Question Paper Code: 91301

B.E/ B.Tech DEGREE EXAMINATION, NOVEMBER/DECEMBER 2014

Seventh Semester
Chemical Engineering
CH2401 CHEMICAL REACTION ENGINEERING- II
(Regulation 2008/2010)
Time: Three hours Maximum: 100 marks
Answer ALL questions.
PART A—(10 x 2 = 20 marks)
1. What is the mean residence time distribution function of an ideal CSTR?

2. What are the single parameter models that describe the non-ideal flow in the reactor?
 Dispersion model
 Tanks-in-series model
 Segregation model
 Compartment model
3. What are promoters and inhibitors?
Catalyst promoters are substances which do not act as catalyst but enhance the efficiency or activity
or selectivity or stability of catalyst and prolong catalyst life. For example, the catalytic activity of
V2O5 in oxidation of SO2 is enhanced appreciably when sulphates of alkali metals are added in
small amounts.
Catalyst inhibitors are substances which decrease the rate of reaction, or activity or selectivity or
stability of the catalyst. For example in the oxidation of ethylene, ethylene oxide is the desirable
product. At the same conditions CO2 and H2O are also formed by complete oxidation, but this
reaction is undesirable and needs to be suppressed. In this process silver supported alumina is a
good catalyst but if halogen compound is added, CO2 and H2O formation is reduced.
4. What is dissociative adsorption?
Adsorption with dissociation into two or more fragments, both or all of which are bound to the
surface of the adsorbent. The process may be homolytic, as in the chemisorption of hydrogen:

5. Define Effectiveness factor.

The effectiveness factor (denoted by ‘η’) is defined as the ratio of actual rate for the whole pellet to
the rate evaluated at outer surface conditions. OR It is the ratio of reaction rate with diffusion to the
rate without diffusion resistance.
6. Define Effective diffusivity. (NOV/DEC 2014)
In a porous catalyst, the pores in a catalyst are not straight and they follow tortuous (zig-zag),
interconnecting paths having varying cross sectional area. To account this variation, effective
diffusivity is considered.
Effective diffusion coefficient accounts for the average diffusion taking place at any position in the
catalyst pellet and it is the function of both bulk diffusivity and Knudsen diffusivity. It is denoted by
‘De’. Effective diffusivities in porous catalysts are usually measured under conditions where the
pressure is maintained constant by external means.
7. What are the limitations of Shrinking Core Model?
It is the best simple representation for the majority of reacting gas-solid systems. However, there are
two broad exceptions to this statement;
 First, Slow reaction of a gas with a very porous solid will not fit to the reality.
 Second, when solid is converted by the action of heat and without needing contact with gas
– Such as baking bread, roasting chickens are mouth watering examples of such reactions.
8. Name the three factors that control the design of a fluid solid non catalytic reactor.
 Diffusion of gaseous reactant A through the film surrounding the particle to the surface of
the solid.
 Penetration and diffusion of A through the blanket of ash to the surface of the unreacted
core.
 Reaction of gaseous A with solid at this reaction surface.
9. Define Film conversion parameter.

10. Give examples for absorption with chemical reaction.

PART B—(16 x 5 = 80 marks)

11. a) Explain in detail how the pore volume distribution of a solid catalyst is determined by the
Mercury-Penetration Method
Mercury penetration method
  The mercury-penetration method depends on the fact that mercury has a significant surface
tension and does not wet most catalytic surfaces. This means that the pressure required to
force mercury into the pores depends on the pore radius.
 The pressure varies inversely with a; 100 lb/in2 (approximately) is required to fill pores for
which a = 10,000oA, and 10, 000 lb/in.2 is needed for a = 100oA.
 Simple techniques and equipment are satisfactory for evaluating the pore-volume
distribution down to 100 to 200oA, but special high-pressure apparatus is necessary to go
below a = 100o A, where much of the surface resides.

