Factors affecting lanthanum and cerium biosorption by pinus brutia leaf powder

14-17 October 2008 The Fifth Eurasian Conference

FACTORS AFFECTING

FACTORS AFFECTING

LANTHANUM AND CERIUM

LANTHANUM AND CERIUM

BIOSORPTION

BIOSORPTION

BY

BY

Pinus Brutia

Pinus Brutia

LEAF POWDER

LEAF POWDER

Ceren Kütahyalı, Şenol Sert, Berkan Çetinkaya, Süleyman İnan,Şenol Sert, Berkan Çetinkaya, Süleyman İnan, Meral EralMeral Eral

Ege University, Institute of Nuclear Sciences, 35100, Bornova, Izmir, Turkey

Outline

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14-17 October 2008

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The Fifth Eurasian Conference ₃

Rare earth elements are widely used in the fields

 Nuclear energy  Chemical engineering  Metallurgy  Electronics  Computers

Introduction

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Introduction

High purity grade cerium and lanthanum is required

• nuclear power production

• catalyst for automobile and nuclear industries

Current applications of lanthanum as a pure

element or in association with other compounds are in super alloys, catalysts, special ceramics, and in organic synthesis.

Introduction

 In environmental point of view

 _{increasing demand of the rare earth elements for} several industrial areas,

 _{monitoring and removal studies from waters and} waste waters are important.

Removal Technics  _{Precipitation}  Ion exchange  _Oxidation  Solvent extraction  Filtration  Electrochemical treatment  _{Membrane technologies}

advantages and limitations in application

ineffective or extremely expensive

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This has initiated research in new, low-cost materials for possible use as adsorbents.

Alternative process;

Adsorption/biosorption of heavy metals from aqueous solutions by biological materials.

In contrast to traditional methods biosorption is

 Competitive  Effective  Economical  eco-friendly technology.

Introduction

 Biosorbent materials for concentration and recovery of strategic or

valuable heavy metals, nuclear fuel, or radioactive elements.

Objective

Biosorption



 The term biosorption refers to metal uptake by (microbial) biomass which

may even be dead.

 Biosorbent materials  _seaweed  _yeast  _bacteria  _fungi 14-17 October 2008

Biosorption

In general, biomass considered could be an industrial waste or naturally grown and collected material.

Biosorbents can be highly  _selective,

 _efficient,  _cheap.

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Biosorption

Plant leaves have also been recommended as a simple inexpensive method to remove heavy metals from solutions.

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 Al-Subu described the removal of lead from aqueous solutions using

leaves of three different plant species; cypress (Cupressus

sempervirens), cinchona (Eucalyptus longifolio) and pine (Pinus halepensis).

 _{Bhattacharyya and Sharma used dry Neem leaf powder, as an}

adsorbent for removal of toxic heavy metals such as Pb(II).

 _{Kumar et al., investigated the potential use of untreated Tectona grandis}

L.f. biomass as metal sorbent for zinc from aqueous solution.

 _{Ucun et al., used ovulate cone biomass of Pinus sylvestris as a}

biosorbent for Cr(VI) from artificial wastewaters and studied to determine the constants of the adsorption isotherm relation.

Biosorption

M.M. Al-Subu, Adv. Environ. Res. 6 (2002) 569-576.

H. Ucun, Y. K. Bayhan, Y. Kaya, A. Cakici, O. Faruk Algur, Bioresource Technol. 85 (2002) 155–158. K. G. Bhattacharyya, A. Sharma, J. Hazard. Mater. B113 (2004) 97–109.

Y. P. Kumar, P. King, V.S.R.K. Prasad, Chem. Eng. J. 124 (2006) 63–70.

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Despite their strategic and economic importance, only in the last few years some investigations have been published related to the removal of REEs by biomaterials;

 _{Diniz and Volesky investigated the biosorption of La, Eu and Yb using}

Sargassum biomass. This study focuses on exploring the biosorption potential in the recovery of a light (La), intermediate (Eu) and a heavy (Yb) rare earth elements using Sargassum biomass in single- and multi-component metal systems.

 Texier et al., investigate the selective sorption of three trivalent

lanthanide (La, Eu, and Yb) ions by biomass from P. aeruginosa.

