LECTURE 14

ADSORPTION
ADSORPTION

4/2/2018
 Mass transfer operation
 Substances present in a liquid phase are adsorbed or
accumulated on a solid phase
 Removed from the liquid

2
ADSORPTION

4/2/2018
 GAC

Granular activated carbon (20- 50 μm) and

 PAC
 Powdered activated carbon (0.5-3 mm)

3
4/2/2018
4
4/2/2018
5
4/2/2018
6
ADSORPTION PHENOMENA

4/2/2018
 Adsorption process
 Dissolved species are transported into the porous
solid adsorbent granuals by diffusion

 Chemisorption
 Dissolved species are concentrated on the solid surface of by
chemical reaction
 Physical adsorption
 Physical attraction to the surface

7
COMPARISON OF ADSORPTION MECHANISMS
BETWEEN PHYSICAL AND CHEMISORPTION

4/2/2018
Parameter Physical Chemisorption
Adsorption
Use for water Most common type of Rare in water
treatment adsorption treatment
mechanisms
Process speed Limited by mass Variable
transfer
Type of bonding Nonspecific binding Specific exchange of
mechanisms, such as electrons, chemical
van der wall forces, bond at surface
Type of reaction Reversible, Typical
exothermic nonreversible,
exothermic
Heat of adsorption 4-40 kJ/mole > 200 kJ/mole
8
APPLICATION OF ADSORPTION MATERIALS

4/2/2018
 Commercially available adsorbent
 Zeolites
 Small pore

 Exclude synthetic organic compounds (SOCs)

 Synthetic polymers,
 have only micropores

 Prevent them from adsorbing NOM

 Activated carbon
 Wide range of pore sizes

 Can accommodate large organic molecules

 Natural organic matter (NOM)

 Synthetic organic compounds (SOCs) (solvents

9

and fuels)
4/2/2018
10
 MANUFACTURING, REGENERATION, AND
REACTIVATION

4/2/2018
Pyrolytic carbonization
volatile material is removed
graphite is formed
Activation
carbon is removed from selectively from an opening of closed porosity 11
average size of the micropores is increased
MANUFACTURE FROM RAW MATERIALS

4/2/2018
 Direct production method
 Sizing of raw material, carbonization, activation, and
sieving of the product
 Coconut shell,
 relatively hard coal

 Reconstruction and pretreatment

 Peat,
 lignite,
 petrol coke, and
 bituminous coals
12
MANUFACTURE FROM RAW MATERIALS

4/2/2018
 Activation
 Chemical activation: materials contains cellulous
(combined carbonization and activation)

 Addition of dehyrading chemical (ZnCl2, H3PO4) at elevated

temperature

 Prolytical heating (degradation of the cellulose)

 Extraction of activating agent

 Low density, low proportion of micropores

 Unsuitable for removal of micropollutants
13
MANUFACTURE FROM RAW MATERIALS

4/2/2018
 Activation

 Carbon produced for water treatment

 Endothermic thermal activation process

 Contacting of a gaseous activating agent (steam with

char)

 At elevated temperature (850-1000oC)

14
 MANUFACTURE FROM RAW MATERIALS

4/2/2018
 Fig 15-2
Activation
steam
CO2

pore structure is determined by the raw material or by pretreatment

the type of activating agent, and the length and temperature of activation can have a major influence 15
on the adsorbent properties
MANUFACTURE FROM RAW MATERIALS

4/2/2018
Base material and pores
Classification of Pore size (IUPAC)

Classification of Pore size (IUPAC)

Micropores: dp <20 nm
Mesopores: 20 nm <dp<500 nm
Macropores: 500 <dp

16
 4/2/2018
(a) (b)
(c) (d)

17
 REGENERATION AND REACTIVATION OF
SPENT GAC
Table 15-4 MWH

4/2/2018
 Regeneration
 adsorbed solute molecules are removed from the carbon
surface
 through desorption in their original or modified state
(with no change in the carbon surface)
 Regeneration of water treatment carbons is seldom practiced
 Thermal, physiochemical, biological

 Reactivation of GAC
 Restoration of the adsorption capacity through partial
desorption of the solute molecules
 Then burn off carbonaceous residual 18

