WELCOME

TO

CL 308: CHEMICAL REACTION ENGINEERING - II

(Jan – May 2019)

INSTRUCTOR
Dr. Vaibhav V Goud & Dr. Nageswara Rao Peela
(email: vvgoud, [email protected], Phone: 2272/3526)

Teaching Assistants
Mr. Atanu Paul (PhD Student)

1
 CL 308 - TEXTBOOKS/RESOURCES
• Course Text books
– Chemical Reaction Engineering
by Octave Levenspiel, 3rd Edition, Wiley & Sons
– Elements of Chemical Reaction Engineering
by H.Scott Fogler, 4th Edition, Prentice Hall

• Reference Text
– Chemical Engineering Kinetics
by J. M. Smith, 3rd Edition, McGraw –Hill

2
 Evaluation Scheme

Components Weightage (%)

 
2 Class Tests (Closed book) 10+10
Mid-Sem Exam (Closed book) 35
End-Sem Exam (Closed book) 45

3
 Why Chemical Reaction Engineering?
• CRE is needed in the development of new and the
improvement of existing technologies.
– search for alternative processes to replace old ones
• novel reactors and novel catalysts
– find routes to make a product from a different feedstock
• novel processes for syn-gas (CO+H2) production
• Hydrocarbon production from syn-gas
• Bio-fuel production
– reduce/eliminate unwanted byproducts
• Fuel-cells for automobiles
• NOx reduction
• CRE is perhaps the key course that differentiates Chemical
4
Engineering from other engineers.
Typical Chemical Process

Reactants

Undesirable
Bi-products

5
 Heterogeneous reactions
Heterogeneous reaction, any of a class of chemical reactions in
which the reactants are components of two or more phases (solid
and gas, solid and liquid, two immiscible liquids) or in which one
or more reactants undergo chemical change at an interface, e.g.,
on the surface of a solid catalyst.

6
 Lecture Topics of CRE – II (tentative)
S. # of
No. Lecture Topic Lectures
1 Introduction to heterogeneous reactions 1
2 Solid catalyzed reactions and kinetics 8
3 Packed bed and suspended solid reactors (bubbling 8
fluidized bed, and circulating fluidized bed)
4 Catalyst deactivation 3
5 Gas-liquid reactions on solid catalysis: trickle bed, 8
slurry, and three-phase fluidized bed reactors

6 Fluid-fluid reaction kinetics and reactor design 7

7 Fluid-particle (solid) reaction kinetics and reactor 5
design
7
For heterogeneous systems: Two complicating factors

1. Complicated rate expressions

2. Complication of contacting patterns for two phase systems

Complicated rate expressions:

• As more than one phase is present
• Movement of mtl. From phase to phase need to be
considered (in rate equation)
• Rate equation - incorporate in mass transfer are different in type
• - different in heterogeneous systems
• No single rate expression has general applications. (WHY?)

8
 How many steps are involved?
TWO

Mass transfer of O2 Reaction at the

to surface surface

9
Non catalytic (G-S) reaction

How many steps are involved?

TWO

Mass transfer of O2 Reaction at the

to surface surface

Here, two steps are involved i.e.

• mass transfer of oxygen to the surface and
• reaction at the surface of the particle
• mass transfer of CO2 to the bulk (through film) (NEGLECT this step
for kinetics)

Under steady state condition step 1, 2 and 3 are equal

10
Thus, step 1 = step 2
• In case of linear conc. we can combine these steps
• If one of the step is non-linear then eqn. become messy (by pass N.L.
step)
• Approximating: rA vs C, curve by Ist-order expression most useful
procedure
• Conc. of materials at intermediate conditions, eliminate in
combining rates

