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

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• 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