Unit Operations 1

UC6. Adsorption (week 7 and 8)

 6.1 Introduction to adsorption

• It is a separation process in which certain components of a fluid

phase are transferred to the Surface of a solid adsorbent.
• Most of adsorbents are porous materials and adsoprtion takes place
primarly on the walls of the pores or at specific sites on the particle.

Figure - uploaded by Yangong Zheng

https://www.researchgate.net/figure/Adsorption-of-an-
acetone-molecule-into-a-zeolite-Y-supercage-window-
74-A-cage-132-A_fig2_225186971

• Warren L. McCabe/Julian C Smith/Peter Harriot “Unit Operations and Chemical Engineering”, 5th edition, Mc Graw Hill/USA, 1993
 6.1 Adsorbents

Zeolitas

Montmorillonita MCM
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 6.2 Adsorption equipment

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 6.2 Adsorption equipment

Uses
• Sugar refining
• Petroleum processing
• Production of pharmaceuticals
or processing of wastewater
• To purify gas streams in
laboratory settings

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6.2 Adsorption equipment

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 6.2 Adsorption equipment
SSB

MSB

Continuos serial

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University of Michigan
 6.2 Adsorption equipment
An activated carbon VOC recovery system

Uses
• Water purification
• Pharmaceutical applications
• Decoloring.

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 6.2 Adsorption equipment

• One or more components in a gas

stream adsorb on a solid
adsorbent.
• Adsorption on pressure. More gas
can be adsorbed at higher
pressures. By adsorbing at one
pressure and then "swinging" to a
lower pressure for desorbing

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 6.2 Adsorption equipment

Uses
Technique used to separate components of a
gas stream cost effectively.
• Chemical processing
• Petroleum
• Medical
• Specialty gases.
Equipment size can vary from small indoor
equipment to large outdoor equipment
 Also used for air separation. Special
zeolites have been developed to
preferentially adsorb the nitrogen, water
and carbon dioxide in air and allow the
oxygen to be separated. Ambient air is
pumped in and compressed before being
sent to the adsorption beds.

Visual Encyclopedia of Chemical EngineeringVisual Encyclopedia of Chemical Engineering - University of Michigan

 6.2 Adsorption equipment
Uses
The pressure swing adsorption unit
shown on the left uses multiple beds to
separate the hydrogen and carbon
monoxide in synthesis gas at a refinery
and petrochemical plant.

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 6.2 Adsorption equipment

• Equipment Design
Both the chemical and physical properties of the adsorbent must be
considered.
Chemical properties that influence adsorbent design include degree
of ionization of the surface, functional groups present on the surface,
and degree to which these chemical properties vary with process
parameters and by contact with the solution.
Physical properties that influence design include surface area, surface
structure, size, and pore distribution.

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 6.3 Equilibria, Adsorption isotherms

Effect of temperature

https://www.slideshare.net/iitabhinav84/surface-chemistry
 6.3 Equilibria, Adsorption isotherms

The adsorption isotherm is the

equilibrium relationship between the
concentration in the fluid phase and
the concentration in the adsorbent
particles at a given Temperature.
For gases, the concentration is usually
given in mole percent or as a partial
pressure or relative pressure.

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 6.3 Equilibria, Adsorption isotherms

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 6.3 Equilibria, Adsorption isotherms

Micropore: < 2 nm
Mesopore: 2-50 nm
Macropore: > 50 nm

Type I: Microporous materials

Type II: non porous or macroporous
materials
Type III: non interaction between
adsorbate and adsorbant
Type IV: mesoporous materials
Type V: mesoporous materials week
interactions
Ype VI: surfaces highly homogeneous

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 6.3 Equilibria, Adsorption isotherms

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 6.3 Equilibria, Adsorption isotherms

Tipo de histéresis H1: Muestra las ramas de

adsorción-desorción paralelas y casi verticales.
Este tipo de histéresis está presente en materiales
formados de aglomerados (reunión de partículas
unidas con rigidez) o compactos de partículas
esféricas ordenadas de una manera uniforma.
Más recientemente, se ha comprobado que el
tipo de histéresis H1 es también característico de
materiales con poros cilíndricos y con un elevado
grado de uniformidad del tamaño de poro
(Esquivel, 2011).

