Katkat07 PDF

Physical Adsorption
Texture and morphology

pore size
pore shape
pore-size distribution (same size or various
sizes?)
pore volume
specific surface area of catalyst
Catalysis and Catalysts - Physical Adsorption
Internal Diffusion
Types of diffusion
Molecular
Knudsen
Surface (also called configurational diffusion)
Knudsen number: Kn = /l
= molecular free path length
l = characteristic pore diameter
Kn << 1
bulk diffusion
Kn >> 1
Knudsen diffusion
Pore Diameters, Shapes??

Pore diameters
micropores (< 2 nm)
mesopores (2 - 50 nm)
macropores (> 50 nm)
Experimental techniques
capillary condensation
Hg intrusion
microscopy
Shapes
cylinder, slit, ink-bottle, wedge, ...
Pore Size and Diffusion Regimes
Configurational diffusion
Surface migration
Pore Diameters and Measurement Techniques
Hg porosimetry
N2 capillary condensation
Micro
Meso
2
Macro
50
10
100
1000
Pore diameter (nm)
10000
Shape Selectivity
Reactant selectivity
+
Product selectivity
CH3OH +
Restricted transition-state selectivity
Pore Shapes
Slit
Cylindrical
Ink-bottle
Wedge
Pore Structures of Zeolites

a
ZSM-5
Mordenite
Barometric Adsorption Measurement

high vacuum
V1
P
pressure
gauge
V2
adsorbate
adsorbent
Conditions??
N2 (77.3 K)
Ar, He, CH4, CO2, Kr
Adsorption Isotherms
25
n ad (mmol/g) 1
20
15
Alumina
N2, 77 K
Desorption
10
5
Adsorption
0
0
0.2
0.4
Interpretation??
p/p
0.6
0.8
Adsorption Isotherms
nad
III
nad
II
nad
B
p/p0
p/p0
nad
VI
nad
nad
IV
p/p0
B
p/p0
p/p0
p/p0
Langmuir Adsorption Isotherm (Type I)
n ad
nad = nm = nm
p /p 0
Assumptions:
homogeneous surface
(all adsorption sites energetically identical)
monolayer adsorption (so no multilayer adsorption)
no interaction between adsorbed molecules
Kp
1+ K p
Type II and IV Isotherms

II
nad
Multilayer adsorption (starting at B)

Common for pore-free materials
B
0
IV
nad
same with
pore condensation at high p
B
p/p0
Type III and V Isotherms
nad
III
p/p0
Strong cohesion force between

adsorbed molecules, e.g. when water
adsorbs on hydrophobic activated
carbon
nad
Similar to III at low p

Pore condensation at high p
p/p0
Surface Area & Monolayer Capacity

specific surface area
(m2/g)
Avogadros number
(molecules/mol)
S = nmAmN
monolayer
capacity (mol/g)
area occupied by one

molecule (m2/molecule)
BET model: SBET
t model: St
Properties of Adsorbates for

Physisorption Measurements
Boiling Point (K)
Am (nm2/molecule)
N2
77.3
0.162
Ar
87.4
0.142
CO2
194.5
0.17
Kr
120.8
0.152
Adsorbate
N2 Adsorption Isotherm in ZSM-5

6
Langmuir Adsorption?
n ad (mmol/g) 1
5
4
3
No:
at low p strong adsorption due to

condensation in micropores
1
0
0
0.2
0.4
0.6
p/p
0.8
at higher p saturation due to finite

(micro)pore volume
BET (Brunauer, Emmett, Teller) Method

Based on Langmuir isotherm
Monolayer and multilayer adsorption
Layers of adsorbed molecules divided in:
First layer with heat of adsorption Had,1
Second and subsequent layers with Had,2 = Hcond
BET isotherm:
nad
p
1
C 1 p
=
+
p 0 p nmC nmC p 0
H ad H cond
C = exp
RT
BET equation does not fit entire adsorption isotherm

different mechanisms play a role at low and at high p
BET Model
reality
1st
For every layer

Langmuir model
model
layer
nth layer
nad = nm (0 + 21 + 32 + ...)
=1
ka0
1 = 1 p 0 = K1 p 0
kd
ka0
n = 1 p n-1 = K n p n-1
kd
k p=k
0
a 0
1
d 1
kan 1 n-1 p = kdn n
Assume
K1 = K1,0 e
K n = K n,0 e
H ads
RT
Hn
RT
K n,0 e
H cond
RT
p
p0
nad
C
=
nm
p
p
1 0 1 + (C 1) 0
p
p
with
C=e
Hads H cond
RT
Non-Porous Silica and Alumina