Overall rate for such process

A diffuses through a stagnant liquid (gas) film on to a plane surface

consisting of B,

reacts there to produce R which diffuses back into the mainstream

11
  𝐶 𝐴𝑙 =𝐶 𝐴𝑔

k  s =  k

By Diffusion flux A to the surface is

Rxn. Ist order w.r.t. A, so on unit surface area basis

  } = {1} over {𝑆} {𝑑 {𝑁} rsub {𝐴}} over {𝑑𝑡} = {𝑘} ^ {
−𝑟 𝐴2 𝐶 𝐴𝑠
At steady state:
O2 flow rate to the diffused through film = reaction rate at the surface
𝑟 }𝐴=1 {𝑟} rsub {𝐴 2} rsup {
12
 𝐶
  𝐴𝑙=𝐶 𝐴𝑔

Physical chemical

At high temp: k” = ∞, Rxn. is very fast

 −𝑟 ′ ′ = 𝐶 𝐴𝑔 =𝑘 (𝐶 −𝐶 )     and   here   𝐶   not   measured
𝐴1 𝑔 𝐴𝑔 𝐴𝑠 𝐴𝑠
1
𝑘𝑔

Now, assume for gas is moving in the form of P.F.

13
 𝑋𝐴 𝑋𝐴 Mass transfer controlled
 
𝑉 ′′
=∫ 𝑑 𝑋 𝐴 /− 𝑟 𝐴1 =∫ 𝑑 𝑋 𝐴 /𝑘 𝑔 .𝐶 𝐴𝑔 Reactor design eqn.
𝐹𝐴0 0 0

  𝑋𝐴 𝑋𝐴 Both are controlling

𝑉 ′′
=∫ 𝑑 𝑋 𝐴 / − 𝑟 𝐴 1 =∫ 𝑑 𝑋 𝐴 / ¿ ¿ ¿ ¿
𝐹𝐴0 0 0

At low temp: kg = ∞ (as Rxn. is very slow)

 𝑟 ′ ′ = 𝐶 𝐴𝑔 = 𝑘 𝐶
𝐴1 𝑠 𝐴𝑔
1 Reaction controlled
𝑘𝑠
Slowest step
14
 Reaction controlled

Mass transfer controlled

15
Overall rate for non linear process
let the reaction step be second order with respect to A,

kg = kl
Input Output
Reactor
Kinetics Contacting
• Chemical
Batch, Continuous
• Physical
(PF, MF)
16
 What is a catalyst?
A catalyst is a substance that increases the rate of a
reaction without being consumed in the process

A catalyst is a substance that changes the kinetics but

not the thermodynamics of a chemical reaction
 B

More informative definition: A catalyst is a substance that

transforms reactants into products, through an
uninterrupted and repeated cycle of elementary steps in
which the catalyst participates while being regenerated in
the original form at the end of each cycle during the life of
the catalyst 17
(Source: Hand book of Heterogeneous Catalysts, Edited by Ertl et al., Vol. 1, Wiley-VCH)
How does a catalyst work?

18
 Catalyst Types
• Porous catalysts
 Raney Nickel
• Molecular sieves
 Faujasite-Type Zeolite
• Monolithic
 Catalytic converters in automobiles
 Pt gauze reactor for ammonia oxidation
• Supported catalysts
 Metals supported on alumina or other supports

19
(Source: HS Fogler)
 Properties of Catalysts
• High surface area
• Activity
• Selectivity
– 2 types (product selectivity and reactant
selectivity)
• Yield
• Stability
• Accessibility

10g of a catalyst could give a surface area as

high as a football ground 20
(Source: HS Fogler)
21
Steps Involved in A Catalytic Reaction
1. External mass
transfer
2. Internal diffusion
3. Adsorption
4. Chemical Rxn.
5. Desorption
6. Diffusion
7. Ext. mass transfer

Steps 1,2,6,7 diffusion steps

Steps 3,4,5 Rxn steps
1 to 3 for reactants
5 to 7 for products

22
(Source: HS Fogler)
Collecting Information for Catalytic
Reactor Design

23
(Source: HS Fogler)
The Spectrum of Kinetic Regimes
Consider a porous catalyst particle bathed by reactant A.

