59
5 16.12 19.90
Langmuir Isotherm
10.50 11.50 12.50 13.50 14.50 15.50 16.5013.00
14.00
15.00
16.00
17.00
18.00
19.00
20.00f(x) = 1.23220894398028 x + 0.103447986577191R² = 0.999793524862616
Ce (mg/L)
Ce/q
(g/L
)
Langmuir Isotherm
• KL is the adsorption equilibrium constant which is related to the energy of adsorption (L/mg).
• qmax (mg/g) is the maximum adsorption capacity.
Langmuir Equation qmax (mg/g) KL (L/mg) R2 σ
0.812 11.92 0.9998 0.0471
Freundlich Isotherm
Time (h) Ln qt Ln Ce
1 -0.62 2.37
2 -0.39 2.60
3 -0.25 2.75
4 -0.24 2.76
5 -0.22 2.78
Freundlich Isotherm
2.35 2.40 2.45 2.50 2.55 2.60 2.65 2.70 2.75 2.80 2.85
-0.70
-0.60
-0.50
-0.40
-0.30
-0.20
-0.10
0.00
f(x) = 0.999999999999994 x − 2.99573227355398R² = 1
ln Ce
ln q
t
Freundlich Isotherm
• K (mg/g) (L/g)1/n is the Freundlich constant related to sorption capacity
• n is the heterogeneity factor.
Freundlich Equation KF (mg.L/g2) n R2 σ
Ln qe= -2.9957+ln Ce 0.05 1 1 0.0029
Temkin Isotherm
Time (h) qt (mg/g) Ln Ce
1 0.54 2.37
2 0.67 2.60
3 0.78 2.75
4 0.79 2.76
5 0.81 2.78
Temkin Isotherm
2.35 2.40 2.45 2.50 2.55 2.60 2.65 2.70 2.75 2.80 2.850.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
f(x) = 0.661685346044178 x − 1.03771607722747R² = 0.997567970268554
ln Ce
qt (m
g/g)
Temkin Isotherm• q• R is Gas constant (J/moleK).• A and B are Temkin constants.• B is written instead of RT/b.
Temkin Equation A B R2 σ
0.208 0.6617 0.9976 0.0102
Adsorption Kinetics
Pseudo first order kinetic model
• qe is the adsorbed ibuprofen onto unit adsorbent in equilibrium (mg/g).
• qt is the adsorbed ibuprofen onto unit adsorbent at any time (mg/g).
• K1,ad is the pseudo first order kinetic constant (h-1)Time (h) log(qe-qt)
0 -0.09
1 -0.57
2 -0.88
3 -1.58
4 -1.78
Pseudo first order kinetic model0 0.5 1 1.5 2 2.5 3 3.5 4
-2.00
-1.80
-1.60
-1.40
-1.20
-1.00
-0.80
-0.60
-0.40
-0.20
0.00
f(x) = − 0.439111602544881 x − 0.103230394638158R² = 0.97866983421009
time (h)
log
(qe-
qt)
Pseudo First Order Kinetic Model Equation qe (mg/g) qe,h (mg/g) k1,ad(h-1) R2 σ
Log(qe-qt)= -0.439t-0.1032 0.810 0.788 1.011 0.9787 0.1197
Pseudo second order kinetic model
Time (h) t/qt (g.h/mg)
1 1.87
2 2.97
3 3.85
4 5.07
5 6.20
6 7.441 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
f(x) = 1.10950244985367 x + 0.68251340179705R² = 0.997652520751861
time (h)
t/qt
(g.h
/mg)
Pseudo second order kinetic model
Pseudo Second Order Kinetic Model Equation
qe
(mg/g)
qe,h
(mg/g)k2,ad(h-1) R2 σ
t/qt= 1.1095t+0.6825 0.810 0.901 1.803 0.9977 0.1119
Elovich kinetic model data
• α is the adsorption kinetic at the beginning (mg/g.h) • β is the adsorption constant during the experiments
(g/mg).
