SORPTION

?Is sorption a transfer or transform reaction

Transfer reaction
Objectives
 Introduce the process of sorption and the most common sorbent used.

 Introduce commonly used sorption equilibrium models.

 Design sorption reactors. ?What are the different types of reactors

Batch
CSTR
Plug flow
Dispersed plug flow
Packed bed
Outcomes Fluidized packed bed

 Know how to determine the best sorption isotherm model.

 Know how to design an activated carbon batch system.

 Know how to design an activated carbon packed bed reactor.

Introduction
Sorption is mainly used to remove trace organic compounds, but could
also be used to remove metals and other inorganic chemicals.

Sorption is a process which involves the accumulation of substances at

a surface or within the sorbing material.
?What is the difference between adsorption and absorption
Adsorption: Adherence to the surface of the material
Absorption: Adherence to the entire material

Sorption equilibrium occurs when the concentration of the contaminant

remaining in solution (C) is in balance with that at the surface (S).

C S S

C
Sketch changes in C and S versus t
Equilibrium t
A common sorbent is activated carbon

Sorbate: the chemical which is sorbed

Sorbent: the solid surface where the

chemical is sorbed

Show video 8
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ENOC refinery wastewater treatment plant
(Al Hashimi et al., 2014)

Bottled water flow sheet diagram

(Al Gazali and Al Afeefi, 2015)

Aeration Carbon bed Add

Mg
Brine +

Filter

Bottled
Ground Reverses Osmosis Filter
Water
Water
Ozonation
Filters
G.L

W.T

Well
Equilibrium Sorption Models

S
K
The Linear model .1 * S  KC
1 parameter (K) C

The Fruendlich model .2 * S  kC n

logS
n
log S  log k  n log C
logk
2 parameters (k and n) logC
1 1 1 1
The Langmuir behavior .3 *  
S b ab C

1/S
1/ab
2 parameters (a and b)
1/b
K, k, n, a, and b are constants determined in 1/C
the lab for each sorbate-sorbent combination.

What is the unit of K of the linear [K] = [S] / [C] = (mg/g) / (mg/L) = L/g
Example
Laboratory tests were conducted on a waste containing 50 mg/l phenol.
Five bottles containing 1 liter of the waste were dosed with powdered
activated carbon. When equilibrium was reached, the contents of each
bottle were analyzed for phenol. The results are shown in the following
table. Determine the best sorption isotherm model to be used.
Equilibrium concentration of the Carbon, g Bottle
aqueous phase (C), mg/l
13 0.1 1
6.0 0.2 2
1.0 0.9 3
0.25 1.6 4
0.08 2.7 5
Solution
Determine the equilibrium S, mg/g C, mg/l M, g Bottle
concentration on the solid phase (on 370 13 0.1 1
the carbon) using the mass balance
approach: 220 6.0 0.2 2
CoV=CV+MS
54.4 1.0 0.9 3
where Co is the initial concentration
(=50 mg/l) and V is the volume of 31.1 0.25 1.6 4
solution (= 1 liter for each bottle) 18.5 0.08 2.7 5

For Bottle 1:
(50 mg/L) * (1 L)= (13 mg/L) * (1 L) + (0.1 g) * S
S=370 mg/L

Now plot
• S versus C (linear model)
• log S versus log C (Freundlich model)
• 1/S versus 1/C (Langmuir model)
 420
360 Linear model
300
Based on R2 values, the Freundlich model
would be the best as its R2 is 0.98 (closer to

S, mg/g
240
180
120
y = 30.056x 1.0), then the linear model (R2 =0.96) and then
60
R 2 = 0.9634 the Langmuir model (R2=0.91).
0
0 5 10 15
C, mg/l
But the linear model has one parameter and
3
the Freundlich model has two. To account for
2.5
Freundlich model differences in the number of model
2 parameters, we use the corrected Akaike
log S

1.5
Information Criteria (AICc) to judge between
1
0.5
y = 0.5968x + 1.8582
the Linear and Freundlich models.
R2 = 0.9826
0
-1.5 -1 -0.5 0 0.5 1 1.5
log C

0.06
0.05
Langmuir model
0.04
1/S

0.03
0.02
y = 0.0039x + 0.0086
0.01 R 2 = 0.9073
0
0 5 10 15
1/C
Corrected Akaike Information Criteria (AICc)

 SSR  2( P  1)( P  2)
* AICc  N ln    2( P  1) 
 N  N P

N = Number of data points

420
SSR = Sum of squares residuals 360
P = Number of model parameters 300

S, mg/g
240
180
y = 30.056x
120
R2 = 0.9634
60
0
Residual 0 5 10 15
C, mg/l

Criterion: The smaller the AICc value, the better the model is.
 Linear model
Squares Residual Predicted Estimated
residuals S S C M Bottle
429.6 20.7 390.7 370 13 0.1 1
1573.2 39.6- 180.3 220 6.0 0.2 2
594.8 24.4- 30.1 54.4 1.0 0.9 3
556.0 23.6- 7.5 31.1 0.25 1.6 4
258.7 16.1- 2.4 18.5 0.08 2.7 5
3412.4 SSR

420
360
300
S= 30.056 C
S, mg/g

240
180
120
y = 30.056x S= 30.056 * 13= 390.7
R 2 = 0.9634
60
0
0 5 10 15
C, mg/l
 Freundlich model
Squares Residual Predicted Estimated
residuals S S C M Bottle
1338.9 36.6- 333.4 370 13 0.1 1
96.6 9.8- 210.2 220 6.0 0.2 2
313.1 17.7 72.1 54.4 1.0 0.9 3
0.2 0.4 31.5 31.1 0.25 1.6 4
6.3 2.5- 15.9 18.5 0.08 2.7 5
1755.1 SSR

3
2.5
2 Log S= 0.5968 Log C + 1.8582
log S

1.5
1
Log S= 0.5968 Log 13 + 1.8582
y = 0.5968x + 1.8582
0.5 R2 = 0.9826 Log S= 2.523
0
-1.5 -1 -0.5 0 0.5 1 1.5 S= 333.4
log C
  SSR  2( P  1)( P  2)
* AICc  N ln    2( P  1) 
 N  N P

AICc SSR P+1 P N Model

39.6 3412.4 2 1 5 Linear
43.3 1755.1 3 2 5 Freundlich

The linear model is

better than the
Freundlich model
for this case
Exercise
In the previous example, what is the mass of activated carbon needed to
reduce the concentration of 60 m3 of wastewater from an initial phenol
concentration of 50 to 5 mg/L in a batch reactor?

