ADSORCION DE

COMPUESTOS
ORGANICOS

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 Que es adsorcin?
Adsorcin: proceso de acumular Adsorbente: fase slida, lquida o
sustancias en solucin sobre una gas sobre el que se acumula el
interface apropiada (liquido y adsorbido
solido o gas y solido) Adsorbido o adsorbato:
Operacin de transferencia de constituyente removido de fase
masa : constituyente transferido lquida a la interface
de fase lquida a slida
Remocin por Adsorcin sobre
una superficie activa
Adsorcin
Adsorbentes Adsorbatos
Carbn activado Componentes orgnicos
GAC e inorgnicos de origen
PAC natural o antropogenico
Adsorbentes Sintticos
Polimricos (resinas
de intercambio)
En base a Slica
Oxidos e hidroxidos de
metals y carbonatos
Alumina activada
Zeolitas
Materia orgnica disuelta
 Adsorcin
Molculas de olor y sabor
Materia orgnica natural (NOM) Adsorbato
cidos hmicos y flvicos

C: 88%
O: 6%
S: 1%
Fuerzas qumicas de N: 0.5%
atraccin: H: 0.5%
- Enlace hidrogeno. ASH: 4%
- Interacciones
dipolo-dipolo.
- Fuerzas de
Vander Waals Adsorbente

Grupo de acido carboxlico: -COOH

Oxigeno Grupo hidroxi-fenlico : -OH
Grupo quinon carbonil: >CO
Materia para el carbn
activado
Carbn
bituminoso
Cascara de Coco
Madera
Lignito
Activated Carbon production
The choice of raw material affects the internal pore structure, surface area
distribution, and surface chemistry.
Commercial activated carbon production is a two-step process of
carbonization of the precursor materials and activation.
In the pyrolytic carbonization process, the temperature of the raw material
is raised to the range of 500 to 800 C in the absence of oxygen. Volatile
organic matter of the raw material is thermally released, and the carbon
atoms realign to form a more crystalline structure. The carbonized product
at this point in the process is heavily influenced by the raw materials used.
For activated carbon products used in water treatment, a thermal or
physical activation process then follows in which the temperature of the
carbonized produce is increased to the range of 850 to 1,000 C in the
presence of an oxidizing agent, typically steam or carbon dioxide.
Activation increases the pore sizes and creates a continuous pore structure,
which increases the micropore volume (pore width < 2 nm) and the internal
surface area. The mesopore and macropore volumes (pore width > 2 nm)
are critical to the internal transport of the compound to the micropore
surface area, which is where most of the adsorption occurs.
Activated Carbon characteristics
Activated carbon is a highly porous material with an internal
surface area that typically ranges from about 800 to 1500
m2/g (Bansal et al., 1988). Typically, the manufacturer
provides data that include the BET surface area.
To classify pores according to size, the International Union of
Pure and Applied Chemistry (IUPAC) differentiates between (1)
micropores (<2 nm width), (2) mesopores (250 nm width),
and (3) macropores (>50 nm width) (Sing et al., 1985). PAC
and GAC for water treatment typically exhibit a
heterogeneous pore structure, in which micropores,
mesopores, and macropores are all present.
Influencia de la porosidad del carbn
activado en la eficacia del proceso
Mientras que la mayora, pero no todos, los compuestos
orgnicos de inters en calidad del agua potable son
adsorbible por el carbn activado, es el grado de capacidad de
absorcin lo importante, ya que determina el coste de
utilizacin de carbn activado.
La materia orgnica disuelta consiste en una mezcla de
compuestos de los cuales aproximadamente 90 por ciento son
adsorbibles en algn grado.
Compuestos de gran peso molecular se excluyen de los sitios
de adsorcin internos y los compuestos de MOD hidrfilicos
de cualquier tamao no son atrados a la superficie
adsorbente. Los componentes ms fuertemente adsorbidos
de la MOD son compuestos hidrofbicos de peso molecular
bajo y mediano
Influencia de la porosidad del carbn
activado en la eficacia del proceso
The size of adsorbent pores affects the adsorption of organic
contaminants in two important ways.
First, size exclusion limits the adsorption of contaminants of a given
size and shape if pores are too small.
Second, the strength of adsorbate-adsorbent interactions increases
with decreasing pore size because adsorption potentials between
opposing pore walls begin to overlap once the micropore width is
less than twice the adsorbate diameter (e.g., Dubinin, 1960; Sing,
1995).
Therefore, adsorption of micropollutants preferentially takes place
in the smallest pores that are accessible to a given pollutant.
Example: many micropollutants adsorb in small micropores (<1 nm),
whereas the largest percentage of NOM preferentially adsorbs in
mesopores and large micropores (>1 nm)
Activated Carbon characteristics
Caractersticas carbn activado
N Parmetro
1 Humedad
2 Densidad aparente
3 Distribucin de tamao de
partculas para PAC de
materia prima distinta a la
madera.
4 Distribucin de tamao de
partculas para PAC de
hecho de madera
5 Numero de iodo
6 Impurezas
7 Olor y sabor de sustancias
orgnicas
Valor gua
No deber exceder 8%
0.2 g/cc 0.75 g/cc
No menor 99% pasar la malla N 100.
No menor 95% pasar la malla N 200.
No menor 90% pasar la malla N 325.
No menor 95% pasar la malla N 100.
No menor 85% pasar la malla N 200.
No menor 60% pasar la malla N 325.
No ser menor a 500 mg/g
No contendr sustancias capaces de producir
perjuicio y daos para la salud
Deber determinarse en laboratorio fijando un
eficiencia de remocin
Capacidad de adsorcin del carbn
activado
The iodine number (ASTM Standard D4607-94;ASTM, 2009)
measures the amount of iodine that will adsorb under a
specified set of conditions, and it generally correlates well
with the surface area available for small molecules.
The molasses number or decolorizing index is related to the
ability of activated carbon to adsorb large-molecular-weight
color bodies from molasses solution and generally correlates
well with the ability of the activated carbon to adsorb other
large adsorbates.
Carbon tetrachloride activity, the methylene blue number, the
acetoxime number, the tannin value, and the phenol
adsorption value.
Cintica de la adsorcin
Transporte de solucin.
Resistencia externa
Resistencia del poro.
Adsorcin
Cintica de adsorcin
Ceq: concentracin
de equilibrio en la
fase liquida

