SOLUTIONS TUTORIALS SESSION 7

Tutorial 7.1
a) First the Thiele-modulus needs to be calculated.
Spheres: ’= 8.33.10-5 m Thiele-modulus = 0.08 effectiveness factor  =1
Cubes: ’= 3.33.10-3 m Thiele-modulus = 3.33 effectiveness factor  =0.3
Rods: ’= 2.22.10-4 m Thiele-modulus = 0.24 effectiveness factor  =0.98

b) Intrinsic kinetics can only be measured for porous catalysts in case the Thiele-modulus is smaller than
0.1. This only applies for the spheres!

c) The Thiele-modulus for the rods is equal to 0.24 and the effectiveness factor can be calculated with: 
= tanh’/’ with ’ is the Thiele modulus,  =0.98.

With:
JA = k1CAG.’ mol.m-2.s-1,
a = 6/’ = 10,810 m2.m-3,
Vr = (/4)(dreactor2).H = 3.93.10-3 m3,

As a pure gas is used the concentration of A is not a function of the location in the reactor.
Therefore the amount of A that can be converted is equal to:

JAa Vr = 3.77 mol.s-1,

and the total amount of A that is fed to the reactor is equal to G.CAG,in = 4.10-2 mol.s-1.
Therefore all A is converted.

d) Now the concentration is diluted by a factor 1000. This means that the gas flow does not change!

Compare gas phase resistance, kG = 10-3 to internal catalyst resistance, ’k1 = 2.22.10-3.
Both resistance need to be taken into account!
Mass balance A over gas phase:

G.CAG,x - G.CAG,x+x = -koverall. CAG,x.a.S.x.

Results in:

CAG = CAG, in.exp(-koverall.a.Vr/G) = exp(-29.29) = 0 so XA =100%.

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SOLUTIONS TUTORIALS SESSION 7

Tutorial 7.2
a) First the Thiele-modulus needs to be calculated.

’= 1.67.10-4 m Thiele-modulus = 2.04 effectiveness factor  =0.49

b) Determination of the resistances:

- liquid to catalyst: kLS = (Sh.DMPL)/dp = 10-5,
- internal catalyst: .’.k1 = 2.45.10-6
So both resistance need to be taken into account.
c) Differential mass balance MP for the liquid phase:
- (kov)-1 = (kLS)-1 + (.’.k1)-1
- JMP.as = kov.as.CMP

- L.CMP,x - L.CMP,x+x = -kov. CMPG,x.as.S.x

- CMP = CMP, in.exp(-kov.as.Vr/L)

d) The catalyst is replaced, new diameter is 1.41 mm instead of 1.0 mm.

- First the Thiele-modulus needs to be calculated.

’= 2.35.10-4 m Thiele-modulus = 2.88 effectiveness factor  =0.35, = lower

- as, new = 2.128 m-1, = lower

- kLS = (Sh.DMPL)/dp = 7.09.10-6, = lower.

Three parameters are lower, so the conversion decreases.

Tutorial 7.3
a) This is a three phase system which means that there four resistances in series. This results for the flux
CG
in: N= VS
1 1 1 1
+ + +
k G a GL mk L a GL mk LS a s mk " a
1 s
However, in this tutorial the catalysts is porous and this means that the last resistance,
mk1”as needs to be replaced by: k1’as. Moreover, there is a pure gas, so the first resistance can be
neglected.

b) determination of the three resistances;

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SOLUTIONS TUTORIALS SESSION 7

- 1/kLaGL = 0.541
- 1/kLSaS = 0.031

For the catalyst resistance the Thiele-modulus needs to be calculated:

’= 1.67.10-5 m Thiele-modulus = 2.06 effectiveness factor  =0.49,
- 1/k1’as = 0.122

The greatest resistance is located in the transport from gas-liquid interface to the liquid bulk. However,
not one of the resistances can be neglected.

c) the conversion can be increased via:

- higher kLS, i.e. higher stirrer speed,
-  can be increased via smaller catalyst particles, this also has a positive effect on kLS,
- more catalyst particles.

Tutorial 7.4
a). Monolith:
For the flux to the catalyst surface it can be written: J = k G (COG − CO s )
For the reaction at the catalyst surface it can be written: J = k s CO s O 2,s

There is a very high O2 concentration compared to CO, so it can be assumed that the concentration of O2
at the surface is nearly equivalent to the bulk concentration. This means that the reaction rate equation
is simplified to: J = k s' CO s
CO
Elimination of COs results in: J=
1 1
+
k s' kG

Next MB CO for 1 channel (note: the flow rate can be taken constant because the % CO is very low):

G dCO CO
=− 4a
n dz 1 1
+
k s' k G
dCO n
Resulting in: =− 4adz
CO G 1 1
+
k s' k G

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SOLUTIONS TUTORIALS SESSION 7

n
− 4aL
G 1 1
+
k s' kG
after integration: [CO ] = [CO ] in exp

b) Substitution of the data gives the final concentration that is equal to 182 ppm.

c). Packed Bed Reactor:

