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1.1. For the thermal cracking of ethane in a tubular reactor, the following data were
obtained for the rate coefficient at different reference temperatures:
T(°C) 702 725 734 754 773 789 803 810 827 837
-1
k(s ) 0.15 0.273 0.333 0.595 0.923 1.492 2.138 2.718 4.137 4.665
Solution
E
k A exp
RT
E
ln k ln A
RT
x = 1/T∙ 10³ y = ln k
1.025 –1.897
1.002 –1.298
0.993 –1.100
0.974 –0.519
0.956 –0.080
0.941 0.400
0.929 0.760
0.923 1.000
0.909 1.420
0.901 1.540
The slope and the intercept (ln A) are calculated by linear regression:
x y
xy
E N
2
R x
2
x
N
y m x
ln A
N
E
28497. or E 56623 kcal/kmol or 2.37 10 5 kJ/kmol.
R
1.2. Derive the result given in Table 1.2.4.2-1 for the reaction
.
A
B
Q
S
Solution
A
B
Q
S
dC A
k CACB (1)
dt
CB C B0 (C A 0 CA )
Hence,
CA t
dC A
k dt
C A0
C A (C B 0 C A 0 CA ) 0
or
1 CB CA
kt ln 0
CB0 CA 0 CA 0 CB
CA CA 0 1 x A
CB CB0 CA 0 CA CB0 CA 0 CA 0 1 x A
CB0 CA 0 x A
Hence
1 CB0 CA 0 1 x A
kt ln
CB0 C A 0 C A 0 (C B 0 C A 0 x A )
or
1 M 1 xA
C A 0 kt ln
M 1 M xA
with
C B0
M
C A0
1.3. Derive the solutions to the rate equation for the first order reversible reaction given
in Section 1.2.3.
Solution
1
For A Q
2
dC A
rA k1 C A k 2CQ
dt
k 1C A k 2 C A0 C Q0 CA
or
dC A
k1 k 2 CA k 2 C A0 C Q0
dt
Thus
d k1 k2 t k1 k 2 t
e CA e k 2 C A0 C Q0
dt
and
k1 k 2 t
CA e \ b k 2 (C A 0 CQ 0 e k 1 k2 t
dt K)
k2 k1 k 2 t
CA 0 CQ 0 Ke
k1 k2
k2 k1C A 0 k 2CQ 0 k1 k 2 t
CA CA 0 CQ 0 e
k1 k2 k1 k2
dC A dx A
CA 0
dt dt
d
CA 0 xA x A eq
dt
Then
d
xA x A eq k1 k2 xA x A eq
dt
xA x A eq
ln k1 k2 t 0
0 x A eq
or
xA
ln 1 k1 k2 t
x A eq
1.4. A convenient laboratory technique for measuring the kinetics of ideal gas phase
single reactions is to follow the change in total pressure in a constant volume and
temperature container. The concentration of the various species can be calculated
from the total pressure change.
aA bB ... qQ sS ...
V pt p t0
ξ
RT Δ α
(b) Next show that partial pressure for the jth species can be found from
aj
pj p j0 pt p t0
Δ α
(c) Use the method to determine the rate coefficient for the first-order decomposition of
di-t-butyl peroxide
CH 3 3 COOC CH 3 3
2 CH 3 2 CO C2 H 6
The data given below are provided by J.H. Raley, R.E. Rust, and W.E. Vaughn
[J.A.C.S., 70, 98 (1948)]. They were obtained at 154.6°C under a 4.2-mm Hg partial
pressure of nitrogen which was used to feed the peroxide to the reactor. Determine the
rate coefficient by means of the differential and integral method of kinetic analysis.
