Multiphase Tutorial 7

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Multiphase Reactors

TUTORIALS SESSION 7

Tutorial 7.1
For a reaction: A(g)  P (g), which is irreversible and heterogeneously catalyzed, the reaction rate constant
must be known at 298 K. There are three different heterogeneous, porous catalyst types available;
- spheres of a diameter of 0.5.10-3 m,
- cubes (cube) with an edge of 2.10-2 m,
- round rods with a diameter of 10-3 m and a length of 4.10-3 m.

As a result is found that the first-order reaction rate constant is equal to:

k1 = 10 s-1

Data: DA, gas = 10-5 m2.s-1

a) Calculate for the three different heterogeneous, porous catalyst types the Thiele-modulus.

b) Which of the three catalysts has been used to determine k1 and why?

c) In a packed bed reactor conversion measurements are carried out. For this purpose only the
round rods are available. Calculate the conversion at a reactor height of 0.50 m.
The packed bed reactor can be considered as a plug flow reactor.

Data: DA, gas = 10-5 m2.s-1


s = 0,40
dreactor = 0,10 m
CG,A,in = 40 mol.m-3
gas = 10-3 m3.s-1
Pure gas is used and the amount of P produced is allowed to be neglected.

d) Because the reaction is exothermic, it is not really possible to use a pure gas. Therefore A
diluted in such a way that temperature effects are negligible. Calculate again the conversion
at a reactor height of 0.50 m.

Data: CG,A,in = 0.04 mol.m-3


kg = 10-3 m. s-1

Tutorial 7.2
The component 2-methylpropene (MP) is converted in a packed bed reactor with a large excess of
methanol (MeOH) to MTBE according to:

MP + MeOH  MTBE

For this reaction a solid, porous, spherical ion-exchanger is used as catalyst. The reactants and products are
present in a liquid which almost completely exists of MeOH as this reactant is present in a large excess.

The reaction can, because of the large excess MeOH, be regarded as1st-order in MP according to:

RMP = -k1CMP mol.m-3.s-

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Multiphase Reactors

TUTORIALS SESSION 7

Data: k1 = 3.10-2 s-1


DMPL = 5.10-9 m2.s-1
dp = 10-3 m
DMP,catalyst = 2.10-10 m2.s-1
s = catalyst hold-up = 0,50
as = 6s/dp = 3.000 m2.m-3
Sh = 2 = (kLS.dp)/DMPL

a) Calculate the Thiele-modulus.

b) Determine the where the resistance against mass transfer is located. Sketch the
concentration profiles of MP, MeOH en MTBE (both inside and outside the catalyst).

c) Determine an expression for the MP conversion as a function of the residence time in the
packed bed reactor. The packed bed reactor can be considered as an ideal plug flow reactor.

d) The catalyst with a diameter of 1 mm is replaced by particles with a diameter of 1.41 mm.
What happens to the conversion does it increase or decrease with the new catalyst?

Tutorial 7.3

We are going to study the hydrogenation of -methyl styrene (=liquid) using pure hydrogen and a porous
catalyst study in a stirred tank reactor:

-methylstyrene (l) + H2(g)  saturated product P(l)

The kinetics of the reaction is extensively studied and it was observed that the reaction is first order in
hydrogen and zero order in -methylstyrene. The solid, porous catalyst particles are spherical and have a
diameter of 100 m. The reactor is operated at a constant pressure of 30 bar and a temperature of 50 oC.

Data:
k1 =16,8 s-1 s = catalyst hold-up = 0,0703
DH2,catalyst = 1,1.10-9 m2.s-1 g = hydrogen hold-up = 0,20
as = 6s/dp = 60.000 m2.m-3 aGL = 1.500 m2.m-3
kL = 1,23.10-3 m. s-1 kLS = 0,54.10-3 m. s-1

Solubility H2 in reaction phase = 285 m3.bar.kmol-1 at 50 0C.

a) Derive an expression for the amount of hydrogen that is transferred from the gas phase to
liquid phase.

b) Where is the greatest resistance for the mass transport of hydrogen?

c) Please provide a number of ways to increase the amount of hydrogen transferred or the
amount of converted -methylstyrene increase?

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Multiphase Reactors

TUTORIALS SESSION 7

Tutorial 7.4
An industrial process flow contains a small amount of CO which needs to be removed. To do this, one has
the use of a catalyst that enhances the following reaction:

CO  0.5 O2  CO2

There are two types of catalyst available. A so-called monolith and porous catalyst pellets. The monolith
has a structure of all small, parallel, square channels whose non-porous wall is catalytically active. Gas
flows in plug flow through these channels. On the other hand, porous catalyst pellets are inside in a packed
bed. Also in this case the gas flows in plug flow through the column

Additional information is provided at the end of the problem.

a). Give an explicit expression for the conversion of CO at the end of the monolith reactor. Hint: note that
the concentration of O2 much, much higher than that of CO

b). Calculate these outlet concentration expressed in ppm.

c). Give an explicit expression for the conversion of CO at the end of the packed bed reactor.

d). Calculate these outlet concentration expressed in ppm.

e). Which reactor type would you prefer for either a very fast and relatively slow reaction respectively?
Please motivate your answer.