1. Surface kinetics: (This involve adsorption of reactant A onto the

surface, reaction on the surface, or desorption of product back into
the gas stream.)
2. Pore diffusion resistance which may cause the interior of the
particle to be starved for reactant. (can be reduce by reducing cat
particle size)
3. Particle ∆T or temperature gradients within the particle. This is
caused by large heat release or adsorption during reaction. (It
causes the Rxn rate to vary inside the catalyst)
4. Film ∆T between the outer surface of the particle and the main gas
stream. (resistance to heat transfer within the gas film enveloping
the cat surface)
5. Film diffusion resistance or concentration gradients across the
gas film surrounding the particle. (external diffusion resistance)
24
 Catalytic Rxn.
For gas/porous catalyst systems:
slow Rxn.: Step 1 influences the Rxn.
Bulk
Fast Rxn. : step 2 influences the slow rate
Cat 𝐶
  𝐴𝑠 step 3 or step 4 need to consider
Gas
Reactant
flowing
Film  𝐶 𝐴𝑔 For liquid systems:
 𝐴 𝐶𝑎𝑡 𝐵 Steps 1, 2, 5 influences the Rxn.
→
Rarely, steps 3 or step 4 need to consider

25
 1. External mass transfer Will talk about these terms in later
stage or how to incorporate them
2. Internal diffusion in the rate equation
3. Adsorption
Discuss about these three terms
4. Chemical Rxn. which are important for rate
5. Desorption equation.

6. Diffusion
7. Ext. mass transfer

Overall rate of reaction is the rate of the SLOWEST step in

mechanism. For example porous catalyst diffusion within the catalyst
may LIMIT the rate of reaction

26
 Steps Involved in A Catalytic Reaction
1. External mass transfer of reactant (A)
2. Internal diffusion (pore mouth to immediate
vicinity of catalyst surf.)
3. Adsorption of reactant “A” on the cat. Surf.
4. Chemical Rxn. On the surface 𝐴𝐶𝑎𝑡   𝐵
→
5. Desorption (product “B” desorption from the
surf.)
6. Diffusion (diffusion of product)
7. Ext. mass transfer (mass transfer of product from
the film)
Surface Rxn. Models:
Steps 1,2,6,7 diffusion steps
i. Langmuir Hinshelwood
Steps 3,4,5 Rxn. steps
Formulation
1 to 3 for reactants
ii. Hongen –Watson approach
5 to 7 for products
iii. L-H-H-W approach

27
(Source: HS Fogler)
28
 Internal Diffusion to Catalyst Surface

As the particle size increases kr

At small particle size (kr ) Internal Diffusion is no longer the
SLOW step
29
(Source: HS Fogler)
 Reaction Steps
Adsorption Step
‘S’- represent active site
‘CO.S’- CO adsorbed on
site S (reversible)

Site balance:
Total molar conc. Of active sites per unit mass of Cat. (mol/g.cat)

30
(Source: HS Fogler)
 Reaction Steps
1. Adsorption Step A = CO
Molecular and non-
dissociative ads.
Proportional to no. of collision per
unit time with vacant site (collision rate
pro. to partial pressure of CO)

Proportional to of occupied site

Net rate of ads.

Here, kAis independent of temp., but k-A temp. dependent 31

(Source: HS Fogler)
 CO is the only molecule ads. on the site

Once the system reach to equilibrium net ads. equals ZERO

Left hand side of this

eqn. equal to ZERO
rAD = 0

replace Cv in terms of Cco.s & Ct

= KA Pco (Ct – Cco.s)

Equation for adsorption isotherm

(Langmuir Isoth.)
32
Another way of checking is linearize the model

Another approach is
dissociative ads.

