6 Adsorption 2020
6 Adsorption 2020
6 Adsorption 2020
ADSORPTION
Sorption – Two kinds of processes
• Adsorption: Chemicals adhere to surface of
solid (London-van der Waals forces bind the
adsorbing molecule to the solid substrate).
- NOx from N2
- Normal paraffins from Iso paraffins
liquid phase
- Decolourization
Adsorption
• Collecting soluble substances (adsorbate) on a
suitable surface (adsorbent) by physical bonding
(electrostatic forces + van der waals forces)
– i.e. mass transfer of chemicals in liquid phase onto solid
phase
• Examples:
• Charcoal
• Kaolin
• Bentonite
• Activated carbon
• Silica gel
• Activated alumina
• Zeolite (molecular sieves)
Adsorbents
Activated Carbon (AC)
- amorphous
- hydrophobic
- organic trace removals
- air filters
Adsorbents
• High surface area 500-1600 m2/g
• Pore volume up to 0.95 cc/g
• Granular activated carbon (GAC)
grain size: 0.6-0.9 mm
• Powdered activated carbon
(PAC) grain size: 5-100 um
Powdered AC
Granuler AC
Pelleted AC
Adsorbents
Dehydration&
Carbonization Activation
Coal or wood, heat High T
Nut shells Char AC (nonpolar)
Coconut husks Hydrocarbons w/air Oxidizing gas
(steam+air+CO2)
Activated Carbon Production
Dehydration&
Carbonization Activation
Coal or wood, heat High T
Nut shells Char AC (nonpolar)
Coconut husks Hydrocarbons w/air Oxidizing gas
(steam+air+CO2)
• Activation (T=750-950 oC): Treating the tar with the mixture of steam,
air, heat and CO2 to burn off the amorphous residues (tars). The pores
are enlarged and cleaned.
Carbon regeneration
• For GAC not PAC
• Regeneration: The processes used to recover the
adsorptive capacity of the spent carbon.
– Chemicals to oxidize the adsorbed material
– Steam to drive of the adsorbed material
– Solvents
– Biological conversion processes
Physisorption Chemisorption
Reversible Chemical bonding
Arises from three types of forces: between the surface
1) van der Waals forces and the adsorbate
2) electrostatic forces : if an adsorbate and Covalent bonding
adsorbent have opposite charge
attraction
3) hydrophobic forces : a nonpolar
adsorbent will preferentially adsorb the
more nonpolar component of a polar
solution.
Adsorption Mechanism
Adsorption Mechanism
Pore volume
available to both
adsorbates and
solvent
Pore volume
available only to
solvent and
smaller
adsorbate
molecules
Porosity
available only
to solvent.
Pore size too
small for
adsorption of
impurities from
liquids
Adsorption Mechanism
Mechanisms of selectivity
𝐶
𝐶 1 1
𝐼𝑛 = −𝑘𝑡 1
𝐶𝑜 − = −𝑘𝑡 − + = −𝑘𝑡
𝐶 𝐶 𝐶𝑜
𝐶𝑜
𝐶𝑜
𝐼𝑛 = 𝑘𝑡
𝐶
1 1
− = 𝑘𝑡
𝐶𝑜 𝐶𝑜 𝐶
𝐼𝑛 1 1
𝐶 −
𝑠𝑙𝑜𝑝𝑒 = 𝑘 𝐶𝑜 𝐶 𝑠𝑙𝑜𝑝𝑒 = 𝑘
𝑡 𝑡
Adsorption Equilibrium- Adsorption
Isotherms
• Adsorption isotherms describes the relation between
the amount or concentration of adsorbate that
accumulates on the adsorbent and the equilibrium
concentration of dissolved adsorbate.
– Isotherms are equilibrium relationships that do not describe
the rate of reaction.
