C b Ad

Carbon Adsorption
ti T Technology
h l

Process Design

Dr. Liu Yu

Division of Environmental and Water Resources Engineering

1
 Factors affecting adsorption

1. Temperature: Adsorption capacity decreases as T increases

2. Molecular size and structure: Large molecules tend to be adsorbed

more strongly
g y than similar smaller molecules

• An increase solubility
y of the solute in the liquid
q carrier decreases its
adsorbability

• Branched chains are usually more adsorbable than straight chains

An increasing length of the chain decreases solubility.

• Substituent groups affect adsorbability

2
 Carbon Adsorption

Carbon as adsorbent:

•. Granular activated carbon (GAC)

•. Powered activated carbon (PAC)

3
 How to use GAC in water treatment plant?

- GAC is often used as a fixed-bed

fixed bed adsorber.

Raw
water

Coagulation
Sedimentation Filtration

Finish
water

GAC adsorber
d b
4
 Schematic of a fixed-bed GAC adsorber

Ci Ce

Ci

t
Ce
Question:
The GAC adsorber looks like a sand filter,
Would it be used for suspended solids removal?5
 Fixed-bed GAC adsorber
using
i a single
i l column
l

Metcalf & Eddy (2003)

6
Commercial Activated Carbon Adsorbers

Kaeser EverLife

R
Removal
l off Di
Dissolved
l d Organics
O i - VOC's,
VOC' Color,
C l Odor,
Od Taste
T t

7
Some design features of commercial adsorbers:

● Adsorbers from 12 in
in. to 12 ft OD
● Single or multiple adsorber systems
● In
I series
i or in
i parallel
ll l operation
ti
● Automatic or manual valves
● Carbon steel or stainless steel construction

8
Breakthrough of activated carbon adsorber
The breakthrough point is defined as
the volume of water passed through the bed before an
allowable effluent concentration is reached
Ce

Ce=Ci

Where is the breakthrough

point?

Ce=Ca
V
Vbt

9
Question:
What we need to do when the adsorber reaches
its breakthrough state?

The activated carbon must be replaced or regenerated

periodically
pe od ca y when
e itt may
ay beco
become
euunable
ab e to p
produce
oduce water
ate
with required quality

Ce

Ce=Ci

Ce=C
Ca V
Vbt
10
Factors influencing the breakthrough point:

• The breakthrough
g point
p decreases with decreased bed height,
g , Why?
y

• The breakthrough point decreases with increasing particle size of

adsorbent,, Why?
y

• The breakthrough point decreases with increased flow rate, Why?

• The breakthrough point decreases with increased initial solute

concentration, Why?

11
 GAC Regeneration

The activated carbon needs to regenerated when it

becomes unable to produce water with required quality

It is feasible to regenerate spent carbon for economic reason

In the regeneration process, the objective is to remove from the

carbon pore structure the previously adsorbed materials

12
 Ce

Ce=Ci

Ce V

Ce=Ci
GAC to be regenerated
g ×

Ce=C
Ca
V

Vbt at which GAC should be regenerated 13

The modes of regeneration:

→ Thermal to burn off adsorbed organics

→ Steam
→ Solvent extraction
→ Acid or base treatment
→ Chemical oxidation etc

14
Example of GAC Regeneration by Steam

Metcalf & Eddy 2003

15
 Analysis of GAC Adsorber or Contactor
1. Mass Transfer Zone:
The area of the GAC bed in which adsorption is occurring is called
the mass transfer zone (MTZ)

After raw water passes through a region of the bed whose depth is
equal to the MTZ, the concentration of the contaminant in the water
will be reduced to its minimum value

How to interpret this statement?