𝐶𝑂
   + 2 𝑆  ⇔  𝐶 .𝑆  + 𝑂 .𝑆

33
 2. Surface Reaction Step

A. Langmuir-Hinshelwood kinetics
i. Single site:
Reactant ‘A’ decompose
at
ads. site

Because in each step the

reaction mechanism is
elementary, the rate law

 𝑘 𝑠=( 1
𝑠 )
34
(Source: HS Fogler)
 2. Surface Reaction Step
A. Langmuir-Hinshelwood kinetics (continued)
ii. Dual site:
Type I:

Reactant ‘A’ may react with adj.

site (dehydration of butanol (C4H8)

Type II:

𝑔𝑐𝑎𝑡
 
𝑘 𝑠= ( 𝑚𝑜𝑙 . 𝑠) 35
(Source: HS Fogler)
 2. Surface Reaction Step
B. Eley-Rideal kinetics

36
(Source: HS Fogler)
 3. Desorption Step

  𝐴 . 𝑆 ⇔ 𝐴 +𝑆
𝑃𝐴 𝐶𝑣
(
𝑟 𝐷𝐴 =𝑘 𝐷 𝐶 𝐴 .𝑆 −
𝐾 𝐷𝐴 )
 𝑟 𝐷𝐴 =−𝑟 𝐴𝐷𝐴 Rate of desorption is reverse
sign of ads. rate

  1 desorption equill. Const. is

𝐾 𝐷𝐴 =
𝐾𝐴 reciprocal of ads. equil. Const.

 𝑘 𝐷 =( 1
𝑠)

37
(Source: HS Fogler)
 Rate-Limiting Step

At steady state:

38
(Source: HS Fogler)
The rate eqn. for surface kinetics

Step 1. A adsorbed onto the surface and is attached to an active site.

Step 2. A reacts (dual site mechanism or single-site mechanism).
Step 3. Products are desorbed from the surface, which then frees the
site.
Cumene (C) Benzene (B) + Propylene (P)

39
Is Adsorption Rate-Limiting? (continued)
The overall rate equation:

Initial rates:

(Source: HS Fogler)
Is Surface Rxn Rate-Limiting? (continued)

Overall rate:

Initial rate:

When

When

(Source: HS Fogler)
 Is Desorption Rate-Limiting? (continued)
Site balance:

Overall rate:

Initial rate:
 43

(Source: HS Fogler)
44
Pore Diffusion Resistance Combined with Surface Kinetics (Pore Diffusion +
Surface Reaction)
Cylindrical pore of length, x and ‘A’
1 dN A diffuses into pore and reacting on surface
A Pr oduct , rA"    k "C A
S dt by first order Rxn. on wall of the pores

Flow of material in and out of the any

section of the pore. At steady state mtl.
balance for reactant ‘A’ for this section

45
To find out the actual rate, we need to develop first the concentration profile in the
cylinder along the pore length
1. First thing is to develop the profile inside the pore
2. Differentiate the profile and evaluate at any distance i.e. x = L
Which gives an idea what is the flux entered into the pore and reacted at steady state
& i.e. called as the actual rate
output  input + disappearance by reaction = 0
 dC   dC 
 r 2 D  A    r 2 D  A   k "C A  2 r x   0 (1)
 dx out  dx in

By rearranging  dC A 

 dC A 
    "
 dx out  dx in 2k
 CA  0 (2)
x Dr

So taking the limit 𝛥

  𝑥 → 0 We can writ the eqn. in the following form
d 2C A 2k "
 C A  0
dx 2 Dr

Here as the rate is based on unit surface area of the wall of the catalyst pore k" has the units
of length per time (m/s) 46
The interrelation between rates on different bases is given by (rA )V  (rA' )W  (rA" )S 

In terms of rate constant it becomes k V  k 'W  k " S

S "  surface area  "  2 rL  2k "
Therefore for cylindrical catalyst pore k  k k  k  2 
"

V  volume   r L  r

So in terms of volumetric units, Equation (3) becomes [substituting k for 2k"/r in Equation (3), we get]

d 2C A k let , k D  m2
2
 C A  0(4)
dx D
d 2C A
With this eqn. becomes 2
 m 2C A  0
dx
Solution of above eqn. dC A d 2C A
CA  e Ax
 Ae and
Ax
2
 A2 e Ax
dx dx
So Equation (5) become A2 e Ax  m 2 e Ax  0
Hence, A   m
Solution of above eqn.
CA  emx and CA  e mx
47
 General solution of Equation (5) is the linear combination of the particular solutions