teq: tiempo de
equilibrio

qeq: concentracin
de equilibrio en la
fase slida
Equilibrio de adsorcin
Adsorcin

A B AB
Desorcin

A: adsorbato Equilibrio:
B: adsorbante Vadsorc = Vdesorc
AB: compuesto adsorbido

Fuerzas de adsorcin:
1. Enlaces hidrgenos
2. Interaccin dipolo-dipolo
3. Fuerzas de Vander Waals
Cunto de adsorbato puede acumular un
adsorbente?

La relacin de equilibrio a temperatura constante entre la

cantidad de adsorbato por unidad de adsorbente (qe) y su
concentracin (Ce) de equilibrio se llama isoterma de
adsorcin.

1. Isoterma de Freundlich.
2. Isoterma de Langmuir
Ecuacin de Freundlich
1
qe K Ce n

1
log qe log K log Ce
n
qe = masa de adsorbato / masa de adsorbente
Ce = masa/volumen
K = est relacionada con la capacidad de adsorbente por el
adsorbato
1/n = est en funcin a la intensidad de adsorcin.
Si 1/n es pequeo: adsorcin irreversible, independiente de Ce
Si 1/n es grande : enlace de adsorcin dbil, varia con los
pequeos cambios de Ce

Limitacin: cuando el adsorbente esta saturado no aplica la ecuacin de

Freundlich. La capacidad de adsorcin es constante e independiente de
Ce.
Isotermas de adsorcin
Isotermas de adsorcion
100.000 100.000