16
 GAC adsorption is supposed to proceed in a way such that

n MTZs

<MTZ
=MTZ
C

V
0
17
 Estimate of Height of MTZ
The height of MTZ (HMTZ) is related to the column height and the
throughput volumes (Metcalf & Eddy 2003 ):

⎡ VE − VB ⎤
HMTZ = Z ⎢ ⎥
⎣ E
V − 0. 5( VE − VB ⎦
)

Z = height of the adsorption column, m

VE = throughput volume to exhaustion, m3
VB = throughput volume to breakthrough, m3

18
2. Breakthrough Adsorption Capacity

In the field, the breakthrough adsorption capacity of the GAC in a full scale
column is some percentage of the theoretical adsorption capacity determined
from the isotherm. According to Metcalf & Eddy (2003),

⎛x⎞ xb ⎛ Cb ⎞ t b
⎜ ⎟ = = Q⎜ C o − ⎟
⎝ m ⎠ b m GAC ⎝ 2 ⎠ m GAC

(
(x/M) )b = field breakthrough
g adsorption
p capacity,
p y, gg/g
g
xb = mass of substance adsrobed in the GAC column at breakthrough, g
mGAC = mass of GAC in the column, g
Co = influent substance concentration, g/m3
Cb = breakthrough substance concentration, g/m3
tb = time to breakthrough, d
Q = flow rate

19
R
Remarks:
k
Because of the breakthrough phenomenon, the usual practice is either
to use two or more columns in series or to use multiple columns in
parallel so that breakthrough in a single column will not significantly
affect the effluent quality

20
 A basic mass balance equation of GAC Adsorber
For the case where the mass transfer rate is fast and the mass transfer zone is a
sharp wave front, a steady state mass balance around a GAC column can be
expressed as:

Accumulation = inflow – outflow – amount adsorbed

0 = QCot – QCet - mGACqe

Q = inflow rate, L/h

Co = influent solute concentration, mg/L
Ce = final equilibrium concentration of
solute, mg/L
mGAC = mass of GAC, g
qe = adsorption
d ti phase
h concentration
t ti att
equilibrium, mg/g
21
Rearrangement of the mass balance equation gives

mGAC Co − C e
=
Qt qe

adsorption usage rate

Questions:

a. What is the physical meaning of the adsorption usage rate?

b. In practice, a high or low usage rate is preferable?

22
Some common parameters used in design of GAC adsorber

To quantify the operational performance of GAC adsorber, the following

parameters have been developed and commonly used.

1. Empty-bed contact time (EBCT) Q

Vb A bD D
EBCT = = =
Q v f Ab v f
Vb D
Vb = volume of GAC in adsrober, m3
Q = influent flow rate, m3/h
Ab = cross-sectional area of GAC column, m2
D = length of GAC bed in adsorber, m
vf = linear approach velocity
velocity, m/h

23
2. GAC Packed density

The GAC packed density is defined as follows:

Q
mGAC
ρGAC =
Vb

mGAC, Vb
ρGAC = p
packed density
y of GAC, gg/L
mGAC = mass of GAC, g
Vb = bed volume of GAC filter, L

24
3. Specific throughput, expressed as m3 of water treated
per gram of GAC

Qt b Vb t b
Specific throughput, m 3 /g = =
m GAC EBCT × m GAC

Given GAC packed density = mGAC/Vb, thus

Ce
tb
Specific throughput, m 3 /g =
EBCT × ρ GAC

Ce=Ca t
tb
25
4. GAC usage rate (CUR), expressed as gram of GAC per m3 of
water treated

mGAC 1
CUR, g / m3 = =
Qt Specific throughput

5. Volume of water treated for a given EBCT, in liters

Mass of GAC for given EBCT

Volume of water treated, L =
GAC usage
g rate

26
6. Bed life, expressed in days

Volume of water treated for given EBCT

Bed life, days =
Q

These terms are used in the design of GAC adsorber or column

27
The application of the above terms is illustrated in this example

A fixed GAC adsorber has a fast mass transfer rate, and the mass
transfer zone is a sharp wavefront. Based on the data given,
determine the GAC requirement to treat a flow of 1000 L/min and
the bed life.