Here porous catalyst spheres are used. First the Thiele modulus needs to be calculated. As for case
monolith it can be assumed that the concentration of O2 is constant by large excess.
The volumetric pseudo first order reaction rate constant in the porous catalyst is:

k 1 = k s [O 2 ][ CO ]a inwendig = k s' [CO ]

The Thiele modulus wordt nu:

r k s'
= >2 (4.45).
3 DCO
1
Therefore the effectiveness factor becomes:  = (0.225)

This gives for the flux to the catalyst particles: J = k s' DCO [CO ] s
[CO ]
Elimination of [CO]s results in: J=
1 1
+
k s' DCO kG

Mass balance for CO, gasphase, for the packed bed reactor results in:

d [CO ] − [CO ] 6 s 2
G = 0.25d kolom
dz 1 1 dp
+
k s' DCO k G

After integration the CO-concentration as function of the reactor location is obtained:

−1 6 s 1 2
0.25 d kolom L
1 1 d p G
+
k s' D CO kG
CO = [CO ] in exp

d) Substitution of the data gives the final concentration that is equal to 306 ppm

e) For a fast reaction (Thiele modulus >2) only the outer surface of the particles is used. For identical
values of kG the reactor with the highest external (outer) surface is best suited.

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SOLUTIONS TUTORIALS SESSION 7

4aLn 4
Monolith: as = = = 2000 m 2 m −3
2 a
na L

6
Packed bed: as = = 600 m 2 m −3
dp
Here the monolith is the preferred reactor.

For a slow reaction (Thiele modulus <0.2) the internal (“inwendig”) surface of the particles is used.

The monolith is non-porous, and therefore it has no internal surface, and so as,internal = as, outer
4aLn 4
a s ,inwendig = a s ,uitwendig = = = 2000 m 2 m −3
2
na L a

For the catalysts particles in the packed bed, the internal surface is equal to:
a s ,inwendig =  s .a s = 25000 m 2 m −3

For slow reactions the packed bed reactor is preferred.

Tutorial 7.5

a) A = NO and B = CO

′′
𝐽𝑎 = 𝑘𝐺 (𝑐̅𝐴 − 𝑐𝐴,𝑖 ) = 𝑘1,1 𝑐𝐴,𝑖 𝑐𝐵,𝑖

′′
𝐽𝑏 = 𝑘𝐺 (𝑐̅̅̅
𝐵 − 𝑐𝐵,𝑖 ) = 𝑘1,1 𝑐𝐴,𝑖 𝑐𝐵,𝑖

𝐽𝑎 = 𝐽𝑏 and 𝑐𝐴0 = 𝑐𝐵0 resulting in (𝑐̅𝐴 ) = (𝑐̅̅̅)

𝐵 and 𝑐𝐴,𝑖 = 𝑐𝐵,𝑖

′′ ′′ 𝐽
Therefore, 𝐽𝑎 = 𝑘𝐺 (𝑐̅𝐴 − 𝑐𝐴,𝑖 ) = 𝑘1,1 𝑐𝐴,𝑖 2 → 𝐽𝑎 = 𝑘1,1 (𝑐̅𝐴 − 𝑘𝑎 )2
𝐺

And the conversion per m³ reactor (Ra):

′′ 𝑅𝑎 2
𝑅𝑎 = 𝐽𝑎 𝑎 = 𝑘1,1 ∗ 𝑎(𝑐̅𝐴 − 𝑘 )
𝐺 ∗𝑎

3b) Asymptotic situation 1:

′′ 𝑐 ′′
𝑅 ′′ ̅̅̅̅̅ 𝑘1,1
𝑐̅𝐴 ≫ 𝑘 𝐴𝑎 𝑡ℎ𝑒𝑛 𝑅𝑎 = 𝑘1,1 𝑎𝑐𝐴−2 or 𝑘𝐺
𝐴
≪1 kinetic controlled
𝐺

Asymptotic situation 2:
′′ 𝑐 ′′
𝑘1,1 𝐴
If 𝑘𝐺
≫ 1 𝑡ℎ𝑒𝑛 𝑅𝑎 = 𝑘𝐺 𝑎𝑐̅𝐴 mass transfer controlled

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SOLUTIONS TUTORIALS SESSION 7

̅̅̅̅
𝑑𝑐 𝐴
3c) 𝑢 = −𝑅𝑎 (𝑐̅𝐴 ) = (𝑐̅̅̅̅)(1
𝐴0 − 𝑥𝐴 )
𝑑𝑥

𝑑𝑥𝐴 𝑅𝑎
Substitute: 𝑢 =− with cA=cA0 at x=0.
𝑑𝑥 𝑐𝐴0

Tutorial 7.7
a) k1”= 5.13.10-13 m.s-1  = 1.00

b) k1”= 3.31.10-11 m.s-1  = 1.00

c) k1”= 3.47.10--7 m.s-1  = 0.106

d) k1”= 7.59.10-2 m.s-1  = 0.0002

Tutorial 7.8
a)  = 17,5

b) Ratio = 10.5

c) Conversion capacity = 1.65.10-2 kmol.s-1

d) P’=0.91

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