CEB2093

REACTION ENGINEERING II

CATALYST MATERIALS

Content prepared by: Dr Mohd Hizami Mohd Yusoff Prof Ir Dr Suzana Yusup
Edited by: AP Dr Suriati Sufian

1
 Topics

• Physical structure of representative heterogeneous

catalysts
• Preparation and forming of catalysts
• Catalyst properties and characterization
 Learning Outcome

By the end of this chapter, students should be able to;

• Understand the porous materials
• Explain steps in catalyst preparation process
• Describe and apply selected catalyst characterization
methods
 Physical structure of
heterogeneous catalysts
 What are porous materials?
Porous solid: a solid with pores, i.e. cavities or channels
A catalyst that has a large area resulting from pores is called porous catalyst.

Non-porous solid Porous solid

• Low specific surface area • High specific surface area
• Low specific pore volume • High specific pore volume
• The porous structure enables the solid to
have a total surface much higher.

• Most common catalysts have a specific

surface area between 1 and 1000 m2/g,
while their external specific surface area is
in the range 0.01 – 10 m2/g.

• Sometimes pores are very small they will

prevent large ones from entering. This is
called molecular sieves.

• These sieves can form basis for quite

selective catalysts
Pore Size Classification
 Mesoporous materials
• Mesoporous form (2 nm – 50 nm) of silica
• Used as catalyst support due to:
• High surface area
• Large pore size
• Uniform pore SEM of SBA-15
• High stability
• Common type of mesoporous silica
• SBA-15
• M41S family (MCM-41, MCM-48 and MCM-50)
*SBA = Santa Barbara Amorphous
*MCM = Mobil Composition of Matter

TEM of SBA-15
 M41S family

HEXAGONAL CUBIC LAMELLAR

• MCM-41
• MCM-48
• MCM-50

Different structures of the M41S family

Preparation and forming of catalysts
 Preparation of
heterogeneous
catalyst

Bulk preparation Impregnation

Physical mixing
process process

Supports are first prepared by • Mixed agglomerated catalysts

Bulk preparation is mainly
done by the following bulk preparation methods and
then impregnated with the
methods :
catalytically active material. The
• Precipitation process
active materials can be deposited
• Sol gel process
on the supports by:
• aqueous solutions
• liquid solid interface.
are prepared by this method.
• Mixing the active substances
with a powdered support or
precursors of support in ball
mill.
• The final mixture is then
agglomerated and activated.
Basic unit operations
in solid catalyst
preparation
 Preparation and Forming
Preparation of the Support
Pellets Monoliths
-Colloidal sol -Prepare ceramic paste Deposition of Active Component
formation -Extrusion*2 Precipitation or Impregnation (adsorption)
-Gel formation -Calcination Washing
-Aging to form gel -Wash-coating Filtering
-Washing to purify -Drying Drying
-Drying to form -Calcination Calcination
xerogel
-Calcination

Formulation*1 Activation
Redraw
-Pelletization Reduction from C. H.
-Extrusion Sulfiding Bartholome
w et al.,
-Sphere prilling Fundament
als of
Industrial
Catalytic
Forming Processes
2nd ed.,
Wiley
1. Pellet formulation may follow deposition
Interscience
2. Deposition of active components may be done prior to monolith extrusion (2006).
 Preparation of catalyst by impregnation

• Impregnation is achieved by filling the pores

of a support with a solution of the metal salt.