qt (mg/g) ln t
0.54 0.00
0.67 0.69
0.78 1.10
0.79 1.39
0.81 1.61
Elovich kinetic model
0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 1.800.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
f(x) = 0.174739376638871 x + 0.5497925985984R² = 0.956084959836048
ln t
qt (m
g/g)
Elovich Kinetic Model Equation α (mg/g.h) β (g/mg) R2 σ
qt= 0.1747 ln t+0.5498 4.065 5.724 0.9561 0.0257
Intraparticle diffusion kinetic model
• ki is the intraparticle diffusion model kinetic constant (mg/g.h0.5)
• Ci is a constant that gives information about the layer thickness between the adsorbent and adsorbate.
qt (mg/g) t0.5 (h0.5)
0.54 1.00
0.67 1.41
0.78 1.73
0.79 2.00
0.81 2.24
Intraparticle diffusion kinetic model
1 1.5 20.5
0.6
0.7
0.8
0.9
f(x) = 0.221883958415373 x + 0.345124246757174R² = 0.903963037900642
f(x) = NaN x + NaNR² = 0
t1/2 (h1/2)
qt (m
g/g)
Intraparticle Diffusion Model Equation
ki (mg/g.h0.5) Ci (mg/g) R2 σ
qt= 0.2219 t0.5 +0.3451 0.2219 0.3451 0.904 0.0387
The comparison of studies about removal of Ibuprofen by adsorption
Reference Adsorbent
Parameters
Adsorbent Cons.(g/L)
Working Cons. (g/L)
Time (hour) Temperature (°C)
pH Isotherm Model % Adsorption
The present study, 2014
Rice husk 20 0.03 2 25 3 Freundlich 53.8 %
The present study, 2014
Lentil husk 20 0.03 2 25 3 26.32 %
Guedidi et al. 2014
Activated carbon cloth 0.1 0.01 16 25, 40, 55 3, 7 FreundlichLangmuir
23 %
Connors et al. 2013
Filtrasorb 200 GAC, PWA PAC, Purolite A530E, Amberlite XAD-4, Amberlite
XAD-7, and Optipore L-493
0.0006 0.015 24 25 4, 5, 7 FreundlichLangmuir
96 %
Behera et al. 2012
Kaolinite, montmorillonite,
goethite, and activated carbon
1 0.06 6 25 3-11 AC (90 %)Diğerleri
(10 %)
Jodeh, 2012 Agriculture soil 20 0.05 2 25 1-4 Freundlich 88 %
Staiti, 2012 Soil 0.05 (20-50).10-6 10,30,60,120,180 min
15,25,35 1.5-7 FreundlichLangmuir
92 %
The comparison of studies about removal of Ibuprofen by adsorption
Reference Adsorbent
ParametersAdsorbent Cons.(g/L)
Working Cons. (g/L)
Time (hour) Temperature (°C)
pH Isotherm Model % Adsorption
Almendra,
2011
Activated carbon
F400
0.01 100.10-6 2-24 23 4,5-8 Langmuir
Freundlich
80 %
Deng, 2010 Powdered
activated carbon
0.0005-0.07 100.10-6 2, 5, 10, 15,
30, 60 and
120 min
25 4-7 Freundlich 90 %
Serrano et
al. 2010
Activated sludge 0.01 0.1-1 48 25 2.5
Freundlich 90 %
Bui et al.
2009
SBA-15 1-2 0.1 24 25 3 Langmuir
Freundlich
94.3 %
Xu et al.
2009
Agricultural soils 0.001g/kg (0.5,1,2.5,5,
10).10-3
24 20 Freundlich 98 %
Säfström,
2008
Powdered
activated carbon
0.05 25.10-6 2 25 2.6 92 %
Kabak et al.
2008
Activated sludge 3 0.01-0.05 160min 25 7.5-8.3 Freundlich 79 %
CONCLUSIONS• In previous study, ibuprofen which is mostly used by human being
was chosen as pollutant because of its common usage.• For removing ibuprofen, rice husk and lentil husk were chosen as
bioadsorbent for the adsorption studies, since they were agricultural residues and they weren’t harmful to the environment and they are low-cost materials .
• Adsorption capacity was dependent on adsorbent amount, contact time and pH value.
• To achieve these goals, different concentration, pH and temperature values were studied.
• As a result of 6 hours experiments, optimum conditions were; pH 3, room temperature (25 ± 2 ºC), 180 rpm shaking velocity and 20 g/L adsorbent concentration.