- Compound to be removed is an odor-causing organic

- Initial
I iti l concentration,
t ti Co=11 mg/L
/L
- Final concentration, Ce=0.005 mg/L
- GAC packed density = 450 g/L
- Freundlich capacity factor
factor, Kf=28 (mg/g)/(L/mg)1/n
- Freundlich intensity parameter, 1/n=0.62
- EBCT=10 min

28
Step 1 Estimate the GAC usage rate for chemical

mGAC Co − C e
= How to find qe? qe = K f C1 / n
Qt qe

mGAC Co − C e Co Co 1 mg / L
= ≈ = = = 0.036 g GAC / L
Qt qe qe K C1 / n 28 (mg
g / g)(L / mg
g) 0. 62 (1 mg
g / L) 0. 62
f o

Step
S ep 2 Determine
ee e thee mass
ss of
o GAC
G C required
equ ed for
o 10
0 min EBCT
C

The mass of GAC in the bed = VbρGAC = EBCT×Q×ρGAC

=(10 min) ×(1000 l/min) × (450 g/L) = 4.5×106 g = 4500 kg

29
Step 3 Determine the volume of water treated at 10 min EBCT

mass of GAC for given EBCT

Volume of water treated =
GAC usage rate

4.5 × 10 6 g
= = 1.26 × 108 L
0.036 g GAC / L

Step 4 Determine the bed life

volume of water treated for given EBCT

Bed life =
Q
1.26 × 108 L
= = 87.5 days
(1000 L / min)(1440 min/ day )

30
 Design of Fixed Bed GAC Column

1. Scale-up Approach
- The principal information required is a breakthrough curve from
a small column test

- The small column is operated at the same flow rate in terms of bed
volumes per unit time (Qb), as the design column

- It is assumed that the volume (Vb,test) of water treated per unit mass
of GAC for a given breakthrough in the test column is the same as
for the design column

31
The bed volume of the design column is given by

Q
Bed volume (BV) = Q is the design flow rate
Qb

The mass of GAC (M) for the design column is estimated as

M = (BV)× ρGAC ρGAC is packed GAC density

The volume (Vb,test) of water treated per unit mass of GAC in the test
column:
Vbt,test = the breakthrough volume determined from
Vbt,test the breakthrough curve for the small column test
Vb,test =
M test
Mtest = mass of GAC in the small test column

32
The mass (Mt) of GAC exhausted per hour for the design
column:

Q
Mt = Q is the design flow rate
Vb,test

The breakthrough
g time for the design
g column:
M
T= M is the mass of GAC for the design column
Mt

The breakthrough volume for the design column:

Vb,design = Q × T

33
The main advantages of the scale-up approach are

- its simplicity

- relatively few experimental data required from the

smallll column
l test
t t

34
2. Kinetic approach:

The Bohart and Adams model

⎛ Co
ln ⎜⎜
⎞
(
− 1 ⎟⎟ = ln e KN o X /v
)
− 1 − KC o t
⎝ CB ⎠

t = service time
v = linear flow rate
X = depth
p of bed
What we can do with it?
K = rate constant
No = adsorptive capacity
Co = influent concentration
CB = allowable effluent concentration

35
The Bohart and Adams model:
⎛ Co
⎜
ln⎜
⎞
( )
− 1⎟⎟ = ln e KN o X / v − 1 − KCot
⎝ CB ⎠

Since the term KNo X / v is much greater than 1, it can be simplified to

e

N ⎡ v ⎛ Co ⎞⎤ N o X 1 ⎛ Co ⎞
t= o ⎢X − ln ⎜⎜ − 1 ⎟⎟ ⎥ = × − ln ⎜⎜ − 1 ⎟⎟
Cov ⎣ KN o ⎝ C B ⎠⎦ C o v C o K ⎝ C B ⎠

No 1 ⎛ Co ⎞
t= × EBCT − ln ⎜⎜ − 1 ⎟⎟
Co CoK ⎝ CB ⎠

If we plot t versus EBCT, then we can estimate…?

36
 t

EBCT

No 1 ⎛ Co ⎞
● The slope = ● The intercept = − ⎜
ln⎜ − 1⎟⎟
Co Co K ⎝ C B ⎠

- The actual adsorption capacity No can be determined

- The adsorption rate constant K can be determined

37
Example:

Red 3BS dye adsorption by GAC

Source: Jusoh et al. 2004

38
 Concept of the critical bed depth (Xo)
The bed depth, which theoretically is just sufficient to prevent
penetration of concentration in excess of CB at zero time,
is defined as the critical bed depth (Xo)

At t=0 ⎛C ⎞
⎛ Co
ln⎜⎜
⎞
( )
− 1⎟⎟ = ln e KN o X / v − 1 − KCot Xo = −
v
ln ⎜
KN o ⎜ C B
o
− 1⎟
⎟
⎝ CB ⎠ ⎝ ⎠

Minimal bed depth!