0 173.5
2 187.3
3 193.4
5 205.3
6 211.3
8 222.9
9 228.6
11 239.8
12 244.4
14 254.5
15 259.2
17 268.7
18 273.9
20 282.0
21 286.8
∞ 491.8
Solution
a) For 0 α jA j
j
Nj N j0 α jξ
Also,
RT RT
pj N j, pt pj Nj
V j V j
Thus,
ξ α j Nj N j0
j j
V
pt p t0
RT
with Δ α α j
j
V p t p t0
ξ
RT Δ α
b) Use
RT RT
pj Nj N j0 α jξ
V V
RT V p t p t0
p j0 α j
V RT Δ α
α j
p j0 pt p t0
Δ α
c) CH 3 3 COOC CH 3 3
2 CH 3 2 CO C 2 H 6
1 dξ 1 V 1 d
rA pt pt 0
V dt V RT Δ α dt
pA k ( 1)
kC A k pA 0 pt pt 0
RT RT 2
or
d 1
pt pt 0 2k p A 0 pt pt 0
dt 2
Integrating yields:
1
p A0 pt p t0
ln 2 kt
p A0
The integral method uses a plot of ln [ ] vs. t, and the slope gives the value of k.
Alternatively, a linear or nonlinear regression method could be used: k = 0.0193 min-1.
The differential method utilizes slopes from the p t p t 0 data plotted vs.
1
p A0 p t p A 0 , the slope of which, or regression techniques, gives the rate
2
coefficient: k = 0.0196 min-1.
0.5
0.4
1
p A0 pt p t0
2
- ln 0.3
p A0
0.1
0
0 5 10 15 20 25
time(min)
1.5. The results of Problem 1.4 can be generalized for the measurement of any property
of the reaction mixture that is linear in the concentration of each species:
λ j K jC j
The λ j could be partial pressures (as in Problem 1.4) various spectral properties, ionic
conductivity in dilute solutions, and so on. Then the total observed measurement for the
mixture would be:
λ λ j K jC j
j j
α jA j 0
j
ξ
λ λ 0 α jK j
j V
where
λ 0 K jC j0
j
b) After a long (“infinite”) time, the extent ξ can be evaluated for irreversible reactions
from the limiting reagent, and for reversible reactions from thermodynamics. Use this
to formulate the desired relation containing only measured or determined variables
(see Frost and Pearson [41]):
λ λ 0 ξ
λ λ ξ
λ K jC j
j
α jA j 0
j
Nj N j0 ξ
Cj α j
V V V
Thus,
N j0 ξ
λ Kj Kj j
j V j V
ξ
K jC j0 K jα j , constant volume
j j V
b) For infinite time, either ξ can be found from the thermodynamic equilibrium
constant
α j
ξ
KC C j0 α j
j V
ξ
0 C 0,LR α LR
V
ξ λ λ 0
V α jK j
and
ξ λ λ 0
V α jK j
ξ λ λ 0
ξ λ λ 0
1.6. Show that the general expression for the concentration at which the autocatalytic
reaction of Section 1.2.3.3 has a maximum rate is
C CQ
12
CC
1
Q
0
A
0
0
Q
a
x
m
Note that this agrees with the specific results in the example.
Solution
r k1 C0 CQ CQ k 2 C Q2
r
0 k 1C 0 2k 1C Q 2k 2 C Q
CQ
or
1 k1 1 K
CQ max
C0 C0
2 k1 k 2 2 1 K
1 C A0
1
2 C Q0
1.7. Derive the concentration as a function of time for the general three species first
order reactions:
1
A Q
2
4 3 5 6
These should reduce to all the various results for first order reactions given in
Sections 1.2 and 1.3. Also determine the equilibrium concentrations CAeq, CQeq, CSeq
in terms of the equilibrium constants for the three reactions.
Solution
The general solution method is best explained in terms of the complex reaction network
notation where the rate for the jth species is given by:
dy j N
k j1y1 k j2 y 2 ... ' k lj y j ... (1)
dt l 1
λ t
yj Yj0 e (2)
where Yj and λ are constants to be determined. Substituting (2) into (1) gives
λ t λ t λ t
Yj λ e k jl Y1e ... ' k lj Yje ...
or
k j1Y1 k j2 Y2 ... ' k lj λ Yj ... 0 (3)
If equations (3) are written out for each of the j = 1, 2, … N species, they form a set of N
equations for the N unknown, Yj. Note that they are homogeneous algebraic equations
(RHS ≡ 0), and so they only possess solutions if the determinant of the coefficients is
zero.