Regeneration and reactivation not common in case of water treatment carbon

FUNDAMENTAL OF ADSORPTION

4/2/2018
 Adsorbate-water interaction
 solubility of the adsorbate

 Adsorbate-surface interactions
 extent of adsorption is determined by the strength of
adsorbate–surface interactions
 surface chemistry

 Water-surface interactions
 determined by the surface chemistry 19
IMPORTANT FACTORS INVOLVED IN
ADSORPTION

4/2/2018
Pore size and surface area
 number of adsorption sites and the
accessibility of the sites for adsorbates

 Inverse relationship
 Smaller the pores for a given volume,
Greater the surface area
(Ex 15-1)
20
4/2/2018
21
4/2/2018
22
SURFACE CHEMISTRY AND FORCES
INVOLVED IN ADSOPRTON

4/2/2018
 Chemical Adsorption (Chemisorption)
 Adsorbate reacts with the surface to
form a covalent bond or ionic bond

 Specific to particular site or functional

groups

23
CHEMICAL ADSORPTION (CHEMISORPTION)

 Dipole attraction and repulsion

Like charge repel and opposite charge attract

4/2/2018

  
H  O H

 Hydrogen bonding
 Special case of dipole-dipole interactions
 H atom in a molecule has a partial +ve charge
 Not important in water treatment

  
H  O H 24
functional groups

4/2/2018
25
CHEMICAL ADSORPTION (CHEMISORPTION)
 Charged functional groups

4/2/2018
 Not important in water treatment

H  O   H   [55.5 moles/L]
adsorbent   R  
Polar adsorbate  

 Ionic functional group would attract water

than a polar compound (dissolved in water)
 Higher concentration of water (55.5

moles/L) 26
 Water is more polar than most adsorbates
CHEMICAL ADSORPTION (CHEMISORPTION)
 Charged functional groups

4/2/2018
 Oxygen- containing functional groups
 Reduce the activated carbon capacity
 Attract water and charged species from

water to adsorption surface

 Make complex with heavy metals

 Mediate reactions involving phenol, H2S and
HCOOH
 Removal of NOM and phenol

27
CHEMICAL ADSORPTION (CHEMISORPTION)
 Neutral molecules

4/2/2018
 London-van der Wall forces
 Related to polarizability of the adsorbate and the adsorbent

 Ionic functional group can induce dipole in neutral

species
 Attachment of neutral molecules

 Not strong
 Inconsequential in water treatment

 Polar functional group will prefer water to any nonpolar

adsorbate

28
PHYSICAL ADSORPTION

4/2/2018
 Physical forces
 exclude covalent bonding and columbic attractions
difference b/w chemical and physical adsorption may not be
distinct
 Less specific
 weaker forces and energies of bonding

 Operate over longer distances (multiple layer)

 reversible

29
PHYSICAL ADSORPTION

4/2/2018
 Organic adsorbates (from water) onto a
nonpolar adsorbent (activated carbon)
 Crosslined graphite crystallite planes (activated C)

 Form micropores
 Van der wall forces (major attractive force)

30
PHYSICAL ADSORPTION

4/2/2018
For adsorbate that are
 less polar or

 have low solubility

Attraction b/w an adsorbate and

polar solvent are weaker

31
PHYSICAL ADSORPTION
 Attraction b/w an adsorbate and activated C

4/2/2018
 Related to van Der Wall forces
 Increase with increasing polarizability and size

The effect of polarizability on London

forces. Both CH4 and Ne have eight
electrons in the valence shell. In these
CH4 these electrons form a more diffuse,
larger, and less tightly held cloud than in
Ne. This makes the CH4 electrons more
easily polarizable and the intermolecular
forces larger

 More nonpolar and large molecules tend

to adsorb more strongly to nonpolar
adsorbents (activated carbon)
Hydrophobic bonding
32
PHYSICAL ADSORPTION

4/2/2018
Illustration of Traube’s rule. Mass of carboxylic acids adsorbed on carbon versus 33
aqueous concentration; degree of adsorption increases with increasing molecular
length
PHYSICAL ADSORPTION

Adsorbility of various classes of compounds

4/2/2018
Physical forces are
strong? Class A
?