 By equating the force due to surface tension (which tends to keep mercury out of a pore) to
the applied force, Ritter and Drake obtained

 Where θ is the contact angle between the mercury and pore wall (figure)
 Then the working equation for evaluating the radius corresponding to a given pressure is

Nitrogen-desorption method
 As the low temperature nitrogen-desorption experiment is continued to high pressures multilayer
adsorption occurs, and ultimately the adsorbed film are thick enough to bridge the pore. Then
further uptake of nitrogen will result in capillary condensation.
 Since the vapor pressure decreases as the capillary size decreases, decreases, such condensation will
occur first in the smaller pores. Condensation will be complete, as , (p/po= 0) when the entire void
region is filled with condensed nitrogen.
 Now, if the pressure is reduced by a small increment, a small amount of nitrogen will evaporate
from the meniscus formed at the ends of the largest pores.
 Pores which are emptied of condensate in this way will be those in which the vapor pressure of
nitrogen is greater than the chosen pressure.
 The Kelvin equation gives the relationship between vapor pressure and radius of the concave
surface of the meniscus of the liquid.
 Since some of the nitrogen is adsorbed on the surface, and therefore not present because of
capillary condensation, the Kelvin relationship must be corrected for the thickness of the adsorbed
layers.
 With this correction, the pore radius is related to the saturation pressure ratio (vapor pressure ’p’ in
the pore divided by the normal vapor pressure po) by

 Since nitrogen completely wets the surface covered with adsorbed nitrogen, θ = 0 and cos θ= 1. The
thickness δ depends on p/po . The exact relationship has been the subject of considerable study,
but Wheeler’s form

 For nitrogen at – 195.8o C (normal boiling point) , for a-δ in angstroms, becomes

 For a chosen value of p/po , the above equation give the pore radius above which all pores will be
empty of capillary condensate.
 Hence, if the amount of desorption is measured for various p/po, the pore volume corresponding to
various radii can be evaluated.
 Differentiation of the curve for cumulative pore volume vs. radius gives the distribution of volume.

 By combining mercury-penetration and nitrogen-desorption measurements, pore-volume

information can be obtained over the complete range of radii in a pelleted catalyst containing both
macro- and micropores.
 Figure shows the cumulative pore volume for two alumina pellets, each prepared by compressing
porous particles of boehmite (Al2O3.H2O). The only difference in the two is the pelleting pressure.
 Increasing this pressure causes drastic reductions in the space between particles (macropore olume)
but does not greatly change the void volume within the particles or surface area. The derivative of
the volume curves in figure (1) gives the pore volume distribution, and these results are shown in
figure (2).
b) For a bimolecular reaction A + B –>C + D when all the species are adsorbed onto the catalytic
surface and if surface reaction is rate controlling derive the rate expression for the formation of the product
‘c’
Let A – Isobutene (I), B – Water (W) and R – Tertiary Butyl Alcohol (TBA). Thus the given
reaction becomes A+BR
A + X  A.X (Adsorption)
B + X  B.X
A.X + B.X  R.X + X (Surface reaction)
R.X  R + X (Desorption)
 Given, Adsorption of ‘A’ is rate limiting.
 The concentration of reaction components (leaving ‘A’) at equilibrium are
CB = KB CB Cv and CR = KR CR Cv ------ 1
  From the surface reaction, we get KS = [CR Cv]/[CA CB]

Or CA = [CR Cv]/[KS CB]

Using equation 1 and the overall equilibrium constant {K = [KA KB KS]/KR} into
the above, we get CA = (KA/K) (CR Cv/CB) ------ 2

 We know, Cm = CA + CB + C C + Cv
Substituting equations 1 and 2 into the above and simplifying, we get

Cv = Cm /[(KA/K)(CR/CB) + (KB CB) + (KR CR) + 1] ------ 3

 We know, the rate of adsorption of ‘A’ is

rA| = kA [ CA Cv – (1/KA) CA]
Substituting equation 2 into the above, we get
rA| = kA Cv [CA – (1/K) (CR/CB)]
Finally, Sub. equation 3 into the above, we get

rA| = (kA Cm) [CA – (1/K) (CR/CB)] / [(KA/K)(CR/CB) + (KB CB) + (KR CR)
+ 1]

