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http://uchi.vscht.cz/index.php/en/studium/magisterske-studium

1
 N-stage cross-flow adsorber (repeated adsorptions)
with linear adsorption isotherm

mc1 , X0  0 mck , X0  0 mcN , X0  0

Qf , cF Qf , ck 1 Qf , ck Qf , cN

1 k N

X1 X2 XN

2
Analytical solution:

1  Q f 
n

cn     bcF  X 0   X 0 
b  bmC  Q f  
 
X n  bcn
c0  cF

3
Maybe, also counter-current stagewise adsorption could be solved
analytically when isotherm is linear?

4
 mc1 , XA  0 mc 2 , XA  0 mc 3 , XA  0

Vf , cAF Vf , cA1 Vf , cA2 Vf , cA3

1 2 3

XA1 XA 2 XA3

Given values: K = 0.413; n = 0.88; cA3=1000*10-6

cAF = 0.01

To be evaluated? cA1 , cA2 , mci/Vf

5
Solution #1

6
 eq4 was not defined & used

7
8
 Solution #2

Stage-by-stage solution:

9
10
11
12
External mass transfer resistance?
The rate of adsorption (especially from liquids) may be controlled by the rate of mass
transfer from the solution to the surface of the adsorbent.

Possible enhancement?: Stirring or other ways to turbulence (fast flow)?

kca

13
14
 Counter-current multistage adsorber
equilibrium stages

Vf , cAF c A1 c A 2 cA,k 1 c A, k c A, N  2 cA, N 1 c AN

1. 2. k. N-1. N.

XA1 XA 2 XA 3 XA k X A ,k 1 X A , N 1 XA N mC, XA, N 1  0

mC ( X A, N 1  XA1 )  Vf (cAF  cAN )

XA,N1  X A1 Vf operating line


cAF  cAN mC mC ( X A k  X A,k 1 )  Vf (cA,k 1  cAk )
X Ak  feq (cAk ), k  1,..., N
15
The set of 2N+1 equations can be solved:
by graphical method 
by algebraic/numerical methods ???

!!! Problems may occur when solving the equations:

- the adsorption isotherms are nonlinear  solvers may easily
fail,
- stage-by-stage approach seems to be more suitable (when
necessary data are known) for using solvers as Maple, Matlab
or Mathematica.

16
Loop for stage-by-stage solving.

17
18
Ads.7
500 kg/min of dry air at 20 °C, carrying 5 kg water vapour per minute are to be dehumidified
with silica gel to 0.001 kg water per kg of dry air. The operation has to be conducted
isothermally and counter-currently with 25 kg per minute silica gel.
How many theoretical stages will be required and what will be water content of the silica gel
leaving the bottom stage?

Equilibrium data at 20 °C are as follows:

kg water/kg dry silica gel 0 0.05 0.10 0.15 0.20

kg water/kg dry air 0 0.0018 0.0036 0.0050 0.0062

Four stages would be enough, water content in the adsorbent leaving the column will be 0.205 kg
water/kg ads.

19
20
 acceptable fit of Freundlich isotherm to data

parameters of Freundlich isotherm

21
Try to solve, please:

K q0 c A
XA 
1  K cA
22
 Fixed-bed adsorbers (tubular columns)
FEED STREAM

cA
z0
SATURATED ADSORBENT

ADSORPTION FRONT

CLEAN ADSORBENT

ADSORBENT BED

zL SUPPORTING SCREEN

OUTLET STREAM
z z 23
The system for balancing:

V S cA cA  dcA V

z z  dz
z
z0 zL
a surface density (m2/m3 = m-1)

 bed porosity (voidage)

dV  S dz
dVf   S dz
dVC  (1   ) S dz
dmC  C dVC  C (1   ) S dz
dA  a dV  a S dz
24
 FIXED-BED ADSORBERS
V S cA cA  dcA V

z z  dz
z
z0 zL
a

u V / S
dV  S dz
dVf   S dz cA  , z  concentration in fluid phase
dVC  (1   ) S dz q  , z  concentration in adsorbent
dmC  C dVC  C (1   ) S dz
dA  a dV  a S dz
25
Mathematical model:
• mass balance in fluid phase
• mass balance in solid phase
• l-s equilibrium or l-s mass transfer

Assumptions:
1. The system operates under isothermal conditions.
2. The equilibrium of adsorption is described by a nonlinear isotherm.
3. Intra-particle mass transport is due to Fickian diffusion, and it is characterized by
the pore diffusion coefficient, D.
4. Mass transfer across the boundary layer surrounding the solid particles is
characterized by the external-film mass transfer coefficient, kc.
5. The linear velocity of the liquid phase does not vary along the column.
6. 6. The macro porous adsorbent particles are spherical and homogeneous in size
and density.