Activated
?
carbon Class b

? Class
C

34
PHYSICAL ADSORPTION

4/2/2018
 Adsorbility of various classes of compounds
 Interactions and forces are not readily measurable
 Properties of the adsorbate and solvent

 Ex. Solubility

 Direct indication of adsorption strength or magnitude of

the adsorption force

 Low solubility of adsorbate

– higher adsorption

 Solubility alone is not the only indicator 35

PHYSICAL ADSORPTION

4/2/2018
 Polar species
 will NOT be removed
 polar organics and
 adsorbate with ionic functional group

 Strong water-adsorbate forces

 Strong adsorbent-water interaction


H  O   H  

adsorbent   R
R  Polar adsorbate 
 

36
 PHYSICAL ADSORPTION
Polar species

4/2/2018
 Adsorption of acid and bases on nonpolar
adsorbent (AC)

 Depend on pH
 Strong adsorption of neutral form

 pH of maximum adsorbability depends on dissociation

constant
 Charge on activated carbon (neutral in pH 4-5)

HCl  H   Cl
adsorbent   R
H   Cl
37
most ionic organics are negatively charged and adsorbents are negatively charged at neutral pH.
PHYSICAL ADSORPTION

4/2/2018
 Neutral species
 Strongly held to nonpolar surface (graphite surface of
activated carbon)

 Adsorbate-water interaction - solubility

 Adsorbate – adsorbent interaction – polarizability
 Size of the organic compound
 Adsorbent-water interaction –
How many H2O molecules must be pulled away from the
surface of the adsorbent
How many H2O molecules must be removed from surface
the adsorbent
38
 Adorability of neutral organic species

4/2/2018
Solubility in H2O
Polarizability
adsorbent   R Size of the organic compound
adsorbate 
H2O

39
PHYSICAL ADSORPTION

4/2/2018
 Ionic species
 Adsorption of inorganics onto inorganic adsorbents

 Acid-base reactions at a functional group on surface sites

Metal ion adsorbate Hydroxide site on metal oxide adsorbent

MeOH ( aq)  SOH surface  SOMe surface  H 2Oaq

 Removal of heavy metal

 Adsorption onto silicon, aluminum-oxide-based clay and

sands
 Adsorption of ionic species to surfaces
 Electrostatic attraction 40
 Depends on pH and ionic strength
EQUILIBRIUM ISOTHERM

4/2/2018
 The affinity of the adsorbate for an adsorbent is
quantified using adsorption isotherm
 describe the amount of adsorbate that can be adsorbed onto an adsorbent at
equilibrium and at a constant temperature

Known amount of
adsorbate

Various dosage of adsorbent Fixed volume

41
 EQUILIBRIUM ISOTHERM

4/2/2018
 Adsorption isotherm
Equilibrium adsorbent-phase concentration of adsorbate, mg adsorbate/g adsorbent
Volume of aqueous-phase added to bottle, L

V
qe  (Co  Ce ) Equilibrium aqueous-
Mass of adsorbent, g M phase concentration of
Initial aqueous-phase adsorbate, mg/L
concentration of
adsorbate, mg/L

Ex 15-2
42
EQUILIBRIUM ISOTHERM

4/2/2018
 Adsorption isotherm
 Quantify affinity of the adsorbate for an adsorbent

43
EQUILIBRIUM ISOTHERM

4/2/2018
 To describe the equilibrium capacity of
asdsorbent

 Langmuir
 Freuncdlich
 Brunauer, Emmet, and Teller (BET)

44
 LANGMUIR ISOTHERM EQUATION

4/2/2018
 To describe the equilibrium between surface and
solution as a reversible chemical equilibrium
between species (fixed sites on adsorbent)
Adsorbate species bound to surface sites, mmole/m2
Vacant surface sites, mmole/m2

SV  A  S  A
Adsorbate species A in solution, mmole

Assumption
- reaction has a constant free energy change for
all sites
- each site can bind at most one molecule 45
 LANGMUIR ISOTHERM EQUATION
equilibrium condition Free energy change for adsorption, J/mole

