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CATALYTIC REACTION
AND
MASS TRANSFER
CATALYST-DEFINITION
A catalyst is a substance that affects the rate
of a reaction but emerges from the process
unchanged.
A catalyst usually changes a reaction rate by
promoting a different molecular path
("mechanism") for the reaction.
Catalyst affect yield and selectivity
Changes only the rate of reaction; it does not
affect the equlibrium.
CATALYST-EXAMPLE
Example- H2 and O2 to form water; with
Platinum as catalyst
Basis of Catalysis
A catalyst lower the activation barrier for a transformation, by
introducing a new reaction pathway
WITHOUT A CATALYST
WITH A CATALYST
What is Catalysis
also.
Catalysis is the occurrence, study, and use of catalysts
and catalytic processes.
gas
liquid
solid
Classification based on the substances from which a catalyst is made
Research in Catalysis
Research in catalysis involve a multi-discipline approach
Reaction kinetics and mechanism
Reaction paths, intermediate formation & action, interpretation of results obtained under
various conditions, generalising reaction types & schemes, predict catalyst performance
Catalyst development
Material synthesis, structure properties, catalyst stability, compatibility
Analysis techniques
Detection limits in terms of dimension of time & size and under extreme conditions (T, P)
and accuracy of measurements, microscopic techniques, sample preparation techniques
Reaction modelling
Elementary reactions and rates, quantum mechanics/chemistry, physical chemistry
Reactor modelling
Mathematical interpretation and representation, the numerical method, micro-kinetics,
structure and efficiency of heat and mass transfer in relation to reactor design
Catalytic process
Heat and mass transfers, energy balance and efficiency of process
11
Catalyst
Ni
Ni
Ni
N2 + 3H2 2NH3
NH3 NO NO2 HNO3
1920s: CO + 2H2 CH3OH (HP)
Fischer-Tropsch synthesis
SO2 SO3 H2SO4
Fe/K
Pt
(ZnCr)oxide
Co,Fe
V2O5
Industrial catalysis-3
1950s
C2H4 Polyethylene(Z-N)
C2H4 Polyethylene(Phillips)
Polyprop &Polybutadiene(Z-N)
Steam reforming
HDS, HDT of naphtha
C10H8 Phthalic anhydride
C6H6 C6H12
C6H11OH C6H10O
C7H8+ H2 C6H6 +CH4
Ti
Cr-SiO2
Ti
Ni-K- Al2O3
(Co-Mo)/Al2O3
(V,Mo)oxide
(Ni)
(Cu)
(Ni-SiAl)
Industrial catalysis-5
1970s
Xylene Isom( for p-xylene)
H-ZSM-5
Cu-Zn/Al2O3
H-ZSM-5
Catalytic dewaxing
H-ZSM-5
Autoexhaust catalyst
Pt-Pd-Rh on oxide
Hydroisomerisation
Pt-zeolite
SCR of NO(NH3)
V/ Ti
MTBE
C7H8+C9H12 C6H6 +C8H10
Industrial catalysis-8
2000+
Promoters
Substances which themselves are not catalysts, but when
mixed in small quantities with the catalysts increase their
efficiency are called as promoters or activators.
(i) For example, in Habers process for the synthesis of
ammonia, traces of molybdenum increases the activity of
finely divided iron which acts as a catalyst.
(ii) In the manufacture of methyl alcohol from water gas ,
chromic oxide is used as a promoter with the catalyst zinc
oxide .
http://www.emedicalprep.com
Catalytic Poisons
A substance which destroys the activity of the catalyst to
accelerate a reaction, is called a poison and the process is
called Catalytic Poisoning.
(i)
For example, the presence of traces of arsenious oxide in the reacting gases
FeS + H2
Auto Catalysis
When one of the products of a reaction itself acts as a
catalyst for that reaction the phenomenon is called
autocatalysis.
Examples of autocatalysis: (a) Hydrolysis of an ester
CH3COC2H5 + H2O
CH3COOH + C2H5OH
CATALYST-TYPE
HOMOGENEOUS
HETEROGENEOUS
In solution with at
least one of the
reactants
Example;
0xo process for
manufacturing
normal
isobutylaldehyde
Homogeneous Catalysis
Action catalyst
Esterificaton
Conc. H2SO4 catalyses the reaction between acids and alcohols
CH3COOH + C2H5OH
CH3COOC2H5 + H2O
Heterogeneous Catalysis
Catalyst is in different physical phase from the
reactants.
It is also called Contact catalysis.
It possesses great industrial importance.
