ADSORPTION PRINCIPLES

INTRODUCTION TO PROCESS
• SOLID FLUID PROCESS
– RETENTION OF COMPONENTS FROM
FLUID PHASE ON SOLID PHASE
– SEPARATION DUE TO RELATIVE
SOLUBILITY OF COMPONENTS SOLUTES
IN SORBATE
• SOLID CHARACTERISTICS
– MOST ARE POROUS
– INTERNAL SURFACE AREA 1000'S TIMES
GREATER THAN EXTERNAL AREA

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 COMMON TYPES OF
ADSORBENTS
• SILICA GEL, SiO2
http://www.gracedavison.com/
eusilica/Adsorbents/overview_
ads.htm

• MOLECULAR SIEVE –
TETRHEDRAS OF AlO4
AND AND SiO4

• ACTIVATED CARBON

http://www.afssociety.org/education/0705one
minute.htm

COMMON TYPES OF
ADSORBENTS
• ACTIVATED ALUMINA
http://catalog.adcoa.net/viewitems/act
ivated-alumina/grade-f-
200?&forward=1

• POLYMERIC RESINS
http://www.novasep.com/Technologies/ion-adsorption.asp
• ION EXCHANGE RESINS
http://www.rohmhaas.com/ionexchange/

http://www.remco.com/ix.htm

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 ADSORBENT PROPERTIES
• PERRY’S TABLES 16-5 & 16.6 LIST
PROPERTIES
• USES
– DEHYDRATION
– DECOLORING
– REMOVAL OF ORGANICS
– REMOVAL OF METAL IONS
– SELECTIVE REACTIONS
– CHROMATOGRAPHIC SEPARATIONS

http://www.uop.com/adsorbents/7000.html

ADSORBENT
CHARACTERISTICS
• ADSORPTION ISOTHERMS
– INDICATE CAPACITY MASS SOLUTE/MASS
BDS IRREVERSIBLE

– EQUILIBRIUM FAVORABLE

CURVES STRONGLY
FAVORABLE
• FAVORABLE
• STRONGLY
FAVORABLE
• LINEAR UNFAVORABLE

• UNFAVORABLE

FLUID PHASE CONCENTRATION, MASS/VOL

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 TYPICAL ADSORPTION
ISOTHERMS
• IRREVERSIBLE - REQUIRES VERY HIGH
TEMPERATURES FOR REGENERATION
• LANGMUIR (STRONGLY FAVORABLE)
q c
q= 0 q 0 AND K ≡ EMPIRICAL CONSTANTS
K +c
• FREUNDLICH – FAVORABLE

q = Kc n
K AND n ≡ EMPIRICAL CONSTANTS

• LINEAR
q = Kc

DEFINITION OF LOADING
• LANGMUIR ISOTHERM
SURFACE REACTION : A + S ↔ SA
S = SOLUTE A = SITE
x SA
DISTRIBUTI ON COEFFICIEN T : K =
xS x A
x = EQUILIBRIU M MOLE FRACTIONS
θ = FRACTION OF SITES CONTAINING S = x SA
1 − θ = FRACTION OF SITES WITHOUT S = x A
θ Kx S
AT EQUILIBRIU M : K = OR θ =
x S (1 − θ ) 1 + Kx S
q 0c
q= (12 .1 − 3)
K +c

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 LANGMUIR DERIVATION
• ASSUMPTIONS ARE:
– SINGLE MONOLAYER
– FINITE NUMBER OF SITES
– REVERSIBLE ABSORPTION
– FINITE EQUILIBRIUM
• CONFIRMATION OF LANGMUIR MODEL
– REQUIRES LINEARIZATION OF THE DATA
USING (1/q) VS (1/c) PLOT

PLOT FOR LANGMUIR

ADSORPTION
TYPICAL LANG MU IR ADSO RPTIO N

1/q

1/q o

1/c

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 PROFILES FOR OTHER TYPES
OF ISOTHERMS
• SEE PERRY’S SECTION 16 FOR A LIST

BASES OF ISOTHERM MODELS

• FOR GASES, K = K(PTOTAL)
• ADSORPTION THERMODYNAMICS
• .GIBB’S RELATIONSHIP AT SURFACE (NO
PENETRATION)
µi,FLUIDPHASE = µi,SOLID PHASE

• FROM KINETIC MOLECULAR THEORY

− nS ⎛ ∂γ ⎞
• WHERE: Γ= ⎜⎜ ⎟⎟
kT ⎝ ∂nS ⎠
– Γ = MOLECULES/UNIT AREA,
– ns = CONCENTRATION TERM (ps FOR GASES)
– k = BOLTZMAN’S CONSTANT
– γ = SURFACE ENERGY TERM [SURFACE TENSION
FOR LIQUIDS (POLARITY ENERGY/UNIT AREA)]
– (∂γ/∂ns) = SLOPE OF EQUILIBRIUM DIAGRAM

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 LIQUID/LIQUID MODELS
• USE SURFACE TENSION-BASED ENERGY
TERMS
σ kT ⎛ n⎞
= 1 − S ln⎜1 + ⎟
σS σS ⎝ K ⎠
• WHERE:
– σ = SURFACE TENSION SOLUTE,
– σS = SURFACE TENSION SOLVENT,
– n = SURFACE CONCENTRATION SOLUTE,
– nS = SURFACE CONCENTRATION SOLVENT,
– K = ADJUSTABLE PARAMETER

BATCH ADSORPTION
• BATCH ADSORPTION OCCURS WHEN THE
ADSORBENT IS ADDED TO THE SOLUTION
TO REMOVE A CONTAMINANT (SOMETIMES
CALLED ADMIXING)
– SOLID WILL NOT REMOVE ALL CONTAMINANT
UNLESS THERE IS INFINITELY GOOD MIXING
– TOTAL REMOVED IS A FUNCTION OF RELATIVE
AMOUNTS OF CONTAMINANT TO MASS OF
SOLID

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 BATCH ADSORPTION
• OPERATING LINE IS THE MASS BALANCE
q F M + c F S = qM + cS (12 . 2 − 1)

• EQUILIBRIUM LINE IS ONE OF THE

ADSORPTION ISOTHERMS
• .OVER A SHORT RANGE, GENERAL FORM
OF THE EQUILIBRIUM LINE EQUATION IS q =
Acn , WHICH IS LINEARIZED BY PLOTTING ln
q VS. ln c AS SHOWN ON FIGURE 12.1-2

BATCH ADSORPTION
PLOTTING THE EQUILIBRIUM ISOTHERM ON TH
SAME FIGURE (12.2-1, BUT NOTE CHANGE TO
LINEAR AXES) YIELDS THE FINAL
CONCENTRATION AT THE INTERSECTION OF
THE OPERATING AND EQUILIBRIUM LINES.