4/2/2018
Langmuir adsorption equilibrium constant, L/mg
S.A  G o / RT
K ad  e
SV C A
Equilibrium concentration of adsorbate
species A ,mg/L
Total # of sites available or monolayer coverage, moles/m2
S.A
ST  SV  S . A   S.A
Vacant surface sites, mmole/m 2 K ad C A
ST K ad C A ST
S.A  
1  1 / K ad C A 1  K ad C A
46
 LANGMUIR ISOTHERM EQUATION

4/2/2018
Mass loading per mass of adsorbent
K ad C A ST  Aad  MWt K ad C AQM
molecular weight of adsorbate, g/mole

S . A  Aad  MWt  
2
surface area per gram of adsorbent, m /g
1  K ad C A 1  K ad C A
equilibrium concentration of adsorbate A in solution , mg/L

equilibrium adsorbent-phase concentration of

adsorbate A, mg adsorbate/g asorbent
maximum adsorbent-phase
K ad C AQM bAC AQM
qA  
concentration of adsorbate when surface
sites are saturated with adsorbate, ST Aad

1  K ad C A 1  bAC A MWt,
mg adsorbate/ g adsorbent

Langmuir adsorption constant of adsorbate A, Kad, L/mg

47
LANGMUIR ISOTHERM EQUATION

4/2/2018
 Fig 15-7 (a)

48
LANGMUIR ISOTHERM EQUATION
bAC AQM
qA 

4/2/2018
1  bAC A
CA 1 CA
 
q A bAQM QM

 Plot of CA/qA vs CA result in a straight line with

slope = 1/QM & intercept 1/bAQM

49
 FREUNDLICH ISOTHERM EQUATION

4/2/2018
 Describe the data for heterogeneous adsorbents
(activated carbon)
Freundlich adsorption capacity parameter, (mg/g)/(L/mg)1/n
empirical equation

q A  K AC 1/ n
A
Freundlich adsorption intensity parameter, unitless

1
log( q A )  log( K A )  log( C A )
n

50
FREUNDLICH ISOTHERM EQUATION

4/2/2018
 Fig 15-10

Solute-solute isotherm for tetrachloroethane, and 1,1-trichloroethane over a wide concentration range

Nonlinear regression should be used

51
BRUNAUER EMMETT-TELLE (BET)
ISOTHERM EQUATION

4/2/2018
 Extends the Langmuir model from a monolayer
to several molecular layers
 Each molecular layer, above the monolayer, is
assumed to equilibrate with layer below it
 Layers of different thickness are allowed to coexist

 For first layer

ST K ad C A ST
S.A  
1  1 / K ad C A 1  K ad C A

52
 BRUNAUER EMMETT-TELLE (BET)
ISOTHERM EQUATION
ST K C S
 Second layer S.A   ad A T
1  1 / K ad C A 1  K ad C A

4/2/2018
 Assuming that the free-energy change for layer 2 and higher
= free energy of precipitate  Goad

First layer adsorb according to forces b/w the adsorbent &

adsorbate
2nd layer adsorb as if they were forming precipitate layer Goprec
Eqilibrium adsorbent-phase
concentration of adsorbate, qA BAC A Equilibrium concentration of A, mg/L

QM CS , A  C A 1  ( BA  1)(C A / CS , A )
mg adsorbate/g adsorbent

Maximum adsorbent-phase Saturated solution concentration of A, mg/L

concentration of adsorbate
Equilibrium constant for 1st layer , L/mg
when surface sites are  Gads
o
Free energy of adsorption, J/mole
saturated with adsorbate, mg K1,ad e 53
adsorbate/g adsorbent BA    G oprec
K i ,ad e Free energy of precipitation, J/mole
Equilibrium constant for subsequent layer , L/mg
BRUNAUER EMMETT-TELLE (BET)
ISOTHERM EQUATION

4/2/2018
B> 1
b/c -Goad > - Goprec

Fig 15-9

54
4/2/2018
55
EX 15-3 DETEMINATION OF FREUNDLICH
AND LANGMUIR ISOTHERM PARAMETERS
For the experimental data given below, determine the Freundlich and