X + C XC (1)
Y + XC XYC (2)
XYC CZ (3)
CZ C + Z (4)
X+YZ
Adsorption theory
H
Pt
H
Pt
Pt
Pt
Pt
O
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
External
diffusion
Internal
diffusion
Desorption
gas phase
reactant molecule
j
k
l
gas phase
liquid phase /
stagnant layer
mn
o
porous
solid
pore
pq r
porous
carrier
(catalyst
support)
bed of
catalyst
particles
reactants
substrate
reactor
product
reactiondesorption
adsorption
products
catalyst support
active
site
CATALYST-PROPERTIES
catalyst that
has a large
area
small pore
that will
admit small
molecule
can be either
porous or
non-porous
4.Supported catalyst
consist of particles of an active
material dispersed over a less
active substance
5.Unsupported catalyst
Promoters small amount of
active ingredients
Solid Catalysts
Catalyst composition
Active phase
Where the reaction occurs (mostly metal/metal oxide)
Promoter
Textual promoter (e.g. Al - Fe for NH3 production)
Catalyst
Electric or Structural modifier
Support
Poison resistant promoters
Support / carrier
Increase mechanical strength
Increase surface area (98% surface area is supplied within the
porous structure)
may or may not be catalytically active
40
Solid Catalysts
Some common solid support / carrier
materials
Alumina
Inexpensive
Surface area: 1 ~ 700 m2/g
Acidic
Silica
Other supports
Inexpensive
Surface area: 100 ~ 800 m2/g
Acidic
Zeolite
41
Active site
porous
solid
pore
Adsorbate
Adsorbent
Adsorbate
V = V fluid + V catalyst
Void fraction or the fraction of the
reactor volume occupied by fluid
V fluid
Volume of fluid
Volume of reactor
V
Homogeneous Reactors:
volume of fluid in a reactor
=
volumetricflow rate passes through the reactor
Heterogeneous Reactors
V fluid = V
volume of reactor
inlet volumetric flow rate
V
0
dC j
dz
jr
Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press
C A0 C A r
Reactor Residence Time
V
= fluid =
v
V R
v
Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press
Riser Reactor
In riser reactor, no mixing at all, PFTR
Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press
reaction rate:
r
moles
volume time
moles
r
area time
''
rate:
r s g c (1 )r"
Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press
Answer: 2x105
Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press
Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press
Topic 1
Catalytic Reaction and Mass Transfer
Catalytic reactions and reactors
Surface and Enzyme Reaction Rates
Introduction of Porous Catalyst
Transport and Reaction
External Mass Transfer
Pore Diffusion
Catalytic wall reaction
Langmuir-Hinshelwood Kinetic Mechanism
Temperature dependence of catalytic reaction rates
Application of reaction engineering in microelectronic
fabrication
Catalyst deactivation
Silica gels have surface areas up to ~ 500 m2/g, and they are widely
used as supports for catalysts.
The surface area is up to ~ 200 m2/g in crystalline form.
Zeolites are microporous crystalline solids with well-defined
structures. Generally they contain silicon, aluminium and oxygen in
their framework
The activated carbon is a highly porous with high surface area
(usually > 500 m2/g) carbon materials.
Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press
ii.
iii.
iv.
v.
vi.
vii.
CPE624
External
mass
transfer
(diffusion) of the reactants
(e.g., species A) from the bulk
fluid to the external surface of
the catalyst pellet.
Pore diffusion of the reactant
from the pore mouth through
the catalyst pores to the
immediate vicinity of the
internal catalytic surface.
Adsorption of reactant A onto
the active site of catalyst
surface
Reaction on the surface of the
catalyst (A B)
Desorption of the products
(e.g., B) from the surface.
Pore diffusion of the products
from the interior of the pellet
to the pore mouth at the
external surface
External mass transfer of the
products from the external
pellet surface to the bulk fluid
CAb = ??
CAs = ??
CA(x) = ??
k mA
Shl D A
ShL 0.66 Re L2 Sc
ShL
0.036 Re0L.8
Sc
8
ShD
3
For turbulent flow:
ShD
0.023 Re0D.8
Sc
Sh D = 0.98 ReD
4R 2 k mA (C Ab C As ) 4R 2 r" 4R 2 k"C As
By rearranging
C As
C Ab
1 k "
k mA
Eliminating CAs
k " C Ab
"
r"
k eff
C Ab
1 k"
k mA
nonporou
s catalyst
pellet
Reaction limited
k << kmA
CAb
k=kmA
CAs
CA
(d)
Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press
Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press