CONCLUSIONS• When ibuprofen adsorption was examined at various pH values (3, 4
and 5), the most efficient pH value was 3 for ibuprofen adsorption with a percentage of 50.
• When ibuprofen adsorption was examined at various adsorbent concentrations (5, 10, 20 and 40g/L), the most efficient value was 20g/L with a percentage of 53.73.
• When ibuprofen adsorption was examined at various temperatures (25, 30, 40 ºC), the adsorption percentages for temperatures were 53.73%, 53.88% and 51.44%, respectively.
• For optimum conditions adsorption percentage of ibuprofen onto lentil husk was 26.43%.
• For optimum conditions adsorption isotherms (Langmuir isotherm, Freundlich isotherm and Temkin isotherm) and adsorption kinetics (Pseudo first order kinetic model, Pseudo second order kinetic model, Elovich kinetic model and Intraparticle diffusion model) were studied.
CONCLUSIONS• Among all of the isotherm models Freundlich isotherm model
was fitted best. • Pseudo second order kinetic model was fitted best than the
other kinetic models applied.• Consequently, adsorption of ibuprofen onto rice husk gave
better results than adsorption onto lentil husk. But, the result obtained needs still improvement.
Activated carbon can be produced from rice husk for more effective adsorption process.
Fresh rice husk can be obtained to removal of residual ibuprofen.
Adsorption onto rice husk can be done for different pharmaceuticals in the wastewater.
THANKS FOR LISTENING TO US
REFERENCES• Almendra, A. R. P., (2011), “The Effect of Water Inorganic Matrix in Ibuprofen Adsorption onto Activated Carbon for
Water and Wastewater Treatment”, Faculdade de Ciencias e Tecnologia, Universidade Nova de Lisbqa.• Behera, S. K., Oh, S. Y., Park, H. S., (2012), “Sorptive Removal of Ibuprofen from Water Using Selected Soil Minerals and
Activated Carbon”, DOI 10.1007/s13762-011-0020-8, South Korea.• Connors, S., Lanza, R., Sirocki, A., (2013), “Removal of Ibuprofen from Drinking Water Using Adsorption”, Worcester
Polytechnic Institute, Worcester.• Gereli, G., Seki, Y., Kusoglu, I. M., Yurdakoc, K., (2006),"Equilibrium and Kinetics for the Sorption of Promethazine
Hydrochloride onto K10 Montmorillonite", J. Colloid Interface Sci., vol. 299, p.155-162.• Guedidi, H., Reinert L., Soneda Y., Bellakhal N., Duclaux L., (2014), “Adsorption of Ibuprofen from Aqueous Solution on
Chemically Surface-Modified Activated Carbon Cloths”, Saudi Arabia, http://dx.doi.org/10.1016/j.arabjc.2014.03.007.• Jodeh, S., (2012), “The Study of Kinetics and Thermodynamics of Selected Pharmaceuticals and Personal Care Products
on Agriculture Soil”, Chemistry Department, An Najah National University, Nablus, Palestine.‐• Lischman, L., Smyth, S. A., Sarafin, K., Kleygwegt, S., Toito, J., Peart, T., Lee, B., Servos, M., Beland, M., Seto, P., (2006),
“Occurence and Reductions of Pharmaceuticals and Personal Care Products and Estrogens by Municipal Wastewater Treatment Plants in Ontario, Canada”, Science of the Total Environment, Volume 367, pp. 544-558, Canada.
• Roccaro, P., Sgroi, M., Vagliasindi, F. G. A., (2013), “Removal of Xenobiotic Compounds from Wastewater for Environment Protection: Treatment Processes and Costs”, Department of Civil and Environmental Engineering, University of Catania, Viale A. Doria 6, 95125, Vol.32: Pg.507, Catania, Italy.
• Staiti, H. A. S., (2012), “Fate of Amoxicillin, Ibuprofen, and Caffeine in Soil and Ground Water Using Soil Columns”, An-Najah National University, Palastine.
• http://www.saglik.gov.tr/TR/dosya/1-82968/h/faaliyetraporu2012.pdf• http://amrita.vlab.co.in/?sub=2&brch=190&sim=606&cnt=1