Low p/p0:
(B)
nad/nm
BET equation
(A)
filling of micropores
favoured adsorption at most
reactive sites (heterogeneity)
High p/p0:
capillary condensation
p/p0
Range 0.05 < p/p0 < 0.3 is

used to determine SBET
Texture Data of Commercial Catalysts

Mean dp (nm)
SBET (m2/g)
10
200
400
800
10
150
500
Zeolite
0.6-2
400-800
Activated carbon
700-1200
TiO2
400-800
2-50
Aerosil SiO2
50-200
MeOH synthesis (Cu/ZnO/Al2O3)
20
80
NH3 synthesis (Fe/Al2O3/K2O)
100
10
Reforming (Pt/Re/Al2O3)
250
Epoxidation (Ag/-Al2O3)
200
0.5
Material
Catalyst supports
Silica gel
-Al2O3
Catalysts
Adsorption at Pore Wall
Adsorbed layer
Cylindrical pore
Ink-bottle pore
Pore with shape of interstice

between close-packed particles
Kelvin Equation for Nitrogen

p
2VL 1
ln 0 =
p
RT rm
Relative pressure, p/p0
1.0
0.5
VL = 34.6810-6 m3/mol
0.0
= 8.88 mN/m
0.1
10
100
1000
rm (nm)
micro
meso
macro
10000
Hysteresis Loops
p/p0
nad
H2
nad
H3
nad
HI
p/p0
Information on pore shape
p/p0
t-method
t=
nad
0.354 nm
nm
S t = nm Am N
nad
n
0.354 109 Am N t = 5.73 106 ad
t
t
St =
nad
Note:
Proportional to St
t
nad is experimental result

t is calculated from
correlation t versus p
t-method
BET
only valid in small pressure interval
interpretation not very easy
thickness (t) of adsorbed layer can be calculated
0.354 nm
plot of t versus p for non-porous materials is the same (has been
checked experimentally)
t-plot helps in interpretation
Thickness of adsorbed layert (nm)
t-curves
Halsey
5.00
t = 0.354
0
b
ln p / p
13.99
t = 0 .1
0
0.034 log p / p
aHarkins-Jura-de Boer
p/p0
0.333
0. 5
t-plot of -alumina
10
St = 200 m2/g
n ad (mmol/g)
macropores
6
4
mesopores
St,micro= 0 m2/g
V t,micro = 0 ml/g
2
0
0.0
0.2
0.4
0.6
t ( nm)
0.8
1.0
1.2
Shape of t-plots
Adsorption isotherm
t=
nad
nad
0.354 nm
nm
t = f(p)
Non-porous
nad
Micro- and
mesoporous
Microporous
nad
nad
Smesopores
St
t
t-plot of N2 Physisorption on ZSM-5
n1
n ad (mmol/g)
n2
n 1 = liquid N 2
n 2 = solid N2
0
0.0
0.2
0.4
t ( nm)
0.6
0.8
Pore-Size Distribution of -Alumina
0.5
dV /dd (ml/g/nm)
0.4
0.3
0.2
0.1
0.0
1
10
d pore (nm)
100
1000
Mercury Intrusion Porosimetry

Hg does not wet surfaces; pressure is needed to force intrusion
From a force balance:
14860
d=
p
nm
bar
Convenient method for determining pore volume versus pore size
Mercury Intrusion Curve of -Alumina
1.2
V (ml/g)
1.0
0.8
0.6
0.4
0.2
0.0
0.1
10
p (MPa)
100
1000
Surface Areas - SHg and SBET

SHg
SBET
m2/g
m2/g
deg
Iron Oxide
14.3
13.3
130
Tungsten Oxide
0.11
0.10
130
Anatase
15.1
10.3
130
Hydroxy Apatite
55.2
55.0
130
Carbon Black (Spheron-6)
107.8
110.0
130
0.5 % Ru/-Al2O3
237.0
229.0
140
0.5 % Pd/-Al2O3
115.0
112.0
140
TiO2 Powder
31.0
25.0
140
Sintered Silica Pellets
20.5
5.0
140
Zeolite H-ZSM-5
39.0
375.0
140
Norit Active Carbon R1 Extra
112.0
915.0
140
Adsorbent
Discrepancy SHg and SBET

for Microporous Materials
Hg cannot penetrate small (micro)pores, N2 can
Uncertainty of contact angle and surface tension values
Cracking or deforming of samples
Texture Properties
N2-physisorption
Hg-porosimetry
SBET
St
Vp
dp
SHg
Vp
dp
m2/g
m2/g
ml/g
nm
m2/g
ml/g
nm
Wide Pore Silica
78
52
0.91
47
80
0.92
54
-Alumina
196
202
0.49
10
163
0.49
10
-Alumina
0.12
112
12
0.48
150
1057a
28
0.51
0.6
0.46
106
Raney Ni
76
0.14
5.80
ZSM-5
345
344
0.19
0.58
11
1.1
820b
Active Carbon
p/p0 range of 0.01-0.1 was used in the calculation.
intraparticle voids.
N2 Adsorption Isotherms & Pore Volume Distributions