• The catalyst is prepared by adding the

support material to a solution of a suitable
metal salt, followed by drying, and activation
(calcination and reduction).
Impregnation, drying and activation

Porous support
Drying Drying

Filtration Drying-up Filtration Drying-up

Precursor
solution No adsorption Adsorption

Pore filling
 Impregnation, drying and activation
2-1. Making the finished catalysts
(1) Impregnation, drying and activation
- Mass balance of the solution and solute when adsorption does not occur-
Metal content (mass fraction)
Activation (I)
Ms [g] C1M SVSP M
Vsp [L/g] C1M SVSP M + M S

(II)
Metal content (mass fraction)

V [L] C1[mol/L] V [L] C1[mol/L]

Ms = Mass of support [g]

Vsp = Specific pore volume of support [L/g]
V = Volume of metal salt solution [L]
Ci = Metal salt concentration of the solution [mol/L]
No adsorption M = Atomic weight of the metal
 Impregnation, drying and activation
2-1. Making the finished catalysts
(1) Impregnation, drying and activation
- Mass balance of the solution and solute when adsorption occurs -
Metal content (mass fraction)
Activation (III)
Ms [g] (C1 − C2 )V + C2 M SVSP M
Vsp [L/g] (C1 − C2 )V + C2 M SVSP M + M S

(IV)
Metal content (mass fraction)

V [L] C1[mol/L] V [L] C2[mol/L]

Ms = Mass of support [g]

Vsp = Specific pore volume of support [L/g]
V = Volume of metal salt solution [L]
Ci = Metal salt concentration of the solution [mol/L]
Adsorption equilibrium M = Atomic weight of the metal
 Impregnation, drying and activation
2-1. Making the finished catalysts
(1) Impregnation, drying and activation
External surface
The difference of particle
may depend
on the contact
angle
Pore

Center of particle

Cress
section of
particle

C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
 Impregnation, drying and activation
2-1. Making the finished catalysts
(1) Impregnation, drying and activation

*only acting as a reservoir tank

which supplies solution of C0 to
“micro” pore.

Y. Uemura et al., “Formation of Nickel Concentration Profile in Nickel/Alumina Catalyst during Post-Impregnation
Drying,” J. Chem. Eng. Japan, 20 (2), 117-123 (1987).
 Impregnation, drying and activation
2-1. Making the finished catalysts
(1) Impregnation, drying and activation

Y. Uemura et al., “Formation of Nickel Concentration Profile in Nickel/Alumina Catalyst during Post-Impregnation
Drying,” J. Chem. Eng. Japan, 20 (2), 117-123 (1987).
 Impregnation, drying and activation
2-1. Making the finished catalysts
(1) Impregnation, drying and activation

How can we
empirically observe the
concentration profile
before drying?

Y. Uemura et al., “Formation of Nickel Concentration Profile in Nickel/Alumina Catalyst during Post-Impregnation
Drying,” J. Chem. Eng. Japan, 20 (2), 117-123 (1987).
 Impregnation, drying and activation
2-1. Making the finished catalysts
(1) Impregnation, drying and activation

Y. Uemura et al., “Formation of Nickel Concentration Profile in Nickel/Alumina Catalyst during Post-Impregnation
Drying,” J. Chem. Eng. Japan, 20 (2), 117-123 (1987).
 Impregnation, drying and activation
Activation =Calcination + Reduction
The purpose of calcination is to decompose the catalyst precursor to form oxides.
The decomposition temperature [ºC] of the precursors (salts) is as follows:

Group Element Hydroxide Carbonate Nitrate Sulfate

Group 11 – Copper family IB Cu (II) 60-80 220 170 650

Group 12 – Zinc family IIB Zn 125 140-300 NA 740
Group 6 – Chromium family VIB Cr (III)370 NA NA (II)850, (III)160
Group 7 – Manganese family VIIB Mn (IV)210 (II)100, 375 (II)200 NA
Fe (III)350-400, 190 (II)>200 NA (II)>170, (III)480
Group 8, 9, 10 – iron, cobalt,
nickel family VIII Co 300 (II)350, 250 (II)100-105 (II)>720, 700
Ni 230 300 (II)105-110 >700, 840

A. Ozaki et al., Catalyst Preparation Chemistry, Kohdan-sha (1980).

Impregnation, drying and activation
Support

Impregnation Ni(NO3)2 solution

Drying
Ni(NO3)2

Calcination NiO
Activation

Reduction
Ni
 Catalyst Forming

Mainly, solid catalysts are used in industrial

catalytic processes and these are formulated in
different forms such as pellets, extrudates,
granules or sphere form.