CA  M1emx  M 2e mx  Where, m  k D  2k " / Dr

Let us evaluate M1 and M2 using the boundary conditions

(i) At the pore entrance, the concentration is CAs: CA  CAs at x  0)

(ii) There is no flux or movement of material through the interior end of the pore
dC A
0 at x  L(8)
dx
With CA = CAs at x=0 Equation (6) becomes
C As  M 1  M 2 (9)
wehaveC A  M 1e mx  M 2e  mx
dC A
 mM1emx  m M 2e  mx
dx
With dCA/dx = 0 at x = L the above becomes

0  mM 1e mL  mM 2 e  mL
M 1e mL  M 2 e  mL  0 48
 Combining Equations (9) and (10) gives

M 1e mL  (C As  M 1 )e  mL  0 ; M 1 (emL  e mL )  C As e  mL  0
C As e  mL C As e mL
M 1  mL  mL Similarly,M 2  mL  mL 
e e e e
Substituting M1 & M2 in eqn. (6) gives
C As e  mL mx C As e mL
C A  mL  mL .e  mL  mL .e  mx
e e e e
 e  m (L  x)  e m ( L  x ) 
C A  C As   mL 
 e mL
 e 
The dimensionless concentration profile of reactant A within the pore is
CA e m (L  x)  e  m ( L  x ) cosh m (L-x)
  (11)
C As e mL  e  mL cosh m L
The eqn. shows the progressive drop in
e m L  e  mL
[ascosh m L  the conc. (conc. profile of reactant)
2 within the pore and it is seen to be
e m (L  x)  e  m ( L  x ) dependent on the dimensionless
cosh m (L-x) 
2 quantity
ex  ex mL, or MT, called the Thiele modulus
cosh x= ]
2
 Fig. 1: Distribution and -average concentration of reactant in a catalyst pore as a fun of mL (-Thiele
modulus) for first order surface reaction

Now, we define the quantity called the effectiveness factor to measure how much the
reaction rate is lowered due to the resistance of pore diffusion.

It is defined as the ratio of actual average reaction rate within the pore to the reaction
rate at external conditions (Ts CAS) (i.e. in absence of pore diffusion resistance).
50
 actual average reaction rate within pore

reaction rate at external condition
or
actual average reaction rate within pore

reaction ratethat would result of entire pore surface were exposed
to condition at the external surface/pore mouth C As , TS

rA with diffusion

 
 rA without diffusion resistance

In particular, for first order reactions as the rate is proportional to the concentration, the
effectiveness factor is given by  ¿ 𝐶 𝐴
𝐶 𝐴𝑆
Evaluating the average rate in the pore from Equation (11) yields the following
relationship
tanh mL
 C A C As  (12)
mL

51
Let us obtain the relationship given by Equation (11).
For first-order reactions: k .C A C A
  )
k .C As C As
C A is given by,
L

C A cosh m(L-x)  C dx A
1
L
We have,  CA  0
  C A dx
C As cosh mL L
L0
 C A  C As
cosh m(L-x)  dx
0
cosh mL
substituting C A into Equation (12) in terms of C As gives With this C A , Equation (12) becomes
L
1
L
C As cosh m(L-x)dx 1
LC As 0
first order   first order  C A dx(13)
LC As 0 cosh mL
L
C As
LC As cosh mL 0
 cosh m(L-x)dx

L
1
L cosh mL 0
 cosh m(L-x)dx

L
1  -1 
 sinh m(L-x)
L cosh mL  m 
0

1
  0  sinh mL 
mL cosh mL
sinh mL

L cosh mL
tanh mL 52
 first order  (14)
mL
The effectiveness factor as a function of the parameter mL or M,, called the Thiele modulus

the conc. of reactant does not drop appreciably within the pore; thus pore diff. offers negligible resistance
𝑘
small value for  
𝑚𝐿= 𝐿
√ 𝐷 means either a short pore, slow reaction, or rapid diffusion, all three factors
tending to lower the resistance to diffusion
For large mL, or mL > 4, the reactant concentration drops rapidly to zero on moving
into the pore, hence diffusion strongly influences the rate of reaction. We call this the regime of strong
pore resistance