-alumina
25
25
20
20
n ad (mmol/g) 1
n ad (mmol/g) 1
wide-pore silica
15
10
10
0
0
0.2
0.4
p/p
0.6
0.8
0.10
0.5
0.08
0.4
dV /dd (ml/g/nm)
dV /dd (ml/g/nm)
15
0.06
0.04
0.02
0.2
0.4
p/p
0.6
0.8
0.3
0.2
0.1
0.00
0.0
1
10
d pore (nm)
100
1000
10
d pore (nm)
100
1000

25
25
20
20
15
10
15
10
0
0
0.2
0.4
0.6
p/p
0.8
0.2
0.4
p/p
0.010
0.5
0.008
0.4
dV /dd (ml/g/nm)
dV /dd (ml/g/nm)
activated carbon
n ad (mmol/g) 1
n ad (mmol/g) 1
-alumina
0.006
0.004
0.002
0.6
0.8
0.3
} Tensile strength effect

0.2
0.1
0.000
0.0
1
10
100
d pore (nm)
1000
10
d pore (nm)
100
1000

ZSM-5
25
25
20
20
n ad (mmol/g) 1
n ad (mmol/g) 1
Raney Ni
15
10
10
0
0
0.2
0.4
p/p
0.6
0.8
0.2
0.4
p/p
0.10
0.6
0.8
10
dV /dd (ml/g/nm)
0.08
dV /dd (ml/g/nm)
15
0.06
0.04
8
6
4
2
0.02
0.00
1
10
d pore (nm)
100
1000
0.0
0.5
1.0
d pore (nm)
1.5
2.0
Hg Intrusion Curves & Pore Volume Distributions

-alumina
1.2
1.0
1.0
0.8
0.8
V (ml/g)
V (ml/g)
wide-pore silica
1.2
0.6
0.6
0.4
0.4
0.2
0.2
0.0
0.0
10
p (MPa)
100
0.1
1000
0.08
0.5
0.06
0.4
dV /dd (ml/g/nm)
dV /dd (ml/g/nm)
0.1
0.04
0.02
10
p (MPa)
100
1000
1000
10000
0.3
0.2
0.1
0
1
10
100
d pore (nm)
1000
10000
0.0
1
10
100
d pore (nm)

activated carbon
1.2
1.0
1.0
0.8
0.8
V (ml/g)
V (ml/g)
-alumina
1.2
0.6
0.4
0.4
0.2
0.2
0.0
0.0
0.1
10
p (MPa)
100
0.1
1000
0.010
10
p (MPa)
100
1000
1000
10000
dV /dd (ml/g/nm)
0.005
0.008
dV /dd (ml/g/nm)
0.6
0.006
0.004
0.003
0.004
0.002
0.002
0.001
0.000
0.000
1
10
100
d pore (nm)
1000
10000
10
100
d pore (nm)

ZSM-5
1.2
1.2
1.0
1.0
0.8
0.8
V (ml/g)
V (ml/g)
Raney Ni
0.6
0.4
0.6
0.4
0.2
0.2
0.0
0.1
10
100
0.0
1000
0.1
p (MPa)
0.10
100
1000
dV /dd (ml/g/nm)
0.005
0.08
dV /dd (ml/g/nm)
10
p (MPa)
0.06
0.04
0.004
0.003
0.002
0.02
0.001
0.00
1
10
100
d pore (nm)
1000
10000
0
1
10
100
1000
d pore (nm)
10000
100000
BET- & t-plots

-alumina
wide-pore silica
0.5
0.4
0.3
0.2
2
S BET = 78 m /g
0.1
C = 146
0.0
0.00
0.05
0.10
0.15
p/p 0
0.20
0.25
0.4
0.3
0.2
0.1
0.30
2.5
10
2.0
1.5
1.0
S t,micro=28 m2/g
0.5
S BET = 196 m2/g

C
0.0
0.00
n ad (mmol/g)
n ad (mmol/g)
p /[n ad(p 0-p )] (g/mmol)
0.5
0.05
0.10
0.15
p/p 0
0.25
0.30
6
4
S t,micro= 0 m2/g
V t,micro = 0 ml/g
V t,micro = 0.013 ml/g
0.20
= 97
0.0
0.0
0.2
0.4
0.6
t ( nm)
0.8
1.0
1.2
0.0
0.2
0.4
0.6
t ( nm)
0.8
1.0
1.2
BET- & t-plots