The techniques:
• Pellet formation
• Granulation
• Extrusion
• Spray drying
 Catalyst
granule

PELLET FORMATION GRANULATION

EXTRUSION
Spherical catalyst
SPRAY DRYING
Catalyst properties
& Characterization
 Catalyst properties
& Characterization
1. Whole catalyst (active component and support)
1) Size and shape
2) Densities
3) External surface area/volume
4) Parameters for pore
Porosity, specific pore volume, specific surface area and
average pore diameter
5) Specific surface area
6) Pore size distribution

2. Metal (active component) on support

1) Content and fraction of reduced metal
2) Particle size
3) Radial concentration profile of active component
 Characterization of heterogeneous catalyst
“Determination of its physical and chemical characteristics, which are
responsible for its performance in a reaction”

Characteristics
Physical of Catalyst Chemical
Properties Properties
• Surface area • Chemical composition
• Pore analysis Morphological • Acidity/basicity

Properties
• Internal structure (TEM)
• External structure (SEM)
Analystical Equipment & Its Function
 Physical Properties

Surface Area and pore analysis

• Determination of surface area and pore distribution of catalysts is
important to understand the extent of dispersion possible for the
active metals.
• Higher surface area of support results in higher dispersion of the
active metals.
• Hence supports of higher surface area are desirable.
• N2 adsorption-desorption analysis is commonly used.
 Physical Properties

• The specific surface area was measured using the Brunauer-Emmett-

Teller (BET) method
• Pore size distribution was measured using the Barrett-Joyner-
Halenda (BJH) model.
• The total pore volume was measured based on the nitrogen
adsorption at relative pressure (P/Po) of 0.98.
• The micropore area was estimated based on the correlation of t-
Harkins and Jura (t-plot method).
 N2 adsorption-desorption isotherms

BET range?

N2 adsorption-desorption isotherms of SBA-15, ZrSBA-15 and SZSBA-15.

 Determination of surface area
using BET Equation
x 1 c −1
= + x
v(1 − x) vm c vm c
From the linear plot, vm
can be obtained.
From vm [cm3/g], the surface area can be calculated:

vm − 20
S= N A Am 10
22414
= 4.35vm
S = specific surface area [m2/g]
vm= the amount of adsorbate required to form one monolayer over the entire
adsorbent surface [cm3/g]
NA = the Avogadro number
Am = the surface area occupied by one molecule [Å2], 16.2 for N2
 Pore Analysis

• Pores are usually formed during drying or calcination of hydroxides

precipitates or gel.
• The size and number of pores determines the internal surface area.
• Pore size also determines the accessibility of reactants to the active
sites and the ability of diffusion of products back to the bulk fluid.
• Hence pore structure and surface area must be optimized to provide
maximum utilization of active sites for a given feed stock.
 Measurement methods for
pore size distribution
Definition

1)Macropore: >50 nm Mercury porosimetry

2)Mesopore: 2-50 nm Nitrogen adsorption

3)Micropore: 0.8-2 nm

4)Sub-micropore: <0.8 nm
 Pore Size Distribution

Pore size distribution of SBA-15, ZrSBA-15 and SZSBA-15

catalysts.
 Textural Characteristics

Textural characteristics of SBA-15, ZrSBA-15 and SZSBA-15

 Thermogravimetric Analysis (TGA)

• To determine:
• thermal stability
• content of moisture
• volatile material, if any,
• decomposition of inorganic and organic material in the catalysts.
• Analysis is carried out by raising the temperature (up to 1000oC) of
the sample gradually in a flow of air or inert gas such as N2.
• The change in mass of samples is monitored with an increase in
temperature at specified gas environment and heating rate.
TGA Profiles
 Morphological Properties

Scanning Electron Microscopy (SEM)

• Most widely used type of electron microscope for study of microscopic
structure.
• Image is formed by focused electron beam that scans over the surface
area of specimen.
 Surface Morphology

SEM images of SBA-15 at a

magnification of 5000 X (a) after
being incorporated with zirconia and
(b) after subsequent sulfation with
sulfuric acid.