The actual
Th t l bed
b dd
depth
th mustt
be much deeper than Xo 39
Exercise:

A lab-scale continuous carbon adsoprtion test was performed on a

raw water containing 25 mg/L of an odorous compound. The maximum
Allowed concentration of this compound is 1 mg/L. Assume that
temperature, pH and other factors are constant during the test.

The experiment used 2.5 cm GAC columns and tested at four flow rates
and
d having
h i various
i bed
b d depths.
d h

40
No. of test
of test Flow rate 
Flow rate Bed depth (m)
Bed depth (m) Time (h)
Time (h) Through Vol
Through Vol
(m3/m2.min) (m3)
1 0.081 0.61 600 1.48
1 22
1.22 1520 3 77
3.77
1.83 2450 6.07
2 0.163 1.22 430 2.13
2.44 1110 5.5
3.66 1780 8.82
3 0.326 1.52 180 1.78
3.05 530 5.25
4.57 900 8.92
4 0 652
0.652 1 52
1.52 70 1 39
1.39
4.57 430 8.52
7.62 800 15.85

41
Using
g the Bohart and Adams model:

No 1 ⎛ Co ⎞
t= × EBCT − ⎜
ln ⎜ − 1 ⎟⎟
Co CoK ⎝ CB ⎠

We can prepare the necessary plots of time versus EBCT

from the information given, and further determine K, No
and Xo

42
Bohart-Adams plots of No, K and Xo vs. flow rate:

No

Xo, m

K
Xo

0.084
43
The lab data are used to evaluate the performance of
an GAC column with 1 m diameter and 1.5 m deep. The
water flow is 95 m3/h.

Determine the service time (e.g. hours per cycle)

44
Service time:

- Water flow rate to the column = 95 m3/d = 0.066 m3/min

- Cross-section area of the column =

π π
d =
2
× ((1 m)) 2 = 0 .785 m 2
4 4
- Water flow velocity through the column =
0.066 m 3 /min
2
= 0.084 m 3
/m 2
.min = 5.04 m/h
0.785 m

- From the figure given, for a flow rate of 0.084 m3/m2.min,

No = 185 kg/m3 K = 0.37 m3/kg.h

45
Service time at X=1.5m:
No X 1 ⎛C ⎞
t= × − ln ⎜⎜ o − 1⎟⎟
C o v C oK ⎝ C B ⎠

185 kg/m 3 1.5 m 1 ⎛ 0.025 kg/m 3 ⎞

= × − ln ⎜ − 1⎟
3 3 3 ⎜
5.04 m/h (0.025 kg/m ) × (0.37 m /kg.h) ⎝ 0.001 kg/m 3 ⎟
0.025 kg/m ⎠

= 1849 h/cycle = 77 days

How to interpret this figure?

46
 Industrial applications
pp

• GAC has been selected as the best “broad spectrum” adsorbent for
the removal of organic compounds from drinking water

• GAC has been used in the water treatment industry for removal of
t t and
taste d odor
d

47
 How to use PAC in water treatment plant?

1 2 3 4
Raw Finish
water water
Coagulation
Sedimentation Filtration

Question:

PAC adsorption is employed to remove tastes and odors,

identify possible locations at which PAC can be added?

48
●. General Rule:
PAC, in slurry form, is added
→ before coagulation
g or
→ immediately before the filters

Raw Finish
water water
t
Coagulation
Sedimentation Filtration

PAC can be removed by subsequent sedimentation and filtration!

49
●. Specific Rules:
Case 1:
When relatively low doses are required (10 mg/L or less),
PAC is best added ahead of the filters

Case 2:
When relatively high doses of PAC are required,
required PAC
is best added ahead of the coagulation-flocculation
unit so that as much may be removed by sedimentation
as possible
ibl

50