10.000 10.000

y = 75.497x0.5013

q mg/g AC
q mg/g AC

R = 1
y = 75.553x0.5016
R = 1

1.000 1.000

0.100 0.100
0.00001 0.0001 0.001 0.01 0.1 1 10 0.0001 0.001 0.01 0.1 1
C, mg/L C, mg/L
Parmetros de adsorcin
Isotermas de adsorcion
Ecuacin de Langmuir
qmaxb Ce
qe
1 b Ce
qe = masa de adsorbato / masa de adsorbente
Ce = masa/volumen
qmax = representa el valor mximo de Qe a medida que Ce aumenta
b = relacionado con la energia de adsorcin y aumenta a mediad
que la densidad del enlace de adsorcin se incrementa.
Que afecta el equilibrio ?
Caractersticas del adsorbente
rea superficial: <1500 m2/g
Distribucin de tamaos de poros
Microporos d < 2 nm: gran rea superficial, molculas
pequeas.
Mesoporos 2nm<d<50 nm.
Macroporos d>50 nm (molculas grandes)
Qumica de la superficie
Que afecta el equilibrio ?
Caractersticas del adsorbato
Solubilidad.
Estructura molecular.
Soluciones ionizadas no son adsorbables.
pH.
Polaridad de las molculas: baja polaridad OK
Interferencias: OH-, amino, carbonil, sales de Fe, Mg y Ca (sus
precipitados pueden depositarse en el adsorbente)
Competencias por sitios de adsorcin.
Factores que afectan la adsorcin
Dimetro de la partcula de carbn
Concentracin del soluto.
Temperatura.
Peso molecular del soluto .
Estructura (cadenas ramificadas son mas absorbibles que las
largas).
Tiempo de contacto.
Solubilidad del soluto.
Adsorcin con PAC
The primary advantages of using PAC are the low capital
investment costs and the ability to change the PAC dose as the
water quality changes. The latter advantage is especially
important for systems that do not require an adsorbent for
much of the year. The disadvantages, according to Sontheimer
(1976), are high operating costs if high PAC doses are required
for long periods of time, the inability to regenerate, the low TOC
removal, the increased difficulty of residuals management
(increased solids loading, residuals are more abrasive), and the
difficulty of completely removing the PAC particles from the
water
Mtodo de tratamiento con AC
Mtodo de tratamiento con AC
Punto de aplicacin del PAC
(1) the provision of good mixing, or good contact between the
PAC and all the water being treated.
(2) Sufficient time of contact for adsorption of the contaminant
(3) minimal interference of treatment chemicals with
adsorption on PAC, and
(4) no degradation of finished water quality. The PAC must be
added in a way that ensures its contact with all the flow.
Ventajas y desventajas de puntos de
aplicacin del PAC
Sistema de inyeccion
Sistema de inyeccin
Sistema de inyeccin
Sistema de inyeccin
Sistemas de adsorcin pac
Fundamentos - Adsorcin
1. Transporte por el volmen de la solucin
Movimiento del adsorbido a travs del volmen lquido hasta el
borde de la capa de pelcula lquida fija alrededor del
Adsorbente
Adveccin

Dispersion

2. Transporte difusivo por pelcula

Transporte difusivo del adsorbido a travs de pelcula lquida
estancada a la entrada de poros del Adsorbente
Difusin

3. Transporte por Poros

Transporte de adsorbido a travs de poros
Difusin molecular por poro lquido

Difusin a lo largo de superficie de Adsorbente

Fundamentos - Adsorcin
4. Adsorcin (sorcin)
Fijacin de adsorbido al Adsorbente en un sitio de
sorcin disponible
cargas no Coulombicas

Punto de carga y un dipolo

interacciones dipolo-dipolo

especies de Punto de carga neutral

Fuerzas de Van der waals

Enlace covalente con reaccin

Enlaces Hidrgeno
Fundamentos - Adsorcin