-alumina
activated carbon
0.5
p /[n ad (p -p )] (g/mmol)
0.4
0.3
0.4
2
S BET = 1057 m /g
C = 1057
0
p/p = 0.01 - 0.1
0.3
0.5
0.2
2
S BET = 9.3 m /g
0.1
0.2
0.1
C = 142
0.0
0.00
0.0
0.05
0.10
0.15
0
p/p
0.20
0.25
0.00
0.30
0.05
0.10
0.15
p/p
0.20
0.25
0.30
15
0.25
n ad (mmol/g)
n ad (mmol/g)
0.20
0.15
0.10
10
5
2
S t, micro= 1.4 m2/g
0.05
S t,micro = 856 m /g
V t,mcro = 0.001 ml/g
0.00
V t,micro = 0.42 ml/g
0.0
0.2
0.4
0.6
t ( nm)
0.8
1.0
1.2
0.0
0.2
0.4
0.6
t ( nm)
0.8
1.0
1.2
BET- & t-plots

Raney Ni
ZSM-5
0.5
0.4
0.3
0.2
0.5
S BET = 76 m /g
0.1
0.0
0.00
C = 46
0.05
0.10
0.15
p/p 0
0.20
0.25
0.4
0.3
0.2
= -245
0
p/p : 0.01 -0.1
0.1
0.0
0.00
0.30
S BET = 345 m /g
0.05
0.10
0.15
0
p/p
0.20
0.25
0.30
nad (mmol/g)
nad (mmol/g)
4
3
2
St,micro = 0 m2/g
2
2
St,micro= 344 m /g
Vt,micro = 0 ml/g
Vt,micro = 0.18 ml/g
0.0
0.2
0.4
0.6
t ( nm)
0.8
1.0
1.2
0.0
0.2
0.4
0.6
t ( nm)
0.8
1.0
1.2

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Physical Adsorption

Texture and morphology

Catalysis and Catalysts - Physical Adsorption

Catalysis and Catalysts - Physical Adsorption

Pore Diameters, Shapes??

Catalysis and Catalysts - Physical Adsorption

Pore Size and Diffusion Regimes

Pore Diameters and Measurement Techniques

Pore diameter (nm)

Catalysis and Catalysts - Physical Adsorption

Restricted transition-state selectivity

Catalysis and Catalysts - Physical Adsorption

Catalysis and Catalysts - Physical Adsorption

Pore Structures of Zeolites

Barometric Adsorption Measurement

Catalysis and Catalysts - Physical Adsorption

Langmuir Adsorption Isotherm (Type I)

Type II and IV Isotherms

Multilayer adsorption (starting at B)

Catalysis and Catalysts - Physical Adsorption

Type III and V Isotherms

Strong cohesion force between

Similar to III at low p

Catalysis and Catalysts - Physical Adsorption

Surface Area & Monolayer Capacity

area occupied by one

Catalysis and Catalysts - Physical Adsorption

Properties of Adsorbates for

Boiling Point (K)

Catalysis and Catalysts - Physical Adsorption

N2 Adsorption Isotherm in ZSM-5

at low p strong adsorption due to

Catalysis and Catalysts - Physical Adsorption

at higher p saturation due to finite

BET (Brunauer, Emmett, Teller) Method

BET equation does not fit entire adsorption isotherm

Catalysis and Catalysts - Physical Adsorption

For every layer

kan 1 n-1 p = kdn n

Catalysis and Catalysts - Physical Adsorption

Non-Porous Silica and Alumina

Catalysis and Catalysts - Physical Adsorption

Range 0.05 < p/p0 < 0.3 is

Texture Data of Commercial Catalysts

MeOH synthesis (Cu/ZnO/Al2O3)

NH3 synthesis (Fe/Al2O3/K2O)

Catalysis and Catalysts - Physical Adsorption

Adsorption at Pore Wall

Catalysis and Catalysts - Physical Adsorption

Pore with shape of interstice

Kelvin Equation for Nitrogen

Information on pore shape

Catalysis and Catalysts - Physical Adsorption

Catalysis and Catalysts - Physical Adsorption

nad is experimental result

Thickness of adsorbed layert (nm)

Catalysis and Catalysts - Physical Adsorption

Catalysis and Catalysts - Physical Adsorption

t-plot of N2 Physisorption on ZSM-5

Catalysis and Catalysts - Physical Adsorption

Pore-Size Distribution of -Alumina

Catalysis and Catalysts - Physical Adsorption

Mercury Intrusion Porosimetry