4/2/2018
Langmuir isotherm parameters. Apply linear regression to determine
the isotherm parameters. A spreadsheet can be used for this purpose.
Experimental data:
Carbon type: F-400 Carbon size: 200x400
Chemical: trichloroethane Temp: 13oC
pH 7.5-8 Equilibrium time: 31day
Sample # TCE liquid phase TCE adsorbent-phase
concentration CA, μmol/L concentration qA,
μmole/g

1 23.6 737
2 6.67 450
3 3.26 318
4 0.322 121
56
5 0.169 85.2
6 0.114 75.8
SOLUTION
 Determine langmuir isotherm parameters

4/2/2018
CA 1 C
  A
q A bAQM QM

Slope=1/QM=0.0013g/μmole  QM= 769.23 μmole/g = 1.01×105 μg/g

Intercept=1/QMbA = 0.0033g/L = > bA= 3.00 ×1-3 L/μg

57
 SOLUTION

4/2/2018
 Determine Freundlich isotherm parameters

Best fit
1
 slope  0.4327
n
log K  int ercept  2.2831

0.4327
mole  L 
K  191.9  
g  mole 
0.4327
mole 139.39 g 1mg  L mole 1000 g 
 191.9       58
g mole 1000 g  mole 131.39 g 1mg 
0.4327

mg  L 
 60.68  
g  mg 
POLANYI CORRELATION FOR LIQUID

4/2/2018
 Many organic compounds of interest in
water treatment (to be removed)

 Parameters are not available (for all)

 Experimentation Or correlation?

 Correlations to estimate isotherm

parameters
 To evaluate feasibility of using adsorption
59
POLANYI CORRELATION FOR LIQUID

4/2/2018
 Polanyi potential theory (Polanyi, 1916)
 Assumptions
1. A fixed pore volume exists that is close to

the adsorbent surface where adsorption

occurs;
2. The adsorptive forces originate from

London-van der Waals interactions

3. Adsorbing molecules will concentrate at

high-energy sites on the adsorbent surface

and undergo enhanced precipitate within
the pores of the adsorbent 60
 POLANYI CORRELATION FOR LIQUID

4/2/2018
 Adsorption potential “ε”
The work or free energy required for any molecule to
move from the bulk solution to the adsorption space
(Polanyi, 1916) Aqueous solubility of adsorbate, mg/L
C 
  RT ln  s 
C Concentration of adsorbate in bulk solution,
mg/L

Minimum energy required to extract a dissolved species

in water

61
 Close to 0

4/2/2018
 Fig 15-10

maximum

Schematic model of aqueous adsorption with equipotential surfaces 62

 ADSORPTION PARAMETER DERIVED FROM
POLANYI THEORY

4/2/2018
 Correlation to obtain adsorption parameter
 Plotting volume adsorbed vs adsorption potential
molar volume, polarizability, and
parachlor
Adsorption potential/normalizing physical property accounting
for the major cause
Polanyi constant determined
σ
for adsorption
Maximum volume of for particular adsorbent, (L/J)
adsorbate adsorbed on
Adsorption potential, J/mole
Adsorbent-phase adsorbent, mL adsorbate/g
concentration of adsorbate, adsorbent Polanyi constant determined for
 particular adsorbent, unitless
mg adsorbate/g adsorbent    
q  lW  lWo     
Liquid density of adsorbate, g/L   Vm  
Molar volume of adsorbate, L/mole
Volume of adsorbate adsorbed on
adsorbent, mL adsorbate/g adsorbent


  
ln q  ln( l W )     ln( l Wo )
 Vm  63
4/2/2018
64
 ADSORPTION PARAMETER DERIVED FROM
POLANYI THEORY
Isotherms with F400 carbon plotted as volume adsorbed versus adsorption potential
divided by the molar volume

4/2/2018
 Table 15-7
 K and 1/n

Figure 15-9
Correlation of aqueous adsorption isotherm data, using the Polanyi potential theory for isotherms, for
halogenated aliphatic organic compounds on F-400 using molar volume as a normalizing factor. The 65
best-fit line was obtained by weighting all of the data equally (adapted from Crittenden et al., 1999).
The individual compounds studied are shown on Fig. 2 of the original paper, along with a discussion of
appropriate methods of data analysis.
 4/2/2018
 Table 15-8