Proper measure of particle size:

A characteristic size of particle of any shape is defined as

  𝑣𝑜𝑙𝑢𝑚𝑒   𝑜𝑓   𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒
L=
𝑒𝑥𝑡𝑒𝑟𝑛𝑎𝑙  surf . available  for   reactant   penetration
  𝑎   ×   b  ×  c 𝐶 𝑡h𝑖𝑐𝑘𝑛𝑒𝑠𝑠
For flat plates without end effects (of thickness c): 𝐿= = =
2  ×   a   ×   b   2 2
2
  𝜋   ×   R × L 𝑅
For cylinders (of radius R) : 𝐿= =
2   𝜋 RL 2
3
  4/ 3  ×   𝜋   ×   R 𝑅
𝐿= =
For sphere (of radius R) : 4  𝜋 R
2
3
54
Measures of reactions rates:

However, for porous catalyst particles rates based on unit mass and on unit volume of
particles, r' and r"' are the useful measures

55
The
  relationship between (effectiveness factor) and (Thiele modulus)for the various
particle shapes are

Given for a first order isothermal surface reaction of the type:

 A → R, - = k

 = tanh .... for flat plates/slabs with sealed edges

 = .... for cylinders with sealed ends

Where,
  and represent zero and first order modified Bessel functions of the
first kind

 = .... for spheres (spherical catalyst pellets)

  where =L  Where, k is
56
Aris related with MT for various particle shape by defining MT
  𝑘 .𝐶 𝑛𝑏 −1
𝑀𝑇=
𝑉
𝑆𝑥 √ 𝐷𝑒 This equation was used and after
normalization, we get following
eqns.
 = tanh .... for flat plates/slabs with sealed edges

 = .... for cylinders with sealed ends

 = .... for spheres (spherical catalyst pellets)

Here for all shapes in MT ∞ (large value)

  1
¿
𝑀𝑇 57
Rxn.
controlled

Effectiveness factor as a function of MT for porous particles of various shapes

This entire discussion is to find out effectiveness factor for the catalyst. By using
the above graph effectiveness factor can be calculated.

For any designed catalyst we can determine whether catalyst is effective or not,
because that determines the Kinetics

How to get effectiveness factor ? 58

For that we should know MT and to calculate MT it requires k”’ De and bulk conc. out
of which bulk conc. is measurable but k and De are not known (but co relation are
existing) but k is not possible to estimate without the presence of mass transfer

There are some criteria (Wagner-Weisz-Wheeler modulus) which eliminates k value

and make use of (MT)2 and

  𝑛 −1   𝑛 −1
𝑀 2𝑇 𝐷 𝑒
𝑉 𝑘 .𝐶 𝑘 .𝐶
𝑀𝑇=
𝑆𝑥 𝐷𝑒 √ 𝑏
¿𝐿

Using original equation

√
𝐷𝑒
𝑏  
𝑘 = 2 𝑛− 1
𝐿 𝐶𝑏

 b
For nth order Rxn. 𝑟  𝑏 =  k .  C𝑛𝑏
Substitute ‘k’ value in above eqn.  (MT)2

59
For Rxn. Controlled what will be the value of effectiveness factor and Thiele
modulus =1 and MT = less than 1 and (MT)2 still less than one
2
 𝑟 𝑜𝑏 ×   L
  ≺  1
𝐷𝑒 . 𝐶 𝑏
For Mass Transf. Controlled what will be the value of effectiveness factor and
Thiele modulus =1/MT and Mt is always greater than 1
2
 𝑟 𝑜𝑏 ×   L
  ≻  1
𝐷𝑒 . 𝐶 𝑏
With this available information we can find out effectiveness factor

 (MT)2

for flat plates/slabs use Thiele modulus eqn.