12. a) A first order catalytic reaction A  R is carried out in a packed bed reactor. The molal
feed rate of the reactant is 12.5 kmol/hr. The following data is available;
W (kg cat) 0.625 1.87 3.125 4.375 6.25 7.5 8.75
XA 0.058 0.139 0.213 0.288 0.381 0.440 0.493

Calculate the weight of the catalyst for 40% conversion in a packed bed reactor, if the molal
feed
rate is increased to 125 kmol/hr.
 Ans : We know

That is, a plot of XA vs. W/FAo will give slope as –rAI.

 From the given data, FAo = 12.5 kmol/hr, we have

W/FAo (X) 0.05 0.15 0.25 0.35 0.5 0.6 0.7
XA (Y) 0.058 0.139 0.213 0.288 0.381 0.440 0.493

 From the plot between XA vs. W/FAo, at XA = 0.4, We get

W/FAo ≈ 0.53

 Now, for the given new FAo = 125 kmol/hr, we get

W = 0.53 * 125 ≈ 66.25 Kg
b) Derive the expression that relates the Thiele Modulus to the Internal effectiveness factor of a
spherical catalyst pellet catalyst as I order irreversible reaction.

By material balance, at steady state, we have

d2CA/dx2 + (2/r) dCA/dx – (k’ ρp/De) CA = 0
 On solving with boundary conditions, we get
CA/CAs = (rs/r) Sinh [3Ф(r/rs] / Sinh (3Ф)

Where ‘Ф’, Thiele modulus = (rs/3) SQRT (k| ρp/De)

 By definition, effectiveness factor (η) = rA, with diffusion / rA, without diffusion
= [dCA/dx]x = L / CAs

 Using the above equations, on solving, finally we get

η = (1/Ф) [(1/ tanh (3Ф)) - (1/3Ф)]
or
13. a) Derive the rate expression that relates the time with conversion for a fluid solid non catalytic
reaction with a stoichiometry A (g) + b B (s)  E (g) + F (s) as per the unreacted core model when surface
reaction controls the which the particle does not change in size.
Diffusion through Gas film
On solving the above equations, with fundamentals, we get

-(dNB/dt) = 4π R2 b kg CAg

Using dNB = 4π ρB rc2 drc into the above equation and on solving the integral, we get
t = (ρB R)/(3 b kg CAg) [1 – (rc/R)3]

For rc =0 (complete conversion), we get

Τ = (ρB R)/(3 b kg CAg)
Or t/Τ = [1 – (rc/R)3]

We know, 1 – XB = (rc/R)3 or 1 – (rc/R)3 = XB

Thus, we get t/Τ = XB
Diffusion through Ash Layer
By stoichiometry and material balance, with fundamentals, we get

-(dNB/dt) [(1/rc) – (1/R)] = 4π b De CAg

 Using dNB = 4π ρB rc2 drc into the above equation and on solving the integral, we get
t = (ρB R2)/(6 b De CAg) [1 – 3 (rc/R)2 + 2(rc/R)3]

 For rc =0 (complete conversion), we get

Τ = (ρB R2)/(6 b De CAg) Or Τ α R2

 From the above, we get

t/T = [1 – 3 (rc/R)2 + 2(rc/R)3]
  We know, 1 – XB = (rc/R)3 or rc/R = (1 – XB)1/3
Thus, we get
t/Τ = [1 - 3(1 – XB)2/3 + 2(1 – XB)]
Chemical Reaction
By stoichiometry, we have
(-rA||) = (-rB||) / b
Or –(1/4π rc2) dNB/dt = b k|| CAg

 Using dNB = 4π ρB rc2 drc into the above equation and on solving the integral, we get
t = (ρB R)/(b k|| CAg) [1 – (rc/R)]

 For rc =0 (complete conversion), we get

Τ = (ρB R)/(b k|| CAg)
Or t/Τ = [1 – (rc/R)]