66
DETERMINATION OF FRUNDLICH
PARAMETER USING POLANYI THEORY

4/2/2018
 If σ =1
Liquid density of adsorbate, g/L

1 RT s

n MWt Molecular weight of adsorbate, g/mole

Wos
K
(Cs )1/ n Aqueous-phase solubility of adsorbate,
mg/L

67
DETERMINATION OF FRUNDLICH
PARAMETER USING POLANYI THEORY

4/2/2018
 If σ 1
 Procedure to determine parameters
 Eq used to calculate the volume adsorbed for several-liquid
phase values in that range     
q   W   W  
l l o
 
V 
  m  

 q values= W × liquid density

 Construct a plot

 C and q are fit using Freundlich isotherm equation

 K and 1/n

 Exp 5-14
68
POWDERED ACTIVATED CARBON

4/2/2018
 Small particle size (mean size 24 μm)

 Added to various location in the water

treatment process

 Used in treatment of taste and odor compounds

 Treatment of low concentration of pesticide

 other organic micropollutants

69
EXPERIMENTAL METHODS FOR
DETERMINING PAC DOSAGES

4/2/2018
 Jar test
 Site-specific bench-scale protocol

70
 4/2/2018
 Fig 5-13
B 34 mg/L PAC

71
 ANALYSIS OF PAC PERFORMANCE FOR
ORGANIC REMOVAL

4/2/2018
 Mass balance on the PAC and Water
Adsorbent-phase
concentration
Water flow rate L/d

QCinf  q M PAC  QCeff
Influent liquid-phase
concentration of Influent liquid-phase
Mass of PAC added per
adsorbate,mg/L concentration of
unit time, g PAC/d
adsorbate, mg/L

Adsorbent-phase concentration of adsorbate in

At equilibrium equilibrium with Ceff, mg adsorbate/g adsorbent

QCinf  q C M PAC  QCeff
eff


Powdered activated M PAC Cinf  Ceff
carbon dosage, g/L D PAC  
Q qC
eff 72
ANALYSIS OF PAC PERFORMANCE FOR
ORGANIC REMOVAL

4/2/2018
 Concentration profile for a single adsorbate in a
GAC bed

 Fig 15-15

73
ANALYSIS OF PAC PERFORMANCE FOR
ORGANIC REMOVAL

4/2/2018
 Mass balance Adsorbent-phase concentration of adsorbate in
equilibrium with influent concentration, mg
adsorbate/g adsorbent

Time to GAC t ex QCinf  q e C M GAC Mass of GAC, g

inf
exhaustion, d

M GAC C
Granular activated D GAC   inf
carbon dosage, g/L t ex Q q e C
inf

q e  KC1e/ n
1   eff  1   C eff 
C
  
D PAC
  C inf 
  C inf 

D GAC q C   C 
1/ n
 eff   Cinf 
eff
 qC  
 in f 

74
 NOM free water

4/2/2018
For 1/n=0.5-0.7
Desire removal is less than 95%
Problem is seasonal
PAC is the most economical
solution

75
FACTORS THAT INFLUENCE PAC PERFORMANCE
TYPE OF PAC
PAC-20B Nuchar SA- HydroDarco WaterCarb WPL

4/2/2018
Atochem, A 20 B Acticarb, D Calgon, E
 Table 15-10
PAC Type and Code
Westvaco, B American
Norit,C

Carbon source

Activation method

Iodine number, mg/g

Tannin value
Molases number

Molases decolo index

Phenol value
Percent ash,%

Por volume, mL/g

Mean particle size, μm

Median particle size, μm 76

Modle particle size, μm

WATER QUALITY OF NATURAL WATER

4/2/2018
Water Utility TOC, Color, Turbidity, pH Alkalinity,
Source mg/L PCU NTU mg CaCO3/L
location
Lake Manatee Manatee 12-24 100-400 1-6 6.5-7.2 11-45
Bradenton, County Public
FL Works
Department
Schuylkill The City of 2-5 10-80 1-76 7.1-8.8 29-105
River Philadelphia
phildelphia, Water
PA Department
Saskatchewan The City of 2-10 125-175 10-25 8.1-8.5 110-150
River Edmonton
Edmonton Water Branch
Alberta
Fox River The city of 2-1 30 35 7.7-8.7 153-321
Elgin, IL Elgin Water
Departmet