60
Wagner-Weisz-Wheeler Modulus (Mw) criteria
 From above equation calculate MT

Once you have MT then replace it in the original equation of slab

to get effectiveness factor

61
In fact we can also calculate k if some correlation can be used for estimation of

Porosity- Space occupied by

Knudson diffusivity solid (mol. movement restricted ) Constriction factor
(due to variable area)

  𝐷 𝐴 ×   𝜙𝑃  ×   𝜎
¿ tortuosity
𝜏
or
  𝑇
𝐷𝑒 =100  ×  𝑟
𝑀
r = avg pore radius
√
T = in degree kelvin
M = M.W.

62
Porous Catalyst Particles:
The results for a single pore can approximate the behavior or particles
of various shapes-spheres, cylinders, etc.

For these systems the following apply.

63
Use of the proper diffusion coefficient
Replace the molecular diffusion coefficient by the effective diffus.
Coefficient of fluid in the porous structure.

• Effective diffusivity nothing but normal diffusivity and all the

factors which hinders the movement of molecule inside the pore
Porosity- Space occupied by
Knudson diffusivity solid (mol. movement restricted ) Constriction factor
(due to variable area)

  𝐷 𝐴 ×   𝜙𝑃  ×   𝜎
¿ tortuosity
𝜏
Tortuosity is always greater than ONE, if it is ONE means the pore is straight without any hindering inside,
practically which is not possible

  - Factors which are dependent on solid morphology, porous structure and these factors will
change from catalyst to catalyst 64
Finding pore resistance effects from experiment

Wagner-Weisz-Wheeler Modulus (Mw) criteria

2 2
𝑀 𝑤=𝑀  effectiveness  factor  = L ¿¿¿
 
𝑇
2
𝑟
  𝑜𝑏 ×   L 2 tanh   M 𝑇 2
 =  effectiveness   factor   ×   M 𝑇 =  ×   M𝑇
𝐷𝑒 . 𝐶 𝑏 𝑀𝑇

Pore resistance limits

When, MT < 0.4 or MW < 0.15 (diffusion free regime i.e. Rxn. Controlled)

At other extreme cond.

When, MT < 4 or MW < 4 (strong pore resis. regime i.e. diffusn. Controlled)

65
 In this region
slight deviation
of 10-15%
Rxn.
controlled

66
 Particles of Different Sizes

Effectiveness factor accounts for pore diffusion resistance. Hence, based on unit
mass of catalyst, considering pore diffusion resistance, the rate is given by
  -= k
In
  absence of gas film resistance : =
 - = k1 for particles size
- = k.2for particles size

In the diffusion free regime = 1,

we have   = = as, 1 and 2 =1

 In the strong pore diffu. resis. regime = , we have

  = =   = = =   as ∝ R

Here the rate of reaction is inversely proportional to the particle size. 67

Arbitary Reaction Kinetics   𝑛 −1
𝑉 𝑘 .𝐶

The Thiele modulus is generalised as

𝑀𝑇=
𝑆𝑥 𝐷𝑒√ 𝑏

  = ……….

 Where, is the equilibrium concentration of A

With
  this v/s curves for all forms of rate expression closely follow the curve for
the first order reaction
This generalised modulus for nth order irreversible reaction
CAe=0
  = L

68
For nth order irreversible reactions
 - =
-=
For irreversible reactions, CAe = 0
  =

  =

 
= L
= L
= L

  = L
69
In the regime of strong pore resistance, nth order reactions behave in an unexpected
way.
For nth order reactions,   -=

  We have , = 1/   ∴ - = (1/)

 
Substituting into the above equation gives
  -=

  =

 = =

  - =

70
  The rate depends on →

So
  in the regime of strong pore diffusion, the measurement /observed reaction
order is related to the true reaction order n as follows:
  =
true order → 0 order becomes 1/2 ← observed order/apparent order
1st order remains 1st order
2nd order becomes 1.5 order

 The rate depends on →

  k’n=
Temperature dependent term:
  ❑1 /2
𝑘𝑛❑

==> 71
Heat effects (Exoth./Endoth.) during Rxn.
(i). Particle ∆T: Temperature gradient mat exist within the pellet

(ii). Film ∆T: A Temp. gradient may exist across the fluid film (betwn. Outer
surface of pellet and main gas stream). The whole pellet is hotter/colder than
the surrounding fluid, though uniform in temp.

following are the simple calculations which gives an idea regarding non-
isothermal effects present or not.