SEM images of SBA-15 at a (a)

magnification of 20000 X and
(b) magnification of 3000 X.
 Surface Morphology

SEM images of (a)

5SZSBA-15, (b)
10SZSBA-15, (c)
15SZSBA-15 and (d)
20SZSBA-15 catalysts
with magnification of
10000X.
 Transmission Electron Microscopy (TEM)
• A microscopy technique where a beam of electrons is transmitted
through a specimen to form an image
• Capable of displaying magnified image of thin specimen with
magnification in range of 103 to 106.
• Information can be obtained:
• Topography : surface features , texture
• Morphology : shape and size of the particles
• Crystallographic arrangement of atoms
• Composition : elements and the their relative amounts
 Transmission Electron Microscopy (TEM)

TEM images of SBA-15 (a) in the

direction perpendicular to the pore
axis (b) SBA-15 in the direction of the
pore axis.

TEM images of SBA-15 after (a)

incorporation of zirconia and (b)
after sulfation.
 Chemical Properties
Temperature-programmed desorption of ammonia (NH3-TPD)
• Provide information about the strength of the acid sites (weak,
moderate, strong) present on the surface.
• Small molecular size allows NH3 to penetrate into all pores of the solid
• NH3 is basic in nature it adsorbs on the acidic sites on the surface.
• The acidic sites are quantified in terms of total ammonia molecules
adsorbing on the surface in μmol/gm of catalysts.
• However, ammonia adsorption cannot distinguish between Bronsted
or Lewis acid sites and only determines the total acidic sites
 NH3-TPD profiles

weak acid site = <200 oC

moderate acid sites = between 200 and 450 oC
strong acid sites = >450 oC

NH3-TPD profiles of 5SZSBA-15 catalyst.

 Temperature-programmed desorption of
carbon dioxide (CO2-TPD)

• To determine the basic strength of catalyst.

• CO2 is an acidic gas and can absorb on basic sites on the catalyst
surface.
• This technique gives the total basic sites quantified by total CO2
molecules adsorbed on the surface in μmol/g of catalyst
 Energy dispersive X-ray (EDX)
• To identify the elemental composition of materials

EDX results of the catalyst and support

Energy dispersive X-ray (EDX)

Element Weight% Atomic%

O 70249.55 77.13
Si 34222.39 21.40
S 867.41 0.48
Zr 5169.10 1.00

Totals 110508.50
 Yield vs Conversion
Comparison of palmitic acid conversions
and monopalmitin yield using SBA-15,
ZrSBA-15, SZSBA-15 and without
catalyst
SZSBA-15 has higher activity
due to high acidity of catalyst.
SZ has the lowest activity due to
low surface area and low acidity
of catalyst.
Large pore size allowed the
formation of byproducts.
The agglomeration of the catalyst could
explain the formation of bulkier
molecules (di-and triglycerides) from the
reaction on the external surface and
within the voids of SZSBA-15.
 Reaction Machi
Category Size Shape ne
Feed
system

Size & shape Powders Suspension 0.1-80mm

Crush
er
Lump

Crush
Granules Fixed bed 2-14mm Lump
er
20- Spray-
small Fluidized bed Slurry
100mm dryer
Spher mediu Fluidized bed,
0.5-5mm Fryer Sol
es m fixed bed
Fixed bed, Rotating Powde
large 5-25mm pan r
moving bed
Pellets, tablets & Pelletize Powde
rings Fixed bed 3-20mm r r
0.5- Extrud
Extrusions Fixed bed er
Paste
20mm
Honeycomb Extruder Paste
Fixed bed - etc etc
(monolith)
Weaving
Screen (gauze) Fixed bed - machine Wire