Data
Gas flow 1.10-2 m3s-1 (at 1 bar and 800 K)
[CO]in = 1000 ppm [O2]in = 19%
P = 1 bar T=800 K
RCO = -ks[CO][O2] molm-2catalysts-1 ks = 2.10-3 m4mol -1s-1
DCO = 1.10-5 m2s-1 DO2 = 5.10-5 m2s-1

kG = 1.10-3 ms-1 mass transfer coefficient to wall of the channel (in case of the monolith) or to
the outer surface of the porous catalyst particle (packed bed)

Monolith Packed bed


Lchannels = 1 m Height of the packed bed = 1 m
Edge channel = 2.10-3 m hold-up catalyst particles = 0.5
Total number of channels = 2500 internal surface catalyst = 50,000 m2m-3catalyst
The thickness of the catalyst layer Diameter particle 5.10-3 m
on the outer surface of the channels is Diameter packed bed 0.16 m
negligible.

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Multiphase Reactors

TUTORIALS SESSION 7

Tutorial 7.5
A column reactor is filled with small, non-porous, catalyst particles (a packed bed
reactor).
Flue gas, containing the two reactive components NO (A) and CO (B) is fed into the
column.
At the catalyst surface A and B react according to:

NO + CO → N2 + CO2

With

With cAi and cBi the local concentrations near the catalyst surface.

The following data are known:


- Gas flows as plug flow
- Specific catalyst surface area is: a [m-1]
- Mass transfer coefficient to catalyst is: kG [m/s]
- Feed concentrations and are equal

a. Derive and (implicit) expression for the local conversion rate per m 3 reactor
(RA) as function of a, kG, and the local bulk concentration of A ( ).

b. Derive simplified solutions for the asymptotic cases of complete kinetic and
complete mass transfer control, respectively.

c. Derive an equation for the conversion as function of reactor height, if the


superficial gas velocity is u [m/s].

Tutorial 7.6
The gas phase reaction; A(g)  P (g), is carried out in a packed bed reactor. Inside the
packed bed reactor spherical, porous catalyst particles are present. The packed reactor
can be regarded as an ideal PFR and there are no pressure and temperature gradients
occurring. The reaction is first-order in A; RA”= -k1”CA mol.m-2.s-1
The reaction on the outer surface of the catalyst is negligible compared to that occurring
at the internal surface.

Data:
k1” = 10-2 m.s-1 DA,eff = 1.10-6 m2s-1
acatalyst, internal = 104 m-1 dcatalyst = 6.10-3 m
kG = 10 m.s -2 -1
s = Vcatalyst/Vreactor = 0.40
CA0 = 10 mol.m-3 Vreactor = 2.0 m3
3 -1
Gas flow = 1 m s (and can be assumed to be constant)

a) Derive an expression for the molflux of A.

b) Calculate the outgoing concentration of A.

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Multiphase Reactors

TUTORIALS SESSION 7

Tutorial 7.7
The influence of a porous catalyst on an irreversible first-order reaction A(g)  P (g),
is studied in a research institute. The catalyst particles are completely spherical and the
diameter is 8 mm. The internal catalyst area is 25 m2.particle-1 and the external surface is
0.1 m2.particle-1. The reaction conditions are isothermal. The diffusion coefficient inside the
catalyst particles can be assumed to be independent of the temperature and is equal to
6.5.10-7 m.s-1. The gas phase mass transfer coefficient is equal to 0.095 m.s-1. The reaction
rate constant, k1”, changes with temperature according to Arrhenius. The conversion in all
the experiments is low so that it can be assumed that the concertation of A remains 0.01
kmol.m-3.

The results of the experiments are given below:

Exp. Feed rate number catalyst temperature conversion A


A mol.h-1 particles (K)
A1 0.1 100 400 4.62.10-4
A2 0.1 100 * 400 4.62.10-4
A3 0.2 200 400 4.62.10-4

B4 1.0 100 450 2.98.10-3


B5 2.0 200 450 2.98.10-3
B6 1.0 100* 450 2.98.10-3

C7 100 100 623 3.44.10-2


C8 200 200 623 3.44.10-2

D9 100 10 1273 6.88.10-2

* The catalyst particles are milled and become a powder (particle size < 0.0001 m).