PCU= platinum cobalt units 77

4/2/2018
78
 LOCATION OF PAC ADDITION

4/2/2018
intake
Sand
Screening Coagulation Flocculation sedimentation Disinfection
filtration

Rapid mix

Sludge treatment

Point of Addition Advantage

Intake Long contact time, good mixing
Rapid mix Good mixing during rapid mix and
flocculation, reasonable contact time
Filter inlet Efficient use of PAC
Slurry contactor Excellent mixing for design contact time,
no interference by coagulants, additional
preceding rapid mix contact time possible during flocculation 79
and sedimentation
IMPACT OF DISINFECTANTS AND
OXIDANTS ON PAC PERFORMANCE

4/2/2018
 Oxidants: -ve impact for removal of odor causing comp.
 Cl2 and KMnO4

MIB 50-75%
 geosmin 20-40%

 PAC addition prior to the addition of oxidants

80
IMPACT OF ORGANIC MATTER ON PAC
PERFORMANCE

4/2/2018
 NOM and organic compounds of anthropogenic
origin
 Reduce the adsorption capacity in PAC
 Can block pores
 Compete with micropollutants for adsorption sites in
smaller pores

81
4/2/2018
82
IMPACT OF CONTACT TIME ON PAC
PERFORMANCE

4/2/2018
Percent MIB remaining as function o PAC dosage for several contact tim
83
USE OF PAC IN UNIT OPERATIONS

4/2/2018
 PAC application with Floc Blanket Reactors

84
USE OF PAC IN UNIT OPERATIONS

4/2/2018
 In full scale
 Typical blanket depth= 2-3m
 Hydraulic loading = 1.3-3m/h

IF
Hydraulic loading, m/h 1.5 4

Blanket depth, m 3 2
PAC dosage, mg/l
Required Blanket 120 480
concentration, mg/L
CRT, h 24
Ex 15-6 85
PAC APPLICATIONS WITH MEMBRANE
REACTORS

4/2/2018
86
PAC APPLICATIONS WITH MEMBRANE
REACTORS

4/2/2018
87
ADVANTAGES PAC/UF PROCESSES

4/2/2018
 CRT can be strictly controlled
 Based on wasting cycle
 More of the PAC capacity for micropollutant
can be utilized
 UF membranes are used for particle and
microorganism removal and PAC can
easily be added to the process
 PAC may reduce fouling b/c OM can be
removed
88
DISADVANTAGES OF PAC/UF PROCESSES

4/2/2018
 High PAC dosage or long filteration time
 Cause high head loss through the memberane

 Builtup of infectous microorganisms in the dead-

end loop.

89
IMPACT OF PAC/UF PROCESS ON
VIGNEUX-SUR-SEINE FINISHED WATER

4/2/2018
Paramter Unit 1997a 1998b Reduction,
%
TOC mg/L 2.6 0.8 69
BDOC mg/L 0.7 0.2 70
UV OD/m 2.4 0.8 67
THM μg/L 73 8 89
Turbidity NTU 0.1 0.1 0
HPC CFU/mL 5 0 100

a before PAC/UF installation, b after PAC/UF installation

HPC= heterotrophic plate count

Table 15-14 90
GRANULAR ACTIVATED CARBON
 GAC operations

4/2/2018
 Trace contaminant removal
 DOC removal
 Physical adsorption (typical mechanism)
 Organics
 Surface reactions, complexation, and ion
exchange with surface functional groups
 Inorganic constituents
 Biological activity
 Extend GAC bed life using adsorbed molecules as
electron donor/acceptor
91
GRANULAR ACTIVATED CARBON

4/2/2018
1. Gravity feed
contractor

2. Pressure contractor

3. Upflow and/or
fluidized-bed
contractors
92
GRANULAR ACTIVATED CARBON

4/2/2018
 Mass transfer zone
 Length of bed needed for the adsorbate to be
transferred from the fluid into the adsorbent