A. Ozaki et al., Catalyst Preparation Chemistry, Kohdan-sha (1980) etc.

 Density
Solid (or material) density Particle density
m m m
Definition  solid = = (1)  particle = (2)
vsolid v particle − v pore v particle

 particle v partcile − v pore v pore

= = 1− = 1 −  particle (3)
 solid v particle v particle

Relationship  particle =  solid (1 −  particle ) (4)

m: Mass of one particle M: Total mass of the particles in the bed

vsolid: Volume of solid part of one particle
vparticle: Volume of one particle
vpore: Volume of pore in one particle
Vparticle: Total volume of the particles in the bed
Vbed: Bed volume Vvoid: Void volume of bed
particle: Particle porosity = 0.4-0.7 bed: Bed porosity = 0.4-0.45
 Density
Particle density Bed (or Bulk) density

Definition m M
 particle =
m
= bed
=
M
=
M
(5)  bed = (6)
v particle v
bed
particle V particle Vbed − Vvoid Vbed

 bed V − Vvoid V
= bed = 1 − void = 1 −  bed (7)
 particle Vbed Vbed

Relationship bed =  particle (1 −  bed ) (8)

m: Mass of one particle M: Total mass of the particles in the bed

vsolid: Volume of solid part of one particle
vparticle: Volume of one particle
vpore: Volume of pore in one particle
Vparticle: Total volume of the particles in the bed
Vbed: Bed volume Vvoid: Void volume of bed
particle: Particle porosity = 0.4-0.7 bed: Bed porosity = 0.4-0.45
 External surface area / volume
Single particle or particles Bed
6
s particle / v particle = S particle / V particle = (9) Sbed / Vbed (10)
d particle

Relationship
6
Sbed / Vbed = ( S particle / V particle )(1 −  bed ) = (1 −  bed ) (11)
d particle

sparticle: External surface area of one particle

vparticle: Volume of one particle
dparticle: Diameter of particle
Sparticle= Sbed: Total external surface area of the particles in the bed
Vparticle: Total volume of the particles in the bed
Vbed: Bed volume
bed: Bed porosity = (Vbed-Vparticle)/Vbed = 0.4-0.45
(S/V)bed is an index indicating external surface area per bed volume.
We need to compare particle bed and honeycomb at the same S/V.

32 cm2/cm3

9 cm2/cm3
from Eq. 7 by
assuming bed =
0.5 12 cm2/cm3

9 cm2/cm3

Cells/in2

C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
 Parameters for pores
Particle porosity, p = pore vol of particle / vol of particle
(dimensionless)

Specific pore volume, Vsp = pore vol of particle / mass of particle

[cm3/g] etc

Specific surface area, Ssp = surface area of particle / mass of particle

[m2/g] etc

Average pore diameter, dpore [nm] etc

From Vsp and Ssp

From pore size distribution: (1) Modal
(2) Volume-weighed average =
 d dVpore

 dV
 Parameters for pores
Specific pore volume, Vsp = pore vol of particle / mass of particle
[cm3/g] etc

m m v particle − v pore
 solid = = −1
 solid =
vsolid v particle − v pore m

m v particle
 particle = −1
 particle =
v particle m

v pore
−1
 particle −  solid = −1
= Vsp
m
 Average pore size

Specific pore volume, Vsp = pore vol of particle / mass of particle

Specific surface area, Ssp = surface area of particle / mass of particle

Average pore diameter, dpore From Vsp and Ssp

L Liq. nitrogen filling


Vsp = 2
d pore L
4 Vsp
d pore d pore = 4
S sp
S sp = d pore L
The BET method
 Average pore size