26
 c c  dc
convective outflow
u c S d
convective inflow
u (c  dc) S d
axial dispersion  S dz dc axial dispersion
inflow outflow

c (c  dc)
 Dax S d z  dz
 Dax S d
z
z z
adsorption

(1   )S dq dz
All terms are related to time interval d

 all inflows = all outflows + accumulation

27
 c c  2c q
  u  Dax 2  (1   )
 z z 

Assuming instantaneous l-s equilibrium (negligible extraparticle mass transport

resistances):
q q c

 c 

Mass balance in particles:

c q   2c 2 c 
p  (1  p ) p  D 2  
   r r r 

28
Initial and boundary conditions:
c  cin z  0,   0
c0 0  z  L,   0

c
Dax  u  cin  c  z  0,   0
z
c
0 z  L,   0
z

q0 0  r  Rp ,   0

q
0 r  0,   0
r
 q  q
kc  c    D , r  Rp ,   0
 Kp
p
r
 
29
Mass balance in particles – derivation of the equation

c q   2c 2 c 
p  (1  p ) p  D 2  
   r r r 
dp

1 p fraction of solid phase within the adsorbent,

solid phase density is p , concentration of
adsorbed component is q (kg A/kg C)

(1   p ) p mass of solid phase per unit of volume

p inner porosity of the adsorbent – pores are filled with liquid,

concentration of solute in liquid is c (kg A/m3 B)
30
 jd,r
jd,r dr  jd,r  dr
r

jd ,r
c
Rp jd,r   D
0 r
r r  dr
r
jd,r  2c
 D 2
r r

dV  4 r 2dr

31
SPHERICAL SHELL BALANCE

 d djrd  c q
4  r  dr   jr  dr   4 r 2 jrd   p 4 r 2dr  1   p  4 r 2dr  p
2

 dr   
inner shell
outer shell surface flux
diffusional accumulation in accumulation of adsorbed
surface
flux density pore liquid component



 d jrd  2 d
 r  2rdr  (dr )   jr  r dr   r jr   p r 2dr c  1   p  r 2dr  p q
2

r j  2r dr j  r
2 d
r
jrd
r
dr  2rdr
d
r
2 jrd
r 
dr  r 2 jrd   p r 2dr
c

 1   p  r 2dr  p
q


jrd c q
2r j  r
d 2
  pr 2  1   p  r 2  p
r  
r

c q jrd 2 d
p  1   p   p   jr
  r r
32
 c
jrd   D
r

c q  2c 2 c
p  1   p   p D 2  D
  r r r

c q   2c 2 c 
p  1   p   p  D 2  
   r r r 

33
Equations to describe the system?
- mass balance of A in liquid phase
- mass balance of A within solid phase
- equilibrium
- mass transfer rate
- rate of diffusion inside particles

34
Pressure drop over the bed of adsorbent?

Carman-Kozeny equation:

particles
constant surface dynamic
density viscosity

p K a  (1   )
2 2
superficial
 u velocity
L  3

bed bed
length porosity
35
EXERCISES -ADSORPTION

36
Ads.1
Experiments yielded equilibrium adsorption data listed in the table:

XA [mg/g] cA [mg/cm3]
0.02 3.2010-9
0.08 3.2810-6
0.10 1.0010-5
0.50 3.1210-2
0.70 1.6810-1
1.00 1.00

Determine parameters of Freundlich and Langmuir isotherms using the above data.
Results: Freundlich isotherm: X A  1.00 cA0 2.0 . Langmuir isotherm does not fit the data.

37
Ads.2
Experiments yielded equilibrium adsorption data listed in the table:

XA [kg/kg] cA [kg/m3]
0.4142 0.05
0.7558 0.1
1.294 0.2
1.924 0.5
2.587 1
2.790 2
2.910 3

Determine values of parameters of the Langmuir isotherm using above given data.
Result: 0.09498 cA
XA 
1  2.7534 cA

38
Ads.3
Clear fermentation broth after separation of cells contains 810-5 mol dm-3 of immuno-
globulin G. 90% of the immunoglobulin present in the solution has to be separated by an
adsorption to a synthetic nonpolar adsorbent. Adsorption equilibrium can be described by
the isotherm:
XA  5.5  105 cA0,35
where XA is the equilibrium concentration in the adsorbent (mol cm-3) and cA is the
equilibrium concentration in the liquid (mol dm-3).
Evaluate minimum amount of the adsorbent required for treatment of 2 m3 of the broth in
a single stirred adsorption stage.

Result: 0.16 m3 of the adsorbent.

39
Ads.4
Into the vessel filled with a bed of granules of the activated carbon a solution of the acetic acid was poured in such
a way that void volume between the particles has been just filled up. The acid adsorbs to the carbon particles at
60°C. The vessel performs as an equilibrium stage. The equilibrium is expressed by relation
Xm A  3.019 cAL
0,4119

where XmA is equilibrium concentration of acetic acid within

, the adsorbent (moles CH3COOH per 1 kg of carbon)
and cAL is equilibrium concentration of CH3COOH in liquid (mol dm-3). Total volume of the bed of the adsorbent is
Vb = 1.34 m3, porosity of the empty bed is e = 0.434, inner porosity of the carbon particles is p = 0.570, density of
nonporous adsorbent is C = 1820 kg m-3. Determine amount of carbon necessary for adsorption, volume of the
acetic acid solution within the bed and concentration of acetic acid in the liquid after reaching equilibrium. Initial
concentration of acetic acid in solution is 0.25 mol dm-3.
Results: 594 kg of the adsorbent, volume of the solution 0.582 m3, concentration of acid 0.0022 mol dm-3.