1 0 200 75 - -
15
X/M (mg/mg*100)
2 50 200 44 0.124 12.4
3 100 200 30 0.089 8.90
10
4 200 200 17.50 0.0575 5.75
5 500 200 6.75 0.0272 2.72 5
6 800 200 3.90 0.0177 1.77
7 1000 200 3.00 0.0144 1.44 0 25 50 75
qe
𝑠𝑙𝑜𝑝𝑒 = 𝑘
Ce
Adsorption Isotherm Models
2. Langmuir Isotherm:
• Assumptions:
– This isotherm equation assumes that fixed individual sites exist
on the surface of the adsorbents, each of these sites being
capable of adsorbing one molecule, resulting in a layer that one
molecule thick over the entire carbon surface
– All sites adsorb the adsorbate equally
S
Adsorption sites
Gas or solute molecules
Adsorption Isotherm Models
𝑄𝑜: the number of moles (or mass) of adsorbate
𝒃𝑪𝒆 adsorbed per unit mass of adsorbent at complete
𝒒𝒆 = 𝑸𝒐 surface coverage
𝟏 + 𝒃𝑪𝒆
qe: the number of moles (or mass) of adsorbate
adsorbed per unit mass of adsorbent
b: a constant
qe 𝑩𝑪𝑸𝒐
𝒒𝒆 =
𝑪
(𝑪𝒔 − 𝑪) 𝟏 + (𝑩 − 𝟏)( )
𝑪𝒔
Linearized form:
𝐶 1 𝐵−1 𝐶
= 𝑜
+ 𝑜
( )
(𝐶𝑠 − 𝐶)𝑞𝑒 𝐵𝑄 𝐵𝑄 𝐶𝑠 𝐶
(𝐶𝑠 − 𝐶)𝑞𝑒 𝐵−1
𝑠𝑙𝑜𝑝𝑒 =
𝐵𝑄 𝑜
1
𝐵𝑄 𝑜
C/Cs
Information obtained from isotherms
• Effectiveness of AC for a particular situation,
efficiencies of different AC’s
• Dosage needed
• Changes in qe with Ce (the effects of changes in
waste concentration)
• Effects of operational parameter (T, pH, water or
ww compositions)
Information obtained from isotherms
qe
Log qe
Log Ce Ce
C1
qe
Ce
Information obtained from isotherms
qe
Log qe
logbCe Ce
C1
qe
Ce
Factors influencing the rate and the
extent of adsorption
• Adsorbent characteristics • Adsorbate characteristics
– Carbon surface area – Compound solubility
– Carbon pore structure – Molecule size
– Carbon particle size – Compound ionization
– Surface polarity – Compound polarity
Pore sizes:
- Iodine: 0-2 nm
- MB : 2-5 nm
- Molasses: > 2 nm
Adsorbent Characteristics
the concentration of activated carbon in milligrams
𝑇𝑎𝑛𝑛𝑖𝑛 𝑛𝑢𝑚𝑏𝑒𝑟 = per liter required to reduce the standard tannic acid
concentration from 20 mg/L to 2 mg/L
• Used in determining the best PAC for geosmin and 2-MIB removal
• The lower the tannin number, the greater the quantity of tannic acid
adsorbed by the PAC and the lower the percentage geosmin remaining
after treatment with PAC i.e. the better the geosmin adsorption by that
PAC.
Adsorbate Characteristics
Solubility:
• Solubility is a very important factor. Soluble
compounds have strong ability for their solvent and
thus more difficult to adsorb. Yet there are
exceptions.
• As solubility decreases, the adsorption capacity
increases.
• Factors such as pH, T and ionic strength which
affect solubility will also affect adsorption.
Adsorbate Characteristics
Effect of MW,molecule structure and polarity:
• Adsorption is stongest when the pores are just large
enough to permit the molecules to enter
• Usually,
1) The increase in MW improves adsorption. However, there is a
max MW. If MW approaches to polymer size, adsorption is
inhibited.
2) Branched chains are more soluble than straight chains.