Average pore
diameter

Y. Uemura et al., “Formation of Nickel Concentration Profile in Nickel/Alumina Catalyst during Post-Impregnation
Drying,” J. Chem. Eng. Japan, 20 (2), 117-123 (1987).
 BET Equation

 p
vm c 
v=  p0  0.05<p/p0<0.35

  p    p   p 
1 −   1 −   + c 
  p0     p0   p0  
v = the amount of adsorbate on adsorbent at equilibrium [mol/kg] or [cm3/g] etc.
vm= the amount of adsorbate required to form one monolayer over the entire
adsorbent surface [mol/kg] or [cm3/g] etc.
c = system constant (function of kinetic constants and heats of adsorption), ≈100
p = partial pressure of adsorbate (subscript 0 denotes saturation)
S. Brunauer, P.H. Emmett na dE. Teller, J. Am. Chem.Soc., 60, 309 (1938).
 BET Specific Surface Area
x 1 c −1
= + x From the linear plot, vm

v(1 − x) vm c vm c can be obtained.

From vm [cm3/g], the surface area can be calculated:

vm − 20
S= N A Am 10
22414
= 4.35vm
S = specific surface area [m2/g]
vm= the amount of adsorbate required to form one monolayer over the entire
adsorbent surface [cm3/g]
NA = the Avogadro number
Am = the surface area occupied by one molecule [Å2], 16.2 for N2
 Pore Size Distribution
Lower
nitrogen
The Kelvin equation for pressure
capillary condensation

p − 2 Vliq cos 
ln( ) = Pores filled with
liquefied N2
2r k
Empty pores
p0 rk RT p
p0
At p, the pores less than rk are
filled with liquid nitrogen.
Higher
nitrogen
pressure
2r k
p = the pressure of nitrogen (subscript 0 denotes saturation)
= the surface tension of liquid nitrogen [N/m] Vliq = the molar volume of liquid nitrogen [m3/mol]
= contact angle between liq and solid rk = the Kelvin radius [m]
R = the gas constant [J/mol•K] T = the absolute temperature [K]
Pore Size Distribution
Gas vol to liq vol

Accumulated amount

dVsp/d(logdpore)
of nitrogen, Vsp
[cm3/g]
Pore diameter, dpore [nm]
(log scale)

P/P0 to rk, rk to dpore

 Pore Size Distribution

The modal pore diameter

Seon-Ju Park et al., “Influence of bimodal pore size distribution of Ru/Co/ZrO2–Al2O3 during Fischer–Tropsch
synthesis in fixed-bed and slurry reactor,” Journal of Molecular Catalysis A: Chemical, 298, 81-87 (2009)
More Characterization
More Characterization
More Characterization
More Characterization
More Characterization
More Characterization
 Metal: Active Component

1) Content and fraction of reduced metal

Metal content
a) Dissolving the catalyst (whole or metal part) and analyzing the
concentration of ion (Atomic Absorption Spectrophotometer or Induction
Coupled Plasma Spectrophotometer)
b) Estimation from the preparation condition
b-1) Impregnation: from the precursor concentration used and the pore
volume of the support
b-2) Co-precipitation: from the amounts of precursors for co-precipitation

Fraction of reduced metal

a) Measuring the consumption amount of air or oxygen during oxidation
of the catalyst
a-1) Breakthrough of oxidation agent pulse
a-2) Thermo-gravimetry
 Metal: Active Component
2) Particle size
a) Transmission electron microscopy
b) Powder X-ray diffraction
c) Hydrogen adsorption
The surface-average is recommended.
2.5wt% Pt/SiO2 (TEM)
 i
d 3

d 32 = i

 i
d
i
2

J.R. Anderson, Structure of Metallic Catalysts, Academic Press (1975).

