Fine Chemicals Technology

CLL786
Catalysis in Fine Chemicals Technology
Prof. Rajesh Khanna
Department of Chemical Engineering
Indian Institute of Technology Delhi

February 15, 2016

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Introduction

Generic potential energy diagram showing the effect of a catalyst in a hypothetical

exothermic chemical reaction X + Y Z . The presence of the catalyst opens a
different reaction pathway (shown in red) with a lower activation energy. The final
result and the overall thermodynamics are the same.

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Usage in chemical industry

Over 80% of the industrial bulk chemical

processes.
much less usage in fine and speciality chemicals
processes.
huge potential is there.

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Framework
1. Chemists approach: potential of catalysis in
different classes of reactions

selective reduction
selective oxidation
CC bond formation

2. Engineers approach
2.1 principles of catalysis
2.2 properties of catalysts (activity, selectivity and
stability)
2.3 physical and chemical structure of catalysts
2.4 preparation of catalysts

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Mechanism of Catalysis: heterogenous

catalysis
Solid catalysts and a single fluid phase
1. diffusion from bulk to the catalyst particle
2. diffusion to the active sites
3. adsorption at the active site
4. reaction at the surface
5. desorption of products
6. diffusion to outer surface of the particle
7. diffusion from particle to the bulk
Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Adsorption of hydrogen on nickel

N atom facilitates the dissociation of H2 by

providing NiH bonding.
Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Chemisorption on metal surfaces

Metal surfaces provide ample opportunity for

chemisorption.
Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Catalytic hydrogenation of ethylene

Ethylene hydrogenation requires chemisorption of

ethylene and hydrogen
Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Physical appearance of catalysts

soluble (homogeneous)
bio-catalysts (enzymes)
solid catalysts (heterogeneous)

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Chemical composition of solid catalysts

Metals/alloys (Raney Ni,Co,Ru,Fe;

Pt,Ni/Al2 O3 ; Ni/SiO2 ; Pt,Pd/C)
Oxides (Silica, alumina, zeolites, clays, Fe2 O3 )
Sulfides (CoS MoS2 /Al2 O3 )
Chlorides (CuCl2 /Al2 O3 )
Ion exchange resins

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Shape and size of solid catalysts

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Shape and size of solid catalysts..

heat and mass transfer characteristics

catalyst wetting
mechanical strength (structural integrity, fines
in slurry reactors)
ability to settle
number of surface atoms
dispersion =
total number of atoms

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Shape and size of solid catalysts..

minimum pressure drop

minimum pore diffusion resistance
maximum mechanical strength
minimum cost

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Shape and size of solid catalysts

Monolith reactors offer low pressure drop, ease of

handling and high resistance to fouling.
Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Shape and size of solid catalysts

Porous structures are used to get large surface area

and low pressure drops.
Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Catalyst Production
Why?
utilization of catalysts
custom requirement
Three types of production activities:
production of bulk catalysts
production of supports
attaching the catalyst to the supports

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Bulk Catalysts: Raney-nickel

Murray Raney invented it in 1924

react powdered nickel-aluminium alloy with aq.
sodium hydroxide to remove aluminium
sensitive to poisoning and reaction conditions
regeneration is not easy.
little reproducibility
pyrophoric because of fast oxidation.
Hydrogen and organic vapours worsen the
situation.
Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Catalysts Support

to maximize the dispersion of active phase by

providing large area.
area in the range of 100 700 m2 /g
texture
regenerability
can show some activity also.

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Silicagel

starting material is sodium silicates SiO2 /Na2 O

dissolve in water at right pH and concentration
repeated condensation to get silanol groups
and polycondensate particles
3D network (hydrogel) by interparticle
condensation
the gel is dried to xerogel/silicagel/silica

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Sol-Gel Technique

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Alumina formation

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Zeolites

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology

Activated Carbon

stability in acid and basic solutions

high adsorption capacity for organic molecules
flexibility of texture
resistance to high temperature
formation of fines
catalytic activity

Catalysis in Fine Chemicals Technology

Fine Chemicals Technology