3) Molecules with low polarity are more sorbable than highly polar
ones.
Adsorbate Characteristics
4) Substituent groups affect adsorbability:
- Hydroxyl groups reduces adsorbability because of increased polarity.
- Amino group have similar but greater effect than hydroxyl group.
- Many amino acids are not adsorbed to any appreciable extent.
- Carbonyl groups have a variable effect depending on the host molecule
- Sulfonic groups decreases adsorbability.
- Nitro groups often increases adsorbability.
2) Turbidity
- As turbidity increases, the rate of adsorption decreases.
Aqueous System Characteristics
3) Agitation
- If little agitation thick-film rate-limiting step: FILM DIFFUSION
- If adequate mixing rate-limiting step: PORE DIFFUSION
4) Temperature
- T affects both the rate and the extent of adsorption.
- As T increases, the rate of adsorption also increases; however, the degree of
adsorption decreases (adsorption is exothermic)
- In general, lower T seem to favor adsorption
- T effect is highly complicated must be carefully analyzed to ensure
optimum process design Active
Amount
adsorbed adsorption
Physical
adsorption
T
Aqueous System Characteristics
5) Competing solutes
- Most WWs contain a mixture of compounds representing many different sizes
of molecules Danger of molecular screening
- Large molecules blocking the pores will prevent the entrance of small
molecules.
- Small molecules with greater mobility diffuse faster and enter the pores
ahead of the large molecules
Continuous adsorption columns
Fixed bed adsorption columns
Q, Co
Sorption zone (hz):
Zone where mass transfer occurs.
Sorption
hz
zone
Above this zone there is equilibrium
h Zone between solute in liquid and solute
movement
adsorbed.
AL
EBCT = CT = EBCT ∗ porosity (0.4 − 0.5)
Q
EBCT: Empty bed contact time
Q, C
(7-20 min, ave.10 min), for 1m bed depth
Fixed bed adsorption columns
Co
Effluent Concentration
Ce=0.95Co exhaustion
Cb=0.05Co
Volume treated
Ve
Vb Vs
Ce
Co-C
Cb
∆V Volume treated
Vb Ve
Ce
Cb
Volume treated
Vb Ve
𝑉𝑒
Am𝑜𝑢𝑛𝑡 𝑎𝑑𝑠𝑜𝑟𝑏𝑒𝑑 𝑢𝑝 𝑡𝑜 𝑒𝑥ℎ𝑎𝑢𝑠𝑡𝑖𝑜𝑛 = 0 𝐶𝑜 − 𝐶 𝑑𝑉
𝑉𝑒
𝐴𝑚𝑜𝑢𝑛𝑡 𝑎𝑑𝑠𝑜𝑟𝑏𝑒𝑑 𝑓𝑟𝑜𝑚 𝑏𝑟𝑒𝑎𝑘𝑡ℎ𝑟𝑜𝑢𝑔ℎ 𝑡𝑜 𝑒𝑥ℎ𝑎𝑢𝑠𝑡𝑖𝑜𝑛 = 𝐶𝑜 − 𝐶 𝑑𝑉
𝑉𝑏
Fixed bed adsorption columns
A = Mass of
adsorbate
B discharged from the
column
qe: capacity
qe
Co
Ce
Application
Methodology
Schematic of activated carbon
adsorption systems
Common configurations
in in
out
out
Down-flow in series Down-flow in parallel
Each bed is replaced as complete unit, Each bed is replaced as a single unit
Recharged bed is moved to polishing Due to time delay, exhaustion occurs
position sequentially
Counter curren operation
Simple operation
Ability to serve as a filter
Common configurations
out
in
Q1 Q2 Q1 Q1
Fixed bed Counter current flow Fludizied bed
moving bed
• Q1:liquid flow
• Q2:carbon flow
Schematic of activated carbon
contactor.
Two Carbon Beds on The Right
Mobile Adsorbers