 We know, 1 – XB = (rc/R)3 or rc/R = (1 – XB)1/3

Thus, we get t/Τ = [1 - (1 – XB)1/3]

b) A fluidized bed reactor is operating at steady state with a solid feed of varying size distribution as
mentioned below;
50µm – 20%, 80µm – 20%, 100µm – 25%, 150µm – 15% and 200µm – 20%.
The fluidizing gas phase reactant has uniform composition. The time for complete conversion is 4,
8, 12, 16 and 19 minutes respectively of the above mentioned particles. The feed rate is 1.3 kg/min
and the reactor contains 15 kg of solids. Assuming the solids are hard and remain unchanged in
size & weight and also that chemical reaction is rate controlling, calculate the average fractional
conversion of the solid particles.
Ans: We know, for mixture of particles under mixed flow (fluidized bed) and chemical reaction
controls

 Given (50) = 4 min, (80) = 8 min, (100) = 12 min, (150) = 15 min, (200) = 18
min and F(50)/F = 0.20, F(80)/F = 0.20, F(100)/F = 0.25, F(150)/F = 0.15 F(200)/F = 0.20;
Also, W = 15 Kg and F = 1.3 Kg/min.

 Substituting the given data along with = W/F = 15/1.3 = 11.5385 min into the above
equation, we get

≈ 0.204 or ≈ 0.796

14. a) i) what is Enhancement factor.

The liquid enhancement factor (E) is defined as the ratio of rate of take up of gaseous ‘A’ when
reaction occurs to the rate of take up of gaseous ‘A’ for straight mass transfer, at same CAi, CA, CBi, CB
in the two cases. Or Enhancement factor E is defined as the ratio between the Sherwood number
with chemical reaction and that without reaction.

ii) Write a note on Absorption with slow and instantaneous reaction.

Absorption with instantaneous reaction
Reaction occurs on a plane in the liquid film - With low CB
 The rate of transfer of ‘A’ from gas to liquid is given by the rate expressions;
For the gas film, -rA|||| = (kAg a) (PA – PAi)
On rearranging and dividing by ‘HA’, we get
 (-rA||||)/[(kAg a) HA] = (PA/HA) – (PAi/HA)
For the liquid film, -rA|||| = (kAl a) (CAi – 0) (xo/x) = (kBl a) (CB – 0) (xo/(xo - x))
On rearranging, we get
xo/x = [(kBl/b kAl) CB + CAi]/CAi
 Substituting the above into the rate equation for liquid film, we get
[-rA||||/(kAl a)] = (kBl/b kAl) CB + CAi
= (kBl/b kAl) CB + (pAi/pA), by Henry’s law.
 Adding the above equation with the rate of gas film, we get
-rA|||| = {[(kBl/kAl) (CB/b)] + (pA/HA)}/[1/(kAg a) + (HA/kAl a)]
 By two film theory, we know that (kBl/kAl) α (DBl/DAl). Thus, finally we get
||||
-rA = {[( DBl/DAl) (CB/b)] + (pA/HA)}/[1/(kAg a) + (HA/kAl a)]

Reaction occurs on the G-L interface - With high CB

 If the concentration of ‘B’ is raised, only the resistance of the gas-phase controls the
reaction and the rate is not affected by increase in CB.
 Thus, the above final equation becomes
-rA|||| = (kAg a) pA, which is a first order rate with respect to ‘A’.

Absorption with slow reaction

b) i) What are the reaction steps in a slurry reactor?
ii) Writ a note on the parameters based on which a good contractor for a gas liquid solid catalyzed reaction
is selected

Reactor design basically means which type and size of reactor and method of operation we should employ
for a given conversation
Parameters
• Volume of reactor
• Flow rate
• Concentration of feed
• Reaction kinetic
• Temperature
Catalytic reactor selection parameter and design

• Reaction type
• Reactor type
• Economics
• Rate of deactivation
• Other process requirement
Reaction type

• Chemical kinetics of reaction can be known by knowing the type of reaction

• For reactor selection reaction type will tell us about heat of reaction either reaction is endothermic
or exothermic.
• Selectivity is defined as reaction rate ratio for two parallel reaction.
• Catalyst are used to increase reaction rate and selectivity for a specific reaction.
• We can determine what type of catalyst will be used.
• Reaction temperature range will be determined.
Reactor type
• Reactor may be a plug flow or mixed flow or batch flow reactor or other.
• Contacting pattern of reaction will be known.
• In case of expensive catalyst and high heat transfer rate required, mixed flow(fludized bed) reactor
are used.
• For high mass transfer plug flow (packed bed) reactor will be used.
Economics

• For reactor design overall economics should be considered.

