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Adsorption of dyes from

water by modified
cellulosic wastes
Jesus Beltran de Heredia 1 &
Elena Beltran de Heredia 2
1Department of Chemical Engineering and Physical Chemistry,
University of Extremadura, Badajoz, Spain

2 Atomic, Molecular, and Nuclear Physics Department


Faculty of Physical Sciences, University Complutense of Madrid,
Madrid, Spain
Fundamentals of adsorption
Fluid phase Solid phase

Adsorbate
Adsorbent
Fundamentals of adsorption
Fluid phase Solid phase

Applications
Potable water
Wastewater treatment
Gas purification

Adsorbate
Adsorbent
Characteristics of
adsorbents

Adsorbent Advantages Disadvantages

Active carbon - high capacity - difficult to regenerate


- high surface area - expensive
- slow kinetics

Cellulosic derivatives - high capacity - requires pelletizing


- cheap - low surface area
- versatile
Cellulosic derivatives
Etherification

Esterification Silanization

Oxidation Urethanization

Phosphorylation Xanthogenation
(poster SDEWES2016-0033)

Sulfophosphorylation
Bulrush

Fennel

Cellulosic wastes
Water hyacinth
Thistle

Cornish mallow Retama


Adsorbent preparation
Pretreatment Esterification
Washing with water 5 g of biomass was mixed
at room temperature with 100 mL of 1M citric acid

Dried at 60 ºC Evaporation of water at 60 ºC

Milled to 0.25 mm in diameter Dry residue was heated to 120 ºC for 3 h

Washing with ethanol Washing with water/Na2CO3 at


at room temperature room temperature until neutral pH

Dried at 60 ºC Dried at 60 ºC
Reaction mechanism
COOH CO
- H2 O O
HO COOH HO CO
Δ
COOH COOH

CO
O - H2 O
HO CO +
Δ
COOH

COOH COO Na+


HO COOH HO COO Na+
CO CO

NaHCO3

n n
Analytical methods

Methylene
Blue Fuchsine

Dyes wavelength analysis


Dye Wavelength (nm)
Victoria Blue Brilliant
Green Brilliant Green 625
Fuchsine 553
Methylene Blue 665
Victoria Blue 615
Screening of dyes

Cornish mallow Water hyacinth

Effectiveness: high and independent of the type of dye


Screening of adsorbents

Fuchsine Victoria Blue

Efficacy: high for all derived biomass adsorbents


Comparison with raw material

Bulrush

Significative
improvement in the
effectiveness of citrate
derivatives with respect Retama
to raw material
Influence of pH

Fennel Thistle

No influence of pH on the adsorption efficiency


Influence of temperature

Bulrush Water hyacinth

No influence of temperature on the adsorption


efficiency
Evolution of dye concentration
Bulrush Fennel

Thistle Water hyacinth


Kinetic models

Lagergren model (1st order)


d qt
= K L ( qe  qt ) qt  qe  qe ·exp(  K L ·t )
dt

Ho et al. model (2º order)


d qt qe2 ·K H ·t
= K H ( qe  qt )2 qt =
dt 1 + qe ·K H ·t

( C0  Ct )·V
qt 
W
Kinetic study

Bulrush Fennel

Thistle Water hyacinth


Kinetic study

Kinetic models parameters for the adsorption


of Methylene Blue
Adsorbent KL (min-1) r2 KH (g/(mg min)) r2
Bulrush 8.37 10-3 0.9713 2.88 10-5 1.0000
Cornish mallow 7.31 10-3 0.9503 1.67 10-5 0.9998
Fennel 44.2 10-3 0.9669 15.6 10-5 1.0000
Retama 6.87 10-3 0.9761 2.27 10-5 1.0000
Thistle 6.64 10-3 0.9607 1.36 10-5 0.9998
Water hyacinth 26.7 10-3 0.9879 10.3 10-5 1.0000
Equilibrium models

Langmuir model qmax


qmax ·Ce
qe 
Ke  Ce
Ke

Freundlich model n
qe  K f ·Cen
Kf

( C0  Ce )·V
qe 
W
Equilibrium isotherm
Fennel
Bulrush

Retama Water hyacinth


Equilibrium isotherm

Equilibrium isotherms parameters for


adsorption of Methylene Blue
Adsorbent qmax (mg/g) Ke (mg/L) r2 Kf (Ln/(g·mg(n-1))) n r2
Bulrush 644 2.33 0.9231 367 0.14 0.9034
Cornish mallow 603 1.50 0.7698 218 0.26 0.5641
Fennel 767 3.58 0.9724 261 0.29 0.8482
Retama 1074 10.2 0.9702 168 0.47 0.8924
Thistle 617 2.25 0.9157 378 0.11 0.7364
Water hyacinth 1188 10.9 0.9534 159 0.52 0.9186
Characterization of adsorbents

Cornish mallow Water hyacinth

Carbon (%) 39.1 34.0


Hydrogen (%) 4.81 5.01
Nitrogen (%) 0.46 0.53
Sulfur (%) 0.02 0.03
Oxygen (%) 55.6 60.4

Pore volume (mL/g) 1.68 2.19

Surface BET (m2/g) 2.12 6.67


Infrared spectrum
Cornish mallow Water hyacinth
Scanning electron microscopy

Cornish
mallow
Scanning electron microscopy

Water
hyacinth
Thank you very much
for your attention!!