Activated Carbon Process

DECEMBER 1st, 2010

DOOIL KIM
PH.D.
CENTER FOR ENVIRONMENTAL TECHNOLOGY RESEARCH
KOREA INSTITUTE OF SCIENCE AND TECHNOLOGY
Activated Carbon

• Types of Activated Carbon

- PAC (Powdered Activated Carbon)
- GAC (Granular Activated Carbon)
- FAC (Fibrous Activated Carbon)

• Target of adsorption process

- Natural organic matter (NOM)
- Taste and odor (MIB, Geosmin)
- Synthetic organic compounds (e.g., pesticides)
Activated Carbon

• Macro-pores (above 50 nm diameter)

• Meso-pores (2-50 nm diameter)
• Micro-pores (under 2 nm diameter)

Pellet type
Adsorption Isotherm (Experimental Method)

C0 C0 C0
Same initial adsorbate concentration
with different amount of adsorbent
m1 m2 ••• m3

C0 = initial adsorbate concentration (mg/L)

Ce,i = equilibrium adsorbate concentration (mg/L)

mi = mass of adsorbent (g AC)

Cc = adsorbent concentration (g AC/L)

C 0  C e ,i
qe , i 
Calculate Cc
Adsorption Isotherm

• Constant temperature equilibrium relationship between solid phase

concentration (qe)and liquid phase concentration (Ce)

Log qe

Adsorbate per unit of

adsorbent (mg / g AC)

Log Ce
Equilibrium solution
concentration (mg/L)
Langmuir Isotherm

• Assumption
- Physisorption of monolayer
- Every adsorption site is equivalent
- One adsorbate molecule adsorbed per site
- No interaction between adsorbed adsorbate
• Langmuir Isotherm equation

qmax bC Mono-layer
qe 
1  bC

• Fractional coverage

Number of adsorption sites occupied q

  e
Number of adsorption sites available qmax
Langmuir Isotherm
d
• Rate of adsorption  K a C (1   )
dt
d
• Rate of desorption  K d
dt

• At equilibrium K a Ce (1   )  K d

K a Ce ( K a / K d )Ce
 
K d  K a Ce 1  ( K a / K d )Ce

qmax Ka
 b
qe Kd

qmax bC
qe  Theoretical formula
1  bC
Freundlich Isotherm

• Empirical adsorption model for solid-liquid system

- most widely used for PAC adsorption isotherms

Related to the strength of adsorption

qe  K C 1/ n
e
(Smaller 1/n = stronger adsorption)

Related primarily to the capacity of adsorption

(Bigger K = bigger capacity)
• Linearized form

1
log qe  log K  log Ce
n
Various Isotherm

Isotherm Linearized form

qma bC 1 1 1
Langmuir qe   
1  bC qe qmax bC qmax

1
Feundlich qe  K C 1/ n
e
log qe  log K  log Ce
n


V

cX X

1

 c  1 X
BET Vm (1 - X) 1  c(c - 1)X  V  1 - X  cVm cVm

BET: Isotherm for multi-layer adsorption (Langmuir model applies adsorption in each layer)
Vm = Volume corresponding to monolayer
X = ratio of adsorbate gas pressure to vapor pressure of pure liquid
c = constant Stephen Brunauer, Paul Hugh Emmett, Edward Teller
PAC Application
• Advantage
- Low capital cost
- Added either powder or slurry
- Easy to respond to water quality change

• Disadvantage
- High operating cost when high PAC doses are required for long time
- Inability to regenerate
- Low TOC removal
- Increased difficulty of sludge disposal
- Difficulty of complete removal of PAC particles from water

• Factors needed to be considered

- Types of carbon (Surface area, pore size distribution etc.)
- Degree of mixing to provide good contact between PAC and contaminants
- Contact time for maximum use of carbon
- Interference by treatment chemicals
- Water composition (pH, divalent ion, etc.) - Removal of PAC
Adsorption Kinetics
• Assumptions
- Concentration gradients exist only in radial direction.
- Surface diffusion is more greater than pore diffusion.
- Surface diffusion is described by Fick’s law.
- Activated carbon surface is homogeneous.
- No reaction on surface.
q
qs

r
Δr r q

q + Δq
 g / mg 
 L3 
Mass balance on PAC
• Mass accumulation = mass in – mass out