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 6.3 Equilibria, Adsorption isotherms
Cada una de esta isotermas esta asociada con una, o varias,
estructuras porosas, por ejemplo la isoterma H1 es obtenida
de adsorbentes que tienen distribuciones de poros muy
angostas, como por ejemplo los materiales MCM-41 (poros
cilíndricos abiertos y cerrados) o aglomerados de partículas
esféricas de tamaños y distribuciones aproximadamente
uniformes. La mayoría de los óxidos inorgánicos (sílica gels)
producen la tipo H2 , que por cierto, es la más común. Los
lazos tipo H3 y H 4 se obtienen al trabajar con aglomerados de
poros de placa paralelas (slit- shaped), como lo son las arcillas
pilareadas. La tipo H4 también es característica de los carbones
activados, pero en este caso la distribución de tamaños de
poros está en el rango de los microporos. En estas últimas
secciones hemos visto como la geometría y el tamaño de los
poros afecta la forma de la isoterma. Esto nos lleva a que, a
grandes rasgos se puede clasificar a un material dada la
isoterma que se obtiene, y esto es justamente de lo que se
trata la caracterización de materiales.
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 6.3 Equilibria, Adsorption isotherms

Visual Encyclopedia of Chemical EngineeringVisual Encyclopedia of Chemical Engineering - University of Michigan

 6.3 Equilibria, Adsorption isotherms

Visual Encyclopedia of Chemical EngineeringVisual Encyclopedia of Chemical Engineering - University of Michigan

 6.3 Equilibria, Adsorption isotherms

Visual Encyclopedia of Chemical EngineeringVisual Encyclopedia of Chemical Engineering - University of Michigan

 6.3 Equilibria, Adsorption isotherms

Visual Encyclopedia of Chemical EngineeringVisual Encyclopedia of Chemical Engineering - University of Michigan

 6.3 Equilibria, Adsorption isotherms

Visual Encyclopedia of Chemical EngineeringVisual Encyclopedia of Chemical Engineering - University of Michigan

 6.3 Equilibria, Adsorption isotherms

Visual Encyclopedia of Chemical EngineeringVisual Encyclopedia of Chemical Engineering - University of Michigan

 6.3 Equilibria, Adsorption isotherms

• The Langmuir isotherm is given by the relation 𝑊 = 𝑊𝑚𝑎𝑥 𝐾𝑐 1+𝐾𝑐

where W is the adsorbate loading, c is the concentration in the fluid,
K is the adsorption constant.
• The relation Works fairly well for gases that are weakly adsorbed

• The empirical Freundlich equation 𝑊 = 𝑏𝑐 𝑚 where b and m are

constants and m < 1, is often a better fit, particularly dor adsorption
from liquids

Warren L. McCabe/Julian C Smith/Peter Harriot “Unit Operations and Chemical Engineering”, 5th edition, Mc Graw Hill/USA, 1993
 6.3 Equilibria, Adsorption isotherms

https://www.slideshare.net/iitabhinav84/surface-chemistry
 6.3 Equilibria, Adsorption isotherms

https://www.slideshare.net/iitabhinav84/surface-chemistry
 6.3 Equilibria, Adsorption isotherms
• Langmuir adsorption model

https://en.wikipedia.org/wiki/Langmuir_adsorption_model
 6.3 Equilibria, Adsorption isotherms
• Langmuir adsorption model 60
y = 119,13x + 0,2743
R² = 0,9997
50

𝑃
𝜃𝐴 = 40 slope
𝑣
𝜃𝐴 = fractional occupancy of the
30
adsorption sites

teta
P = equilibrium pressure langmuir
20 Lineal (langmuir)
v = quantity adsorbed
𝑃 𝑃 1
𝜃𝐴 = = + 10
𝑣 𝑣𝑚𝑜𝑛𝑜 𝐾𝑣𝑚𝑜𝑛𝑜
0
1 0,0000 0,1000 0,2000 0,3000 0,4000 0,5000
Intercept = 𝐾𝑣𝑚𝑜𝑛𝑜
P/Po

1
Slope = 𝑣
𝑚𝑜𝑛𝑜

https://en.wikipedia.org/wiki/Langmuir_adsorption_model
 6.3 Equilibria, Adsorption isotherms
• BET

E1 = heat of adsorption of 1st layer

E2 = heat of liquefaction (2nd and higher layers

https://en.wikipedia.org/wiki/Langmuir_adsorption_model
 6.3 Equilibria, Adsorption isotherms
• BET
y = 8E-07x - 0,0423
0,02 R² = 0,0606

0
0,00 10000,00 20000,00 30000,00 40000,00 50000,00 60000,00
-0,02

1 𝑐−1 𝑃 1 -0,04
= +

1/a(1-P/Po)
𝑃0 𝑣𝑚𝑜𝑛𝑜 𝑐 𝑃0 𝑣𝑚𝑜𝑛𝑜 𝑐 -0,06
𝑣 𝑃 − 1
-0,08

-0,1
𝑐−1
Slope = 𝑣 BET
𝑚𝑜𝑛𝑜 𝑐 -0,12
Lineal (BET)
-0,14
1
Intercept = 𝑣 -0,16
𝑚𝑐
P/Po
1
𝑣𝑚 =
𝑆𝑙𝑜𝑝𝑒 + 𝐼𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡

https://en.wikipedia.org/wiki/Langmuir_adsorption_model
6.3 Equilibria, Adsorption isotherms
 6.4 Principles of adsorption
• Concentration patterns in fixed beds
Concentrations in the fluid and solid change with
time and position in the bed.
Zona de transferencia de materia (0.95-0.05)
t1 adsorption at the inlet of the bed
t2 far from the inlet
t3,t4 transfer zone moves to the inferior part of
the bed
Curvas de ruptura
Cuando la concentración alcanza el valor
límite permisible, o punto de ruptura, se
interrumpe el flujo o bien se conduce a
otro lecho de adsorbente fresco
Concentración relativa = 0,05 o 0,1
El área hasta el tiempo tb del
punto de ruptura representa
la cantidad real adsorbida.
 6.4 Principles of adsorption
• Concentration patterns in fixed beds
Si la zona de transferencia de materia es
estrecha con relación a la longitud del
lecho se utilizará la mayor parte de la
capacidad del sólido hasta el punto de
ruptura.

Cuando la zona de transferencia de

materia coincide con la altura del lecho
se utiliza menos de la mitad de la
capacidad del lecho
 6.4 Principles of adsorption
• Scale-up
• Adsorbers are scaled up from laboratory tests in a small diameter
bed, and the large unit is designed for the same particle size and
superficial velocity.

• Length of unused bed

• “Los ensayos con diferentes longitudes de lecho dan curvas de
ruptura de la misma forma, pero en lechos de gran longitud la zona
de transferencia de materia representa una fracción menor de forma
que se utiliza una mayor fracción del lecho”
 6.4 Principles of adsorption
• Length of unused bed
• “Los ensayos con diferentes longitudes de lecho dan curvas de ruptura de
la misma forma, pero en lechos de gran longitud la zona de transferencia
de materia representa una fracción menor de forma que se utiliza una
mayor fracción del lecho”
• El cálculo de la longitud de lecho no utilizado a partir de la curva de ruptura
se realiza por integración.
• La capacidad del sólido se obtiene por integración de una curva de ruptura
completa o bien a partir de ensayos de equilibrio.
• La relación entre estas dos cantidades representa la fracción de la
capacidad de lecho utilizado, y 1,O menos esta relación, la fracción no
utilizada.
 6.4 Principles of adsorption
• Length of unused bed
• La fracción no utilizada se convierte a un tamaño de lecho
equivalente LUB el cual se asume constante.
• El tiempo de ruptura se calcula multiplicando el tiempo ideal y la
fracción de lecho utilizado.
 6.4 Principles of adsorption
• Length of unused bed
• For a unit area of bed cross section the solute feed rate is:
𝐹𝐴 = 𝑣0 𝑐0 𝑀
• For an ideal breakthrough curve all the solute fed in time t* is
adsorbed and the concentration of the solid has increased from the
initial value w0 to the equilibrium wsat value
∗
𝐿𝜌𝑏 𝑤𝑠𝑎𝑡 − 𝑤0
𝑡 =
𝑣0 𝑐𝑜
 6.4 Principles of adsorption
• Length of unused bed
• Si un lecho de 20 cm de espesor conduce a un 60% de utilización en el
punto de ruptura, la longitud de lecho no utilizado es 8 cm.
• Si la longitud del lecho aumenta hasta 40 cm, la parte no utilizada es
8/40, o sea 20%
• El tiempo del punto de ruptura incrementa por un factor 40/20 x
0,8/0,6 = 2,67, debido a la mayor longitud de lecho y a la mayor
fracción utilizada.
 6.4 Principles of adsorption
• Length of unused bed
• Example. The adsorption of n-butanol from air was studied in a small
fixed bed (10.16 cm diameter) with 300 and 600 g of carbón,
corresponding to bed lenghts of 8 and 16 cm. (a) from the following
data for effluent concentration, estimate the saturation capacity of
the carbon and the fraction of the bed used at c/c0 = 0,05.
 6.4 Principles of adsorption
• Example 25.2
 6.4 Principles of adsorption
• Example 25.2
 6.4 Principles of adsorption

• Effect of feed concentration

• La capacidad de equilibrio se determina a partir de la isoterma de

adsorción, y el tiempo del punto de ruptura es proporcional a la
capacidad del sólido e inversamente proporcional a la concentración
de la alimentación.
• La adsorción es un proceso exotérmico y puede originarse un
aumento de la temperatura de un lecho entre 10 y 50 °C cuando se
tratan vapores con solamente un 1% de adsorbato

Control T Adiabatically Experiments in a pilot colum

with bigger diameter
 6.4 Adsorber design

• Involves selection of the adsorbent anf particle size, appropriate

velocity to get the bed area, determining the bed length for a given
cycle time…
• Using a shorter bed length– smaller inventory of sorbent and lower
pressure drop in the bed. However, more frequent regeneration, high
cost
• For gas purification, 4*6 or 4*10 mesh carbon is often chosen
UC7.
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