Ads.5
The same final concentration of the acetic acid as in the problem Ads.4 has to be reached by the
adsorption in two consecutive stages. Determine amount of the adsorbent necessary in each stage if
volume of the liquid and other conditions will remain the same as in problem Ads.4.
Result: The first stage: 156 kg of adsorbent, the second stage 87 kg.

40
Ads.6
Albumin in a solution is adsorbed in a stirred one-stage adsorber with ion-exchange resin.
Adsorption vessel is filled with 60000 kg of the solution containing 0.0012 mass % of the
albumin and then 10 kg of dry clean ionex is used for the adsorption. the equilibrium is
described by the Langmuir isotherm
254000yA
XA 
1+30790 yA

where XA is relative mass fraction of the albumin within the adsorbent and yA is the mass
fraction of the albumin in the solution.
Determine albumin concentrations in both the liquid phase and in the adsorbent in equilibrium.
What fraction of the albumin will be transferred from the solution to the adsorbent?
Results: Relative mass fraction in the adsorbent will be 0.07 and mass fraction in the solution
will be 2.7810-7. 97.6% of the albumin will be transferred from the solution to the ionex.

41
Ads.6
An aqueous solution has to be decolourized by treatment with decolourizing adsorbent in a two-stage
counter-current adsorption unit. It is required to reduce the colour of the solution to 20% of its
original value of 9.0.
The equilibrium is described by following data in the table:
XA (adsorbent): 100 200 300 400 600 800 1000

cA (liquid): 0.186 0.59 1.15 1.86 3.64 5.87 8.51

where XA is adsorbate concentration per kg of adsorbent and cA is equilibrium colour units per kg of
solution measured on an arbitrary scale proportional to the concentration of the coloured impurity.
Estimate the amount of adsorbent required for treating 100 kg aqueous solution.

42
Ads.7
500 kg/min of dry air at 20 °C, carrying 5 kg water vapour per minute are to be dehumidified
with silica gel to 0.001 kg water per kg of dry air. The operation has to be conducted
isothermally and counter-currently with 25 kg per minute silica gel.
How many theoretical stages will be required and what will be water content of the silica gel
leaving the bottom stage?

Equilibrium data at 20 °C are as follows:

kg water/kg dry silica gel 0 0.05 0.10 0.15 0.20

kg water/kg dry air 0 0.0018 0.0036 0.0050 0.0062

Four stages would be enough, water content in the adsorbent leaving the column will be 0.205 kg
water/kg ads.

43
Ads.8
Experiments carried out in the laboratory for adsorption of papain from an aqueous solution on the
solid matrix of activated charcol revealed the following equilibrium data:

cA (g papain/L solution) 9.295 18.667 28.754 38.278 48.355

XA (g papain/g charcoal) 0.3511 0.6109 0.6614 1.1953 1.2626

Evaluate the constants of Langmuir and Freundlich isotherms and compare the results.

44
 ION EXCHANGE
Ion exchange is the process through which ions
in solution are transferred to a solid matrix (ion
exchanger) which, in turn releases ions of a
different type but of the same polarity. In other
words the ions in solutions are replaced by
different ions originally present in the solid.

Ion exchange is a rate-controlled process,

usually governed by diffusion in the bead or
the surrounding stagnant liquid film.
45
CATION EXCHANGERS: contain fixed anionic groups and movable
cations
R-SO3 H R-COO H
strong acid weak acid

ANION EXCHANGERS: contain fixed cationic groups and

movable anions

R-CH2 -N(CH3 )3 Cl

strong base weak base

46
 Cation exchange resin schematic showing
negatively charged matrix and exchangeable
positive ions

47
 Since ion exchange occurs between a solution
and the internal surface of a solid it can be
viewed as a special type of sorption process.
 There are many similarities between
adsorption and ion exchange. The two
processes are often analyzed using similar
models.
 Unlike adsorption ion exchange requires an
interchange of materials, i.e., the ions (as
opposed to a unidirectional transfer) since the
electroneutrality of the solution must be
maintained.
48
A+B A+B
resin
solution

Equilibrium constant

C AC B
K AB 
C AC B
49
 zi Ci
xi  fractional concentration of ion i in solution
C

zi Ci
yi  fractional concentration of ion i in resin
R

C ACB yA xB y A  yB  1
K AB  
C ACB yB xA x A  xB  1
only two monovalent ions
present in both phases!
yA xA
 KAB
1  yA 1  xA
50
separation factor (definition)

yA xB
AB 
yB xA

51
ION EXCHANGERS
 Stirred vessels with ion exchanger perticles in
suspension or spouted bed systems.
 Fixed-bed (column) exchangers.

52