• Like instead of different size of mixed flow reactor in series, equal size mixed flow reactor are
economically good.
• If catalyst is not very expensive then we may opt to non-regeneration but for expensive regeneration
must be considered.
Packed bed
• Solid fluid contact will be most efficient
• High amount of catalyst will be used
• Heat transfer will be difficult
• Pressure drop will be high
• Effective for mass transfer control system
• With increase in temperature side reaction will be a problem and less selectivity
• Sintering of catalyst may happen
Fluidized bed
• Industrially most widely used
• Heat transfer are very good
• Pressure drop is low
• Catalyst can easily replaced for regeneration
 • Amount of catalyst necessary is less
• Surface area per unite mass of catalyst will be large

iii) What are the parameters to be considered while selecting the fluid fluid reactor?

Reactor design basically means which type and size of reactor and method of operation we should employ
for a given conversation
Parameters
• Volume of reactor
• Flow rate
• Concentration of feed
• Reaction kinetic
• Temperature

11. a) The reactor is used to carry the reaction A R whose rate is given as -rA = 0.05 CA mol/l.min. the
pulse test carried out in the reactor with a tracer gave the following results.

t, min 0 10 20 30 40 50 60 70
C, mol/lit 35 38 40 40 39 37 36 35
Calculate the conversion as per the tanks in series model.

t, min C, mol/lit ∆t c. ∆t t. c. ∆t t2. c. ∆t

0 35 0 0 0 0
10 38 10 380 3800 38000
20 40 10 400 8000 160000
30 40 10 400 12000 360000
40 39 10 390 15600 624000
50 37 10 370 18500 925000
60 36 10 360 21600 1296000
70 35 10 350 24500 1715000
Σ(c. ∆t) = 2650 Σ(t. c. ∆t) = 104000 Σ(t2. c. ∆t) = 5118000

• Σ(c. ∆t) = 2650 g-sec/m3 Σ(t. c. ∆t) = 104000 g-sec2/m3

Σ(t . c. ∆t) = 5118000 g-sec3/m3
2

• Mean residence time, t = Σ(t. c. ∆t)/Σ(c. ∆t) = 39.245 secs

• Variance, σ2 = {Σ(t2. c. ∆t)/Σ(c. ∆t)} – t2

= 391.54 secs2

• By Tanks-in-series model, we know that

N = 1/σθ2 = t2/σ2 = 3.93 ≈ 4

• Therefore, 1 – XA = 1/{1 + [(k. t)/N]}N

= 1/{1 + [(0.05 * 39.245)/4}4 ≈ 0.20
(or) XA = 80%

b) Following results were obtained for a pulse test on a reactor. The output concentration of the tracer rose
linearly from 0 to 0.5 mol/dm3 in 5 minutes and then fell linearly to 0 in 10 minutes after reaching the
maximum value if 0.5 mol/dm3

Calculate:

1. The mean residence time

2. The reactor volume if the flow rate is 570 l/min.

t, min 0 5 10
C, mol/lit 0 0.5 0

t, min C, mol/lit ∆t c. ∆t t. c. ∆t
0 0 0 0 0
5 0.5 5 2.5 12.5
10 0 5 0 0

Σ(c. ∆t) = 2.5 g-sec/m3 Σ(t. c. ∆t) = 12.5 g-sec2/m3

Mean residence time, t = Σ(t. c. ∆t)/Σ(c. ∆t) = 5 min.

The reactor volume = 570/5 = 114l