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Nanoporous materials = Microporous( ~20nm) + Mesoporous(2~50nm) + Macroporous(50-1000nm)

Nanoporous materials : Bulk materials(Activated Carbon, Zeolites, Metal Organic Frameworks) [Adsorbent, Catalyst]
+ Membranes

Chap 1 -> Commercial adsorbents

Ch.1. Introduction

- Mixing vs. Separation Mixing favored by 2nd law

- Separation processes : Distillation, Centrifuge, Adsorption [PSA,SMB], Chromatography [GC,LC], Membrane

[Filtration], Absorption, Extraction, Crystallization, Drying, Evaporation...

- Adsorption : / Absorption :

Bulk separation vs. Purification

- Bulk separation : Conc. of adsorbed component (adsorbate) > 10wt.% in feed

- Purification : Conc. of adsorbed component (adsorbate) < 2wt.% in feed

Separation processes (Most common 4)

- Distillation : Large-scale, High energy & cost

- Adsorption : Medium-scale, Low energy & cost

- Membrane : Small-scale, Low energy & cost

- Absorption : Medium/Large-scale, High energy & cost

Adsorption processes

Pressure-Swing Adsorption (PSA) : Gas phase

Simulated Moving Bed (SMB) : Liquid phase (when separation factor < 2)

Adsorptive separation

Equilibrium separation (A,B << pore)

- Differences in equilibrium adsorption

(Isotherm )
 : &

(ex. N2/O2 separation using zeolites -> a large majority of processes .. High productivity)

Kinetic separation (A<B<pore)

- Differences in diffusion rates

pore size molecular size

(ex. O2[3.46]/N2[3.68] separation using CMS)

Steric separation (A<pore<B)

- Molecular sieving

(ex. Drying of alcohol using 3A zeolite .. H2O 2.7 / ROH>3)

Kinetic separation

- For CMS(Carbon molecular sieve), D(O2)/D(N2) = 30 -> O2 Selective

But O2/N2 zeolite CMS ( : Equilibrium separation )

Air separation can be accomplished with about 1/4 of the work that is needed for the same separation
by using N2-selctive zeolite

( N2 constitutes about 78% air)

- Other examples

CO2[3.3]/CH4[3.8] separation using CMS

C3H6[4.3]/C3H8[4.5] separation using AlPO4-14

N2[3.68]/CH4[3.8] separation using Sr-ETS-4 (Sr base zeolite)

Commercial adsorbents

- Activated carbon - $1 billion Mask , Water purification, Liquid purification

- Zeolites $100 million Gas separation(Air separation), Liquid bulk separation

Zeolite 13X Zeolite LiX

- Silica gel - $27 million Dehydrogenation

- Activated alumina - $ 26 million

 New and better adsorbents?

- Required properties of adsorbents

High selectivity

High adsorption capacity (Working capacity)

Stability (Hydrothermal, thermal, mechanical)

Regenerability

Fast adsorption/desorption

Cost

Working capacity

- Regeneration

Ch.2. Introduction

2.1. Potential energies for adsorption

Adsorption occurs when the interaction potential energy is equal to the work done to bring a gas
molecule to the adsorbed state

= G = 0 = ( 0 ) ............. (2.1)

Here, the adsorbed state is assumed to be at P0 (saturated vapor P)

total (total potential between adsorbates and adsorbent)

= adsorbate-adsorbate + adsorbate-adsorbent ... (2.2)
total = adsorbate-adsorbent ( - )

Adsorbate-Adsorbent potential for physical adsorption

= D + R + Ind + F +
Here D : dispersion E (-A/r6), R : close-range repulsion E (+B/r12)
Ind : induction E(interaction between electric field and induced dipole)
F : interaction between the electric field(F) and permanent dipole()
: interaction between field gradient(F) and quadrupole(with quadruple moment Q)

D , R : non-specific operative in all sorbate-sorbent systems

dominant for activated carbon or nonpolar sorbate (e.g. CH4)
 Ind , F , : arise from charge (which create electric fields) on the solid surface

Dipole moment : a quantity that describes two opposite charges separated by a distance
=qr

Quadruple moment : Molecules have quadrupole moments dues to the concentration of electric charge at
four separates.

2.2. Heat of adsorption

Isosteric heat of adsorption (H) at low coverage vs. sorbate-sorbent interaction potential ()

- H(=Qs) = RT + F(T) ..(2.10)

where F(T) arises due to vibrational and translational E of adsorbate

- For ambient temperature, H

- Clausius-Clapeyron equation isotherm P T

P1 H 1 1
ln ( ) = ( )
P2 R T2 T1

2.3. Effects of adsorbate properties on adsorption

For a given sorbent, the sorbate-sorbent interaction potential depends on the properties of the sorbate

D, R, Ind Non-electrostatic interactions

Strongly proportional to polarizability ()
Weakly proportional to magnetic susceptibility (x)
& x : increase with molecular weight

F, electrostatic interactions
(1) Sorbents without charges on surfaces (e.g. activated carbon)
D, R dominates ( Ind = 0)
Molecular weight ( & x) of sorbates should be different
e.g.) Xe/Kr : Xe (4.04 * 10-24 cm3) > Kr (2.48 * 10-24 cm3)
Separation is possible (Non-polar )

N2/O2 : N2 (1.74 * 10-24 cm3) O2 (1.58 * 10-24 cm3)