 Metal: Active Component
2) Particle size
a) Transmission electron microscopy
b) Powder X-ray diffraction
c) Hydrogen adsorption

Bobserved
Signal intensity

Bragg angle, 2
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
 Metal: Active Component
2) Particle size
a) Transmission electron microscopy
b) Powder X-ray diffraction
c) Hydrogen adsorption

d i
4
K
d = i
=
d B cos 
43 3
i d
i

B =B2
d
2
observed −B 2
instrument Silicon powder

d 43 = the volume-mean diameter of metal particles [Å]

d i = the diameter of particle i [Å]
K = the Scherrer constant (0.84-0.89)
 = the X-ray wave length [Å]
 Metal: Active Component
2) Particle size
a) Transmission electron microscopy
b) Powder X-ray diffraction
c) Hydrogen adsorption

H2
Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt
Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt
Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt
Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt
Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt

Support Support

Metal dispersion (fraction of metal exposed)

N S (number of surface metal )

DM = 0  DM  1
NT (number of total metal )
 Metal: Active Component
2) Particle size
a) Transmission electron microscopy
b) Powder X-ray diffraction
c) Hydrogen adsorption

d i
3
V i
vM N T vM 1
d 32 = i
=6 i
=6 =6
d
i
i
2
S i
i sM N S sM DM
d 32 = the surface-mean diameter of metal particles [m]
d i = the diameter of particle i [m]
vM = the volume per metal atom in the bulk [m3]
sM = the effective average area occupied by one metal atom in the surface [m2]
 Metal: Active Component

2) Particle size
DM vs. d32 for Ni and Pt
DM

d32 for Ni
d32 for Pt
J.R. Anderson, Structure of Metallic Catalysts, Academic Press (1975).
 Metal: Active Component
2) Particle size
a) Transmission electron microscopy
b) Powder X-ray diffraction
c) Hydrogen adsorption

d i
3
V i
vM N T vM 1
d 32 = i
=6 i
=6 =6
di
i
2
S i
i sM N S sM DM
Calculate the relationship between d32 [nm] and DM(dimensionless) for Ni.
Pay attention to the consistency among the units.

atomic weight
vM = Ni atomic weight = 58.69
density  Avogadro number Ni density = 8.90 g/cm3
The Avogadro number = 6.02x1023
sM = 6.49  10 − 20 [m 2 / Ni atom]
 Metal: Active Component
2) Particle size
Comparison of the methods

From hydrogen adsorption

From XRD, TEM and so forth

C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
 Metal: Active Component
3) Radial concentration profile of active component
a) Electron probe microanalyzer (EPMA)

Probe: electron beam

Signal: X-ray
from the metal
Detection depth
= 1mm
Catalyst

b) Optical photography (qualitative observation)

* In both cases of a) and b), the cross-section must be exposed.
Y. Uemura et al., “Effect of Nickel Concentration Profile on Selectivity of Acetylene Hydrogenation,” J. Chem. Eng.
Japan, 22, 287-291 (1989).
 Metal: Active Component

3) Radial concentration profile of active component

Radial profile control is sometimes useful for:
1) Avoiding the decay by poisoning or coking
2) Controlling the selectivity of successive reaction
3) Improving net effectiveness factor

The keys for S1, S2, U and

Y are corresponding to the
profiles in the last sheet.

Y. Uemura et al., “Effect of Nickel Concentration Profile on Selectivity of Acetylene Hydrogenation,” J. Chem. Eng.
Japan, 22, 287-291 (1989).
 Metal: Active Component
Composite membrane catalyst

EPMA results of LaNi5 membrane (cross section) after reaction

SEM image 2D copper signal (EDX)
 1600
1400

Intensity　[cps]
1200
1000
800
600
400
200
0
20 30 40 50 60 70 80 90
2θ[°]

2500
Cu
2000
Intensity　[cps]

1500

1000

500

0
20 30 40 50 60 70 80 90
2θ[°]

1200
1000 　　C
Intensity　[cps]

　　Ni
800
　　Cuprite
600
400
200
0
Powder XRD spectra of LaNi5; fresh
20 30 40 50 60 70 80 90
(top), Cu-plated (center) and after
2θ[°]
reaction (bottom)
Further
Reading

C. H. Bartholomew et al.,
Fundamentals of Industrial
Catalytic Processes 2nd
ed., Wiley Interscience
(2006).