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Lecture 6

Catalyst characterization

Characterization of heterogeneous catalyst refers to the determination of its physical and

chemical characteristics, which are responsible for its performance in a reaction.
Characteristics of catalysts include:

• Chemical composition of the bulk and surface of the solids

• Surface area and porosity ( micro, meso and macro)
• Bulk solid structure, phase composition, crystallite size
• Surface morphology
• Surface chemical properties such as:
o location and oxidation state of active metals
o acid-base property
o reducible – oxidizable property
• Aggregate properties such as aggregate or particle size, density, mechanical
strength and attrition resistance
• Catalytic properties : activity , selectivity, stability

Objectives of characterization

The primary objective of catalyst characterization is to understand the relationship among

physical, chemical and catalytic properties. For this purpose, the physical and chemical
properties are determined by various characterization techniques and related to its activity
and selectivity. This is essential for design and process optimization. The
characterization is also done to monitor the changes in physical and chemical properties
of the catalyst during preparation, activation and reaction stages for better understanding
and quality control. Determination of the extent of deactivation of catalysts during the
reaction process is also important. Characterization of used catalysts can help to
determine the causes of deactivation and minimize it. It also helps to design procedures
for catalysts regeneration.

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Characterization Techniques

In this section some of the characterization techniques that are most commonly used will
be discussed. These techniques are summarized below.

1. Structural analysis
(a) Surface area
• widely accepted BET ( Brunauer, Emmet and Teller) method used for analyzing
multilayer physisorption isotherms of inert gases to determine the surface area
(b) pore analysis by
• BJH method
• mercury intrusion method
(c) X-Ray Diffraction (XRD) :
• can detect crystalline materials having crystal domains greater than 3-5 nm.
• characterization of bulk crystal structure and chemical phase composition.

2. Chemisorption technique
• determines dispersion of metal in catalysts
• determination of surface metal area

3. Thermal analysis
(a) temperature programmed reduction (TPR) :
• measures the rate of reduction of active metals as function of temperature.
• can be correlated with activity of catalysts
(b) temperature programmed desorption (TPD) :
• measurement of rate of desorption of adsorbed molecules as function of
temperature
• mainly used to of study acid –base property of catalysts
(c) Thermo Gravimetric Analysis (TGA) :
• measurement of weight loss (or gain) as a function of temperature in a
controlled gaseous atmosphere;

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• process associated with mass change can be detected and analyzed

(d) Differential Thermal Analysis (DTA)
• monitoring the temperature difference between sample and reference
• process associated with latent heat of transition can be detected and analyzed

4. Spectroscopic techniques
(a) Infra red spectroscopy
• identify compounds and investigate sample composition
• Study of structure and bonds
(b) Raman spectroscopy :
• study of oxidation state and interaction of metal oxides

5. Microscopic technique
(a) Scanning electron microscopy (SEM):
• image the topography of solid surface
• resolution better than 5 nm.

(b) transmission electron microscopy (TEM) :

• determines the micro –texture and micro structure
• resolution better than 0.2 nm

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Surface area, pore size, pore volume determination

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.

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.

Working principle and instrumentation

The basic components of volumetric physical adsorption analyzer as shown in Fig. 1 are:

1) Analysis manifold of accurately known volume and temperature

2) Vacuum system with valve to manifold

3) Source of adsorptive gas (typically, N2) with valve to manifold

4) Pressure transducer and temperature sensor

5) Sample tube connected to analysis manifold

6) Liquid nitrogen bath

Determination of internal surface area is based on adsorption and condensation of N2 at

liquid N2 temperature, 77K. Initially, the sample is evacuated at 293-523 K (120-250 oC)
followed by cooling to 77 K by liquid N2. Then gradually the partial pressure of nitrogen
above the sample is increased. Some quantity of gas will be adsorbed by the sample and
removed from the gas phase. After stabilization the equilibrated pressure is recorded and
amount of nitrogen adsorbed at each equilibrated pressure is noted. The isotherm, volume
adsorbed as function of relative pressure p/po, is plotted from the data. The pressure over
the sample is gradually increased until pressure reaches near saturation pressure, by when

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the complete adsorption isotherm is developed. The desorption isotherm is measured by

a step-wise reduction in pressure until a low pressure over the sample is achieved.
Although the volumes are adsorbed at different conditions, the values are reported at STP
conditions. Fig. 2 shows a typical N2 adsorption and desorption isotherm at 77 K for
alumina.

Adsorptive gas
(N2)
Valve
Analysis manifold

To vacuum pump Temperature sensor

Pressure Transducer
for evacuation

Sample tube

Liquid nitrogen
container

Fig. 1. Basic components of volumetric physical adsorption analyzer

Isotherm
350

300

250
Volume Adsorbed cc/g (STP)

200

150

100

50

0
0 0.2 0.4 0.6 0.8 1

Relative Pressure Ps/Po

Fig. 2. A typical N2 adsorption and desorption isotherm at 77 K for alumina

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Adsorption using Argon and Krypton

Krypton is used as adsorbate at 77 K for low surface area analysis while, Argon
adsorption at 77 K and liquid argon temperature (87K) is often used for micro and
mesopores analysis.