Calculate for all experiments the reaction rate constant, k1” (m.s-1) and the efficiency
factor.

Tutorial 7.8
A gas mixture consisting of the inert gas N2 and a compound A is fed to a packed bed
reactor. The packing in the reactor consists of catalytically active, porous spheres. At the
catalyst surface A can react either to product P or the undesired product C respectively
according to:

A P, with RP”= kP”CA mol.m-2.s-1

AX, with RX”= kX”CA mol.m-2.s-1

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Multiphase Reactors

TUTORIALS SESSION 7

Data:
kP” = 10-2 m.s-1 kX” = 10-3 m.s-1
acatalyst, internal = 103 m-1 dcatalyst = 10-2 m
DA,eff = 1.10-7 m2s-1 DA,G = 1.10-5 m2s-1
Vreactor = 1.0 m3 s = Vcatalyst/Vreactor = 0.40
CA0 = 0.04 kmol.m-3

For the transport of A to the catalyst it can be assumed that Sh = 2 (kG.dcatalyst/DAG)


Moreover, the conversion of A is negligible, i.e. always much lower 5%.

a) What is the physical meaning of the Thiele-modulus and what is its value?
b) Calculate the ratio of the conversion capacity of the internal catalyst surface to the
external catalyst surface.
c) Calculate the conversion capacity of the reactor set-up (kmol A.s-1).
d) What is the differential selectivity?
e) How can the conversion be increased at constant temperature?

Tutorial 7.9
The oxidation of CO;
CO  0.5 O2  CO2
is catalyzed by platinum.
The reaction is already with small excess of O2 only first-order in CO.A well know
multinational is intending to use this platinum catalyst to oxidize CO in off-gas
streams. There are two suppliers for the catalyst:

1) Has an “egg-shell” porous alumina catalyst with a thin layer of platinum on


the outside of the particle.
2) A porous alumina catalyst with platinum present in the whole catalyst.

The research manager asked three principle researchers to determine, independently


from each other, to determine the activation energy of the CO-oxidation on the platinum
on alumina catalyst. Both the egg-shell and the regular catalyst have the same
dimensions and geometry. The following results have been obtained:

Researcher 1: Used the regular catalyst and the reactor was a fluidized bed in which
very high values can be realized for the mass transfer coefficient in the
gas phase. The measured activation energy was EActivation = 50 kJ.mol-1.

Researcher 2: Used the regular catalyst and the reactor was a very small reactor with
only a small number of catalyst particles. In this reactor only low values
can be realized for the mass transfer coefficient in the gas phase. The
measured activation energy was EActivation = 15 kJ.mol-1. Moreover, it
turned out that the reaction rate was a function of the gas throughput in
the reactor.

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Multiphase Reactors

TUTORIALS SESSION 7

Researcher 3: Used the egg-shell catalyst and the reactor was a fluidized bed in which
very high values can be realized for the mass transfer coefficient in the
gas phase. The measured activation energy was EActivation = 100 kJ.mol-1.

After studying the three reports of the researchers the manager asked Researcher 3 to
redo the experiments of Researcher 2 in the same set-up but using the egg-shell
catalyst. Researcher 3 also measured an EActivation = 15 kJ.mol-1. The manager concluded
that the value of EActivation = 100 kJ.mol-1, as determined by Researcher 3, is correct and
the other Researchers have carried out their test correctly but their interpretation was
wrong.

- Explain the results!

Tutorial 7.10
In a gas-liquid-solid reactor of 10 m3 reactant A is catalytically converted to product P by
means of a spherical, porous catalyst with dcatalyst = 10-6 m. The catalyst is uniformly
dispersed in the liquid. The hold-up of the catalyst is 1 vol%.
The gas phase consists of pure A and the concentration is 40 mol.m-3. The liquid phase
is continuously stirred and gas bubbles are dispersed into the liquid phase. This results
effectively in an interfacial area of 250 m2.m-3reactor. The reaction is first-order in A and
irreversible. The external surface of the catalyst can be neglected compared to its
internal surface area. The volumetric reaction rate constant in the catalyst particles (k 1 =
k1”.acatalyst, internal) is 20 s-1. The solubility coefficient , mA=0.80 (CL/CG). The liquid side
mass transfer coefficient is 10-5 m.s-1. The resistance against mass transfer from liquid to
(external) catalyst surface is negligible. The diffusivity of A in the liquid as wells as
catalyst pores is equal to DA,L=5.10-9 m2.s-1.

a) What is the dimension of the liquid-side mass transfer film according to the film model?

b) What is the effectiveness factor of the catalyst particles?

c) Does enhancement of the mass transfer from gas to liquid occur?

d) What is the consumption of A in the steady state operation?

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