- Mass accumulation = q  4r 2  r

q
- Mass in =  4r  Ds   t
2

r
 q  q 
 4  r  r   Ds   t
2
- Mass out =
r

   2 q  Next page
q  4r  r  4   r
2
 Ds  t
 r  r 
Ds  2 q 
 r 
q r  r 
2

t r
Mass balance on PAC

q 4r 2 r
q   q  q 
 4r 2 Ds t  4  r  r  Ds
2
t
r r
q  q  q 
 4r Ds
2
t  4  r  2rr  r  Ds
2 2
t
r r
q  q 2 q q q 
 4r 2 Ds r  4  r 2 r   2rr  2rr  Ds t
r  r r r r 
 2 q q 
 4 r   2 r r  Ds t
 r r 
   q  
 4   r 2  Ds t
 r  r 
Ds  q 
 r 2 
q r2  r 

t r
Mass balance on PAC

• Governing equation
q Ds   2 q 
 2 r 
t r r  r 
• Initial condition

q( r )  0 t = 0 and 0  r  R

• Boundary conditions
q  qs t  0 and r = R

dq
0 t  0 and r = 0
dr
• General solutions

ir  R 
D 2 2 Ds
2  i 2 2 R 2s t ir  t i  
q( r ,t )    sin 0 r q1 ( r  ) sin dr   iDs ( 1 )  e
i
qs (  )d 
2
e R
Rr i 1 R  R 0

GAC Filtration
Influent
0 C0
MTZ decreases as
Saturated zone
Ce = C0, • Smaller carbon size
q = (qe)0
• Higher temperature

MTZ : Active
• Larger adsorbate diffusion coeff.
Mass Adsorption
Transfer • Greater strength of adsorption of
Zone
adsorbate

Fresh GAC zone

Ce = 0,
q=0

Breakthrough Point
GAC Filtration

• EBCT
Volume of column
Empty bed contact time 
Flow rate
• Bed Volume (BV)
Volume Treated
BV 
VBed
• Breakpoint concentration CB

Maximum acceptable concentration

• Critical depth LCritical

Critical depth that leads to immediate appearance of an effluent

Concentration equal to CB when column start-up

• Minimum EBCT
LCritical
EBCTmin 
Q/ A
GAC Filter Mass Balance : Liquid Phase

• Mass accumulation = mass in – mass out + mass transferred

QL, C0
- Mass accumulation = C  A    x
x
C C
Area = A - Mass in =  A    EL   t  QL  C  t
x
Δx
 C  C 
- Mass out =  A    EL   t  QL   C  C   t
C+ΔC x

- Mass transferred = next page

QL
GAC Filter Mass Balance

Bulk solution
Mass transferred =
C  K L a C  Ci  Axt
qs
Activated Ci Control volume
Carbon

Overall mass balance

C
CAx  AE L  t  QL Ct  K L a C  Ci  Axt
x
 GAC Filter Mass Balance

• Liquid side governing equation

C  2C U L C
 EL 2   K L a  C  Ci 
t x  x
• Initial condition
C  x   0 at t  0

• Boundary conditions
dC
C x 0  C0  E L x=0
dx x 0

dC
0 x=L
dx x 0
GAC Filter Mass Balance : Solid Phase

q
qs

r
Δr r q

q + Δq
GAC Filter Mass Balance
• Mass accumulation = mass in – mass out

- Mass accumulation = q  2r  r

q
- Mass in =  2r  Ds   t
r
 q  q 
- Mass out =  2  r  r   Ds   t
r

  q 
q  2r  r  2  r  Ds  t
  r 

 q 
 r 
q Ds  r 

t r r
 GAC Filter Mass Balance
• Governing equation
q Ds   q 
 r 
t r r  r 
• Initial condition

q( r )  0 t = 0 and 0  r  R

• Boundary conditions
dq
0 t  0 and r = 0
dr
q  qs t  0 and r = R

1/ n
q s  K  Ci

Ci is unknown. Therefore, we need additional equation.

dqs
 K L a C  Ci   Ds
dr rR