λ ' k l1 k12 k13 k1N
k 21 λ ' k l2 k 23 k 2N
0 (4)
k N1 k N2 k N3 λ ' k lN
When multiplied out; (14) will be an Nth order equation, with N-roots. For each of these
roots, a set of the constants Yj can be found from (3): Yjr. Then the general solution will
be
N
yj C r Yjr e λ rt (5)
r 1
where Cr are constants of integration to be found from the initial conditions. For our
specific problem, the determinant, (4), is:
λ k1 k3 k1 k3
k2 λ k2 k6 k6 0 (6)
k4 k5 λ k4 k5
2
λ λ k1 k2 k3 k4 k5 k6 k1 k 4 k5 k6
λ 0
k 2 k3 k4 k5 k3 k5 k6 k 4k 6
or
2
λ λ α λ β 0 (7)
λ 1 0
2
α α 4β
λ 2,3 (8)
2
λ 2t λ 3t
CA C1 YA1 C 2 YA2 e C 3 YA3 e (9)
λ 2t λ 3t
CQ C1 YQ1 C 2 YQ2 e C 3 YQ3 e (10)
λ 2t λ 3t
CS C1 YS1 C 2 YS2 e C 3 YS3 e (11)
for each of the λ r (actually, only two of the equations will be independent, and so two of
the Yjr can be found in terms of the third).
Finally, the integration constants, Cr, are found from the initial conditions:
where YA1 and C1 are known in terms of the kji and initial concentrations. From the
principle of microscopic reversibility, it is also time that each reaction is individually at
equilibrium, leading to:
CQ k1
KI
CA eq
k2
CA k4
K II (15)
CS eq
k3
CS k6
K III
CQ eq
k5
with
K I K II K III 1 (16)
CA CQ CS C A0 C Q0 C S0 C0 (17)
Similarly
C0
C Qe C1 YQ1 (18)
K II 1 K III
C0
C Se C1 YS1
1
K II 1
K III
1
aA bB qQ
2
q' Q b' B sS
(a) Use (1.1.2-15) and (1.1.2-17) to express the time rates of change of NA, NB, NQ,
and NS in terms of the two extents of reactions and stoichiometric coefficients a, b,
b’, q, q’, and s; for example,
dN A dξ 1 dξ 2
a (0)
dt dt dt
(b) In practical situations, it is often useful to express the changes in all the mole
numbers in terms of the proper number of independent product mole number
changes—in this case, two. Show that the extents in part (a) can be eliminated in
terms of dNQ/dt and dNS/dt to give
dN A a dN Q a q' dN S
dt q dt s q dt
dN B b dN Q b q' b' dN S
dt q dt s q s dt
N
α ij A j i 1, 2, ..., M
j 1
The mole number changes in terms of the extents are
dN j N
dξ i
α ij
dt j 1 dt
or
dN T dξ
α
dt dt
T
where N is the N-vector of numbers of moles, ξ is the M-vector of extents, and α is
the transpose of the M x N stoichiometric coefficient matrix. Show that if an
alternate basis of mole number change is defined as an M-vector
dN b
dt
that the equivalent expressions for all the mole number changes are
dN T b T
1 dN b
α α
dt dt
b
where α is the M x M matrix of the basis species stoichiometric coefficients.
Finally, show that these matrix manipulations lead to the same result as in part (b) if
the basis species are chosen to be Q and S.
Solution
aA bB qQ ξ 1
Nj α ij ξ i, Nj N j0 α ijξ i
i i
Thus,
NA aξ 1 (1)
NB bξ 1 b' ξ 2 (2)
NQ qξ 1 q' ξ 2 (3)
NS sξ 2 (4)
Thus,
a a q'
NA NQ NS (7)
q sq
b b r' b'
NB NR NS NS (8)
r s r s
N
0 α ijA j , i 1, 2, ..., M (9)
j 1
N
~
[α ~ ] T ξ (10)
~
N
~
(11)
β α
α~ [α ~ ]α 1, M 1
1, M 1
(12)
(The stoichiometric coefficient matrix can always be arranged to have the new basis
species coefficients first.)