Film ∆T
To find max. ∆T equate the rate of heat removal through the film with the rate of
heat generation by reaction within the pellet

72
73
(i). Particle ∆T: at steady state heat flux within an elementary thickness of the
particle is balanced by the heat generated by the Rxn.

(for pellet as whole integrating the above eqn. from exterior surface to center fo
the pellets)
T = Ts ; CA = CAs to enter of the particle where T = Tcenter ; CA = C

  ¿
 Shoot up
pt.

Rxn.
controlled
regime

Snuffed Mass
out rxn. controlled
regime

For, exoth. condition, where pore resistance starts,

become greater than unity
75
 Performance Eqns. for Reactors Containing Catalyst

For PFR: consider a thin slice of PRF

A steady state material balance for reactant A is

input of A = output of A + disappearance of A by reaction

F (1 - XAin)
Ao = FAo (1 -XA out) + (-rA) ∆W
The above material balance in differential form is
written as :
FAO dXA = (-r’A) dW (-rA) W = (-rA) Vs, Vs - volume of
solids

= (-r’ ) dW = (-r”’ ) dVs

I

FAodXA A A

76
 The above eqn is analogous to performance eqn. for homogeneous reactions.

 𝑓𝑜𝑟 h𝑜𝑚𝑜𝑔𝑒𝑛𝑒𝑜𝑢𝑠 𝑟𝑥𝑛 . 𝜏= 𝑉 . 𝐶 𝐴 0

𝐹 𝐴0

First order catalytic rxn. in PFR

PFR

MFR: For first order catalytic reactions with CAin = CAo and
 cv
MFR

Batch Reactor : (batch of catalyst and batch of gas)

Batch React.
77
Experimental methods for finding rates

• Any type of reactor with known contacting pattern

• kinetics of catalytic reactions.
• only one fluid phase is present in these reactions, the rates can be found as with
homogeneous reactions. (precaution performance equation dimensionally
correct and that its terms are carefully and precisely defined).

Batch reactor (heterogeneous)

Well
mixed

78
Differential reactors (heterogeneous)
A differential reactor determine the rate of reaction as a
function of initial or entering concentration of
reactant.

It consists of a tube containing a very small amount of

catalyst, in the form of thin disk.
W
Change in reactant conc. through the bed of cat. is
extremely small (i.e. ∆XA = should be small)

Reaction rate is considered to be constant at all points

within the reactor and average rate can be used (rA)avg.

Thus each run gives directly a value for the rate at the
 𝑊 𝛥𝑋𝐴 average concentration in the reactor,
=
𝐹 𝐴𝑜 ( −𝑟 𝐴 )𝑎𝑣𝑔 and a series of runs gives a set of rate-concentration
data which can then be analyzed for a rate equation.
79
PFR reactor (heterogeneous) packed bed

xAf

𝑥 𝐴𝑓
 𝑊 𝑑 𝑥𝐴
=∫
𝐹 𝐴𝑜 𝑥 =0 − 𝑟 𝐴
𝑖𝑛

xAin
80
Mixed flow reactor (heterogeneous)

Because, XAin = 0

 𝑊 𝑋 𝐴𝑜𝑢𝑡
=
𝐹 𝐴𝑜 −𝑟 ′𝐴𝑜𝑢𝑡

81
 Recycle Reactor

Fluid out, XAin

Catalyst, W

R=∞ mixed flow condition

(R+1) v
(Rv)

Fluid out, (v, XAout)

82
83