NPTEL – Chemical Engineering – Catalyst Science and Technology

Lecture 10

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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