93
GRANULAR ACTIVATED CARBON

4/2/2018
 Mass transfer zone
 Breakthrough
The time when the concentration exceeds the
treatment objectives in the effluent

 Point of exhaustion
 The time when the effluent concentration
essentially equals the influent
94
MASS TRANSFER ZONE

Mass transfer zone

4/2/2018

 For a single component, constant influent
concentration, and favorable adsorption
C ( z ) q( z )

Cinf qe C
in f

C(z) = liquid-phase concentration of adsorbate at location z within the mass transfer zone, mg/L
Cinf= infuent liquid-phase concentration of the adsorbate,
C(z)/Cinf= nomalized liquid phase concentration at location z within the mass transfer zone,
dimensionless
q(z) = adsorbent-phase concentration of the adsorbate at location z, mg adsorbate/g adsorbent
qe|Cinf=adsorbent-phase concentration of the adsorbate in equilibrium with the influent
concentation, mg adsorbate/g adsorbent
q(z)/qe|Cinf= degree of saturation at location z within the mass transfer zone, dimensionless

95
EMPTY-BED CONTACT TIME (EBCT)

4/2/2018
Volume occupied by adsorber Adsorber area
media including porosity available for flow, m2 Adsorber or media
depth
volume, m3
vF A F L L
EBCT    Superficial flow
Q vAF v velocity, Q/AF, m/h

 EBCT in fixed-bed adsorption= 5-60 min

 For removal of synthetic oganic compounds= 5-3min

 Superficial flow velocity = 5-15 m/h (2-7 gpm/ft2)

96
 SPECIFIC THROUGHPUT

4/2/2018
 Volume fed to the adsorber divided by the mass
of GAC in the adsorber
(to quantify GAC adsorber)
Time to breakthrough (treatment
Volume fed to the adsorber divided by
objective is exceeded),d
the mass of GAC in the adsorber, m3/kg
Qt bk VF tbk VF tbk tbk
Specific throughpu t     Adsorber density or
M GAC EBCT M GAC EBCT  FVF EBCT  F filter bed density, g/L
Mass of GAC, kg

M GAC
F  350- 550 kg/m3

VF
Volume occupied by adsorber media including porosity volume, m 3
97
OTHER IMPORTANT TERMINOLOGY

4/2/2018
 Carbon Usage Rate (CUR)
M GAC 1
CUR  
Qt bk specific throughpu t
 Particle size
 Hardnss
 Particle size
(0.6-2.36 mm) (8×30 US mesh),0.425-1.70mm (12×40 US mesh)

 Bed porosity
 Complicated
 GAC has porosity 0.2-0.7
 Need to be considered when estimating bed porosity

98
Ex 15-7
 DETERMINATION OF SPECIFIC
THROUGHPUT AND CARBON USAGE RATE

4/2/2018
 Total quantity of adsorbate fed to the column to
the ultimate capacity of the GAC in the column
QCinf t bk  M GAC q e C
inf

qe C M GAC C
Maximum specific throughput 
Qt bk
 inf Minmum CUR   inf
M GAC Cinf Qt bk qe C
inf

99
DETERMINATION OF SPECIFIC
THROUGHPUT AND CARBON USAGE RATE

4/2/2018
 Treatment objective Ceff/Cinf or Cto

Adsorbent phase concentration

Specific throughput

If Cto is small (<0.05)

100
DETERMINATION OF SPECIFIC
THROUGHPUT AND CARBON USAGE RATE

4/2/2018
Exp 15-7
Exp 15-8 101
GAC OPERATION

4/2/2018
 BEDS in Series

102
 GAC OPERATION

4/2/2018
 BEDs in Parallel

Concentration of organic compounds remaining in

effluent, mg/L

Number of equal-
capacity adsorber
in parallel

Concentration of organic compound remaining in effluent from ith adsorber, which is determined
by dividing the effluent profile from a single adsorber into a number of intervals, mg/L
103
HW#8

4/2/2018
 15-6

 15-10
 15-11

104