Solution
To determine the mass of activated carbon (M), use the mass balance
approach:

CoV = CV + MS

where Co is the initial concentration (=50 mg/l), C is the final concentration

(5 mg/l), and V is the volume to be treated (= 60 m3).

The sorbed concentration (S) is determined based on the selected

equilibrium model (in this case, S= 30.056 C). Thus,
(50)(60×103) = (5)(60×103) + M (30.056×5)
Hence, M= 17966 g ~ 18 kg
 Design of Carbon Bed Reactors
Laboratory Field
Co
Q

Carbon
bed

Cout
Q

Breakthrough
Callowable point
Scale-up Approach
Design criteria: The hydraulic retention time in the lab and field are the same
V  V 
*  column    column 
 Q laboratory  Q  field

Vcolumn  r 2 L

M
Packed carbon density  The moisture content and the
Vcolumn bulk density should be the
Vwater same in the lab and the field
Moisture content of column 
Vcolumn

 Vtreated   Vtreated 
Design equation : *   
 M laboratory  M  field
Example
A phenolic wastewater having a TOC of 200 mg/l is to be treated by a fixed
bed granular activated carbon with a wastewater flow of 150 m 3/d, and the
allowable effluent concentration is 10 mg/l as TOC. A breakthrough curve
shown in the figure below has been obtained from an experimental pilot
column. The laboratory column has the following characteristics:

Column diameter= 9.5 cm

Length= 1.04 m
Mass of carbon= 2.98 kg
Flow rate= 12.39 liter/hr
Bulk density= 400 kg/m3

Using the scale-up approach determine

The design column volume (i.e., the column volume in the field)
The design mass of carbon (i.e., the mass of carbon in the field)
The breakthrough volume in the field
The breakthrough time in the field
Solution
Vcolumnlab  r 2 L   (4.75) 2 (104) / 1000  7.37 liter

V 
Vcol  field   col   Q field
 Q lab
Vcol-field= [7.37 (liter)/12.39 (liter/hr)] [150 (m3/d)/24 (hr/d)]= 3.74 m3

M 
M field     Vcol  field    Vcol  field
 Vcol lab
Mfield= (400)(3.74)= 1500 kg

From graph, Vtreated-lab= 2000 liters with carbon mass of 2.98 kg. Using
V 
Vtreated  field   treated   M field
 M  lab
.Thus, the breakthrough volume (Vtreated) in the field= 1006 m3

Breakthrough time = Vtreated-field/Qfield= 1006/150= 6.7 days

Kinetic Approach
Design criteria: The hydraulic retention time in the lab and field are the
same. Also, the bulk density and moisture content in the lab and the field
should be the same.
Design equation: Thomas expression

C 1
 k1
Co ( qo M  C oV )
Q
1 e
k1= rate constant
qo= maximum solid phase concentration
V= treated volume
Intercept Slope

 Co  k1 q o M k1C o
* ln   1   V
 C  Q Q
Plot ln (Co/C-1) versus V and determine the slope (-k1Co/Q) and intercept (k1qoM/Q)
 Kinetic Approach
Steps for Solving a Problem

Get lab data

C t V=Q*t ln [(Co/C)-1] (Co/C)-1

ln [(Co/C)-1]

Intercept

Slope

From slope and intercept values

of the best fit line, find qo and
Substitute qo and k1 values in the below equation
k1. These values are the same
and solve for the unknown parameter in the field.
for lab and field conditions.
C  kq M kC
ln  o  1  1 o  1 o V
C  Q Q
Example
For the previous example find the volume treated in the field using the kinetic approach
and assuming the mass of activated carbon in the field column is 1500 kg.

Solution
V= Q*t, where Calculated based on
Given lab data Q=12.39 L/hr Co= 50 mg/L
Plot ln (Co/C-1) versus V 25
20
y = -0.0074x + 18.494

ln (Co/C)-1
15
10
5
0
Slope=-k1Co/Q= -0.0074 -5
0 1000 2000 3000 4000
Intercept= k1qoM/Q=18.494 V

.From the slope and intercept values, find k1 and qo using the data for the lab column
Given M=2.98 kg, Co= 200 mg/l and Q=12.39 liters/hr
Thus k1=0.00046 liter/(hr-mg) and qo=167158 mg/kg

Substitute the values of k1 and qo in the main equation and apply using the field
conditions to determine the treated volume in the field.
C  k q M k1C o
ln  o  1  1 o  V
 C  Q Q
Close to the volume
.Given Co=200 mg/l, C=10 mg/l, Q=150 m3/d, M=1500 kg found by the scale up
Thus, the treated volume is 1053.7 m3 approach =1006 m3
Conclusion
 Sorption is a process that involves the accumulation of sorbate on
the surface or within the sorbent.

 Sorption equilibrium is modeled commonly using either a linear,

Fruendlich or Langmuir models.

 Packed bed reactors could be designed by the scale-up or the

kinetic approach.