 Separation is impossible (Non-polar )

(2) Sorbents with electric charges (e.g. Zeolites)

F, can dominate
e.g.) N2/O2 : QN2 (-1.5) > QO2 (-0.4) N2 selective
CMS : Kinetic separation of N2/O2 mixture

2.4. Basic considerations for sorbent design

For a given sorbate molecule, the following factors are important

(1) Polarizability () of sorbent atoms
(2) Electronic charge (q) & van der Waals radii (ri) of sorbent atoms
(3) Pore size and geometry

Polarizability () of sorbent atoms

Correlated with van der Waals (dispersion) interaction
e.g.) Alkali metal (Li, Na, K), alkaline earth metal (Mg, Ca, Sr, Ba)
very high can cause strong dispersion interaction
e.g.) Cations (Li+ Na+, K+, Mg2+, Ca2+, Sr2+, Ba2+) very low

Electronic char (g) & van der Waals radius (r)

most important for electrostatic interactions
Electronic interaction is proportional to q(F, ) of q2(Ind)
Electrostatic interaction is inversely proportional to r n (where n=2~4) (r : sum of van der Waals radii of
two interacting atoms)
e.g.) Ionic radii (ri) : Li+ (0.68 ) < Na+ ( 0.98 )
-total (kJ/mol) : O2 Li+ (32) > O2 Na+ (20) 13X zeolite uses Na, air separation
N2 Li+ (51) > N2 Na+ (36)
N2 & O2 have similar D, R, Ind

Pore size & geometry

Strongly influences the adsorption potentials
Interaction potential increases with decreasing pore size
Pore geometry determines the extent of potential overlap
[Image of none sided, one sided, two sided, surrounded] ( interaction
)
Ch.3. Sorbent selection

3.1. Equilibrium isotherms and diffusion

Equilibrium isotherm Predominant basis for sorbent selection

Diffusion rate Generally secondary in importance

Equilibrium isotherms of all components in gas mixture, in P&T range of operation, must be considered

Based on isotherms, the following factors that are important to the design of the separation process can
be estimated
Capacity of sorbent, in operating P&T range
Method of sorbent regeneration (e.g. PSA, VSA, PVSA, or TSA)
Length of unusable (or unused) bed (LUB)
ex) PSA : adsorption (5-10 bar) / desorption (0.1-1 bar), T : 20~30

PSA : ,
VSA : ,
PVSA : ,
TSA : , ( : cycle time, )

Langmuir isotherm (for pure component)

<Basic assumptions>
Homogeneous surface (All sites are equivalent)
Each site can hold at most one molecule
No interactions between adsorbate molecules on adjacent sites
q
=( )= (B : Langmuir const.) (3.1)
qm 1+

( = fractional uptake, qm = monolayer adsorption)

At low P Langmuir isotherm reduces to a linear form (Henrys law)

q = K * P (K = B * qm : Henrys const.)

Langmuir-Freundlich (L-F) isotherm (for pure component)

: derived from Langmuir isotherm by assuming each sorbate molecule occupies n sites
1
q
( )= 1 . (3.3)
qm
1+

Extended Langmuir isotherm (for n-component mixture)

Bi
qi = (3.4)
1+
=1
 Here, qmi, Bi : from Langmuir isotherms for pure components
Monolayer amount for component i (qmi) in mixture is assumed to be same with that in pure component
Thermodynamically inconsistent but useful for practical design
* (N2/CO2)
* eq isotherm

Extended L-F isotherm (for n-component mixture) LRC

1


qi = 1 . (3.5)

1+
=1

Very useful for practical design and process simulation

* Dual-site L-F model (L-F )
1 1
1 1 2 2
q = qm1 1 + 2 1
1+1 1 1+2 2

Ideal Adsorbed Solution Theory (IAST) : iteration

<Basic assumptions>
Adsorbed mixture is treated as 2-D phase
At equilibrium, spreading pressures (P for 2-D adsorbed phase..
) are equal for all components)
A powerful tool for predicting mixture gas adsorption from pure component isotherms
For good predictions, pure isotherms should be fitted accurately
It predicts accurately gas mixture adsorption in many adsorbents such as zeolites and MOFs

Adsorption kinetics Diffusional time constants (D/R2)

e.g.) Short-time solution of diffusion eqn
qt 6
=
2

Assumptions : 1. A step change in gas-phase concentration

2. Clean beds initially
3. Micropore diffusion control
* mass transfer
* q-P isotherm q-t

3.3. Simple criteria for sorbent selection

Typical procedure for evaluating sorbents

Many sorbents Adsorption isotherms, D/r2
Breakthrough measurements (single column)
PSA experiments and simulations
 A quick and easily calculable parameter for sorbent selection?
(1) Knaebel(1995) : ratio of Henrys law constants
The simplest method for determining sorbent selectivity
(2) Notaro et al.(1998) : Adsorption Figure of Merit (AFM)
2
AFM = N

(N : working capacity, ads , &

(3) Rege and Yang(2001) : Sorbent Selection Parameter (S)
N1
S= (for Langmuir systems)
2
N1
S= 2
(for non-Langmuirian systems)
2

(4) For purification processes, ads dominating factor

12 1
(5) For kinetic separations, Sk = (K : Henrys constant, D : diffusivity, can be replaced by D/r2)
2 2