To measure very low surface area the number of molecules trapped in the void volume of
sample cell needs to be reduced. The number of molecules left in void volume can be
reduced by using adsorbate such as Krypton with low vapor pressure at liquid nitrogen
temperature. The saturation pressure of Krypton at liquid nitrogen temperature is 0.35
kPa which is much lower compared to that of N2 (101.3 kPa). Consequently the number
of Krypton molecules in free space of sample cell, at any given relative pressure, is
significantly reduced compared to that of nitrogen at liquid nitrogen temperature, though
amount of adsorption will be only slightly less. Hence, Krypton adsorption at 77 K is
much more sensitive and can be applied to measure surface areas down to 0.05 m2. The
cross sectional area used for Krypton is 0.202 nm2.

For analysis of ultramicropores less 0.7 nm, the nitrogen adsorption at 77 K is not
satisfactory. The pore width of 0.7 nm corresponds to bilayer thickness of nitrogen
molecule. For ultramicropores, pore filling occurs at relative pressure of 10-7 to 10-5,
where the rate of diffusion and attainment of adsorption equilibration is very slow.
Consequently measurement becomes time consuming and may also cause non-
equilibrated adsorption isotherms with erroneous results. On the other hand argon fills the
micropores of dimension 0.4-0.8 nm in most cases at much higher relative pressure as
compared to nitrogen. This leads to accelerated diffusion and equilibration process and
result in reduction of analysis time as well as increase in accuracy. Argon adsorption is
advantageous for pore size analysis of zeolites and other microporous materials.

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The typical surface area values of different supports and catalysts are summarized in
Table 1.

Table 1. Typical surface area values of different support and catalyst.

Support/catalyst BET surface Application

area

m2/g

Activated carbon 500-2000 Used as support for various process

Zeolites 500-1200 Used as catalyst and support

Al2O3-SiO2-Zeolites 100-600 Fluid catalytic cracking catalysts

Ni/Al2O3 100-150 Methanation catalyst

Cu/Zn/Al2O3 Methanol synthesis catalyst

MnOx/Al2O3 140-180 Catalyst for total oxidation of volatile

organic carbon

Fe/K/Al2O3 20 Ammonia synthesis catalyst

Determination of surface area using BET Equation

As discussed earlier (lecture 4), the BET equation describes the relationship between
volume adsorbed at a given partial pressure and the volume adsorbed at monolayer
coverage. BET equation can be written in the form :

p 1 c −1 p
= + --------------- (1)
v ( p0 − p ) vm c vm c p0

p = partial pressure ; po =saturation pressure at the experimental temperature ;

v = volume adsorbed at p; vm = volume adsorbed at monolayer coverage ; c =
constant

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p
Monolayer coverage is determined using BET equation. The is plotted as a
v ( p0 − p )

p p
function of . The plot is linear in the range of relative pressures = 0.05 - 0.3. At
p0 p0

higher relative pressure p/po, the BET plot deviates from linearity as non-ideality or pore
condensation was not accounted for the derivation of BET equation.

Slope and intercept of this linear plot is used for determination of monolayer capacity vm .

The intercept and slope from the plot is given as

1 ( c − 1)
Intercept = Slope =
cvm cvm

1
Then the monolayer volume vm is given as , vm = ( STP )
slope + intercept

The total number of N2 molecules adsorbed corresponding to monolayer volume vm can

be calculated as

vm (m3 ) × 6.02 ×1023 (molecules / mol )

No. of N 2 molecules =
0.0224 (m3 / mol )
Now , each adsorbed N2 molecule occupies an area of surface comparable to its cross
section area of 0.162 nm2.

 vm (m3 ) × 6.02 ×1023 (molecules / mol ) 

SA ( m 2
)  3  ×16.2 ×10
−20
(m 2 / N 2 molecule)
 (0.0224 m / mol ) 

Or SA ( m 2 ) = vm ( m3 ) × 4.36 ×106 (m −1 ) = 4.36 × 106 vm

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Solved problem :

1.Nitrogen was employed to determine the surface area of 1.0 g sample of silica gel and
results obtained shown in table below. The sample of silica gel was maintained at the
normal boiling point of liquid nitrogen (77K). One molecule of nitrogen occupies 16.2 ×
10-20 m2 area of plane surface. Calculate the specific surface area of silica gel by the BET
method. The saturated vapor pressure p0 of nitrogen at 77K is 101.3 kPa.

Equilibrium Pressure, p [kPa] 5.0 6.3 7.5 9.0 11.2

Volume adsorbed, (STP), V × 106 6.7 7.0 7.2 7.4 7.7

[m3]

Solution :

p 1 C −1 p
The BET equation in following form is used. = +
V ( p0 − p ) Vm C Vm C p0

p p
The is plotted as function of . The plot is shown in Fig. 3.
V ( p0 − p ) p0

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Table 1. Calculation for plot of BET equation

v p po p/po p/[v(po-
p)]
m3 kPa kPa
m-3

6.7E-06 5 101.3 0.049 7.75E+03

7.0E-06 6.3 101.3 0.062 9.47E+03

7.2E-06 7.5 101.3 0.074 1.11E+04

7.4E-06 9 101.3 0.089 1.32E+04

7.7E-06 11.2 101.3 0.111 1.61E+04

Fig. 3. Linear plot of BET equation

Intercept = 943.5 m- 3 ; Slope = 137486 m- 3

1 1
Monolayer volume =
Vm = = 7.22 ×10−6 m3 (STP)
slope + intercept 137486 + 943.5

Then surface area for 1 gm sample can be determined as :

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 7.22 ×10−6 m3 × 6.02 ×1023 molecules / mol 

SA  −6 3  ×16.2 ×10−20 m 2 / N 2 molecule
 22400 ×10 m / mol 

= 31.4 m2

As initially 1 gm sample was used, specific surface area of sample = 31.4 m2/g

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