 _{Palmieri et al., work on to develop a study on neodymium biosorption}

from acidic solution utilizing different types of biomass in batch experiments.

V. Diniz, B. Volesky, Water Res. 39 (2005) 239–247.

A. Texier, Y. Andrès, P. Le Cloirec, Environ. Sci. Technol. 33 (1999) 489-495.

M.C. Palmieri, O. Garcia Jr., P. Melnikov, Process Biochemistry. 36 (2000) 441–444.

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

Present work;

finely ground Pinus brutia leaf powder for the removal of La

and Ce from aqueous solutions.

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 _{The dried leaves were used as biosorbent without any chemical treatment to avoid extra expenditure.}

Experimental

Collection of the leaves

Washing, deionized water

drying, 80°C for 24 h

grinding

Sieving, 125 μm

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 0.1 g of dry biomass were mixed with 25 mL of metal ion solution.  LaNO₃.6H₂O and CeNO₃.6H₂O (Merck)

 The mixture was shaken in thermostatically controlled shaker  _{Filtered (Whatman filter paper no: 44)}

 The amounts of metal ions adsorbed on biomass were calculated as

the difference between initial and final concentration at equilibrium.

Batch adsorption experiments

Experimental

m

V

)

C

C

(

q





ICP-OES (Optima 2000 DV, Perkin Elmer, USA)

Experimental

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The parameters which affect the La and Ce adsorption were investigated, such as;

 _{pH (2-6),}

 _{shaking time (5-480 min),}

 _{Initial metal ion concentration (25-300 ppm),}  _{adsorbent concentration (2-30 mg/mL)}

 _{Temperature (20-50°C).}

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Initial La and Ce concentrations: 100 ppm Shaking time: 120 min

Temperature: 30°C

Adsorbent amount: 0.1 g

Adsorption tests

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Initial La and Ce concentrations: 100 ppm pH 5

Temperature: 30°C

Adsorbent amount: 0.1 g

Adsorption tests

Adsorption tests

pH 5

Shaking time: 30 min for La, 15 min for Ce Temperature: 30°C

Adsorbent amount: 0.1 g

Effect of initial metal concentration 14-17 October 2008

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Adsorption tests

Initial La and Ce concentrations: 25 ppm pH 5

Shaking time: 30 min for La, 15 min for Ce Adsorbent amount: 0.1 g

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Thermodynamic considerations

H positive and G negative Endothermic and spontaneous

RT H R S K ln _d   0   0 0 0 0 _S G     H° (kJ/mol) S° (kJ/mol K) G° (kj/mol) 292 K 303 K 313 K 323 K La 5.650 0.077 -16.93 -17.78 -18.55 -19.33 Ce 3.325 0.068 -16.59 -17.34 -18.02 -18.70

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Adsorption tests

Initial La and Ce concentrations: 25 ppm pH 5

Shaking time: 30 min for La, 15 min for Ce Temperature: 30°C

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Adsorption isotherms

Langmuir Isotherm Freundlich Isotherm

m e m e e n C bn q C   1 C_e: equilibrium concentration (mg/L), q_e: amount absorbed at equilibrium (mg/g) n_m:monolayer capacity b: energy of adsorption n / e e KC q _ 1

q: amount of solute adsorbed per mass unit

adsorbent

C: equilibrium concentration K and n: Freundlich constants

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Freundlich and Langmiur Constants

Freundlich Constants Langmiur Constants R2 _{n K R}2 n

m (mg/g) b (L/mg)

Lanthanum 0.8925 3.6 3.85 0.8961 22.57 0.021 Cerium 0.9613 3.06 2.67 0.9342 17.57 0.029

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 The initial pH of the aqueous phase strongly affected the uptake of the

ions, with the highest capacity achieved at pH 5.0

 The Langmuir and Freundlich adsorption model were used for

mathematical description of the removal of the La and Ce(III) ions onto Pinus Brutia leaf powder.

 Thermodynamic parameters ΔH°, ΔS° and ΔG° were estimated and

these parameters show that adsorption is more favorable at high temperature, process is spontaneous and endothermic.

 Adsorption onto Pinus Brutia leaf powders showed a good potential to

be an interesting alternative and low-cost method for lanthanum and cerium recovery from solutions.

Thank you very much for your attention…

14-17 October 2008