Now the subset of the mole number change equations for the new basis species are:
b
b
N~ [α ~ ]T ξ (13)
~
which is equivalent to (3)-(4) above. Then solving for the extents gives
b
b 1
ξ [α ~ ]T N~ (14)
~
b
T b T 1
N~ [α ~ ] [α ~ ] N~ (15)
This general result can be used to define any conversion basis in a complex reacting
system.
aA bB qQ
ξ 1
q' Q b' B sS ξ (M = 2)
~ ξ 2
a 0
a b q 0 T b b'
α~ , α~
0 b' q' s q q'
0 s
a 0 aξ 1 0
b b' ξ bξ b' ξ
N [α ~ ]T ξ 1 1 2
~ q q' ξ qξ q' ξ
2 1 2
0 s
0 sξ 2
as in part (a).
b
NQ
N
~
NS
and
b q 0
α~
q' s
b q q'
[α ~ ]T
0 s
s q'
b 0 q
{[α ~ ]T } 1
qs
and
a 0 s q'
T b b b' 0 q
α ~ {[α ~ ]T } 1
q q' qs
0 s
as aq'
1 bs bq' b' q
qs qs qq' q' q
0 qs
Finally,
a aq'
NQ NS
q qs
b b bq' b'
N α T 1
N NQ NS
~ ~ q qs s
NQ
NS
or
a a q'
NA NQ NS
q sq
b b q' b'
NB NQ NS
q s q s
NQ NQ
NS NS
1.9. Show that the overall orders for a free radical reaction mechanism with a first
order initiation step are 3 2 and 1 2 for a β β , respectively μ μ termination.
Solution
(a) β β termination
k1
A1 2R 1
k2
R1 A1 R1 H R 2
k3
R2 R1 A2
k4
R1 R1 A1
dC A1
k1C A1 k 2C R 1 C A1 k 4C 2R 1 (1)
dt
dC R 1
2k1C A1 k 2C R 1 C A1 k 3C R 2 2k 4C 2R 1 0 (2)
dt
dC R 2
k 2C R 1 C A1 k 3C R 2 0 (3)
dt
From (3): k 3C R 2 k 2C R 1 C A1
2k1C A1 k 2C A1 C R 1 k 2C R 1 C A1 2k 4C 2R 1 0
k1
CR 1 CA (4)
k4 1
dC A1 k1 3 2
k2 CA (5)
dt k4 1
k1
A1 2R 1
k2
R1 A1 R1 H R 2
k3
R2 A2 R1
k5
R2 R2 A3
dC A1
k1C A1 k 2C R 1 C A1 (6)
dt
dC R 1
2k1C A1 k 2C R 1 C A1 k 3C R 2 0 (7)
dt
dC R 2
k 2C R 1 C A1 k 3C R 2 2k 5C 2R 2 0 (8)
dt
k1 1 2 k1 k3 k1 1 2
CR 2 CA and CR 1 2 CA (9)
k5 1 k2 k2 k5 1
dC A1 k1 k3 k1 1 2
k1C A1 k 2C A1 2 CA
dt k2 k2 k5 1
k1 1 2
3k1C A1 k3 CA (10)
k5 1
k1 1 2
k3 CA
k5 1
1.10. The thermal decomposition of dimethyl ether
CH 3 OCH 3 CH 4 CO H 2
or
CH 3 OCH 3 CH 4 HCHO
k1
CH 3 OCH 3 CH 3 OCH 3
k2
CH 3 CH 3 OCH 3 CH 4 CH 2 OCH 3
k3
CH 2 OCH 3 CH 3 HCHO
k4
CH 3 CH 2 OCH 3 C 2 H 5 OCH 3
(a) For a first order initiation step, use the Goldfinger, Letort and Niclause
table [1948] to predict the overall order of reaction.
(b) With the help of the steady state assumption and the usual approximation
of small initiation and termination coefficients, derive the detailed kinetic
expression for the overall rate:
d CH 3OCH 3 n
k o CH 3OCH 3
dt
and verify that the overall order, n, is as predicted in part (a). Also find ko in
terms of k1, k2, k3, k4.
(c) If the activation energies of the individual steps are E1 = 80, E2 = 15, E3 =
38, E4 = 8 Kcal/mol, show that the overall activation energy is Eo = 62.5 Kcal/mol.
Solution
(a) The termination is of the type β μ . Hence, for a first order initiation, the overall order of
reaction is 1.
d CH 3OCH 3
k1 CH 3OCH 3 k 2 CH 3 CH 3OCH 3 (1)
dt
d CH 3
k 1 CH 3 OCH 3 k 2 CH 3 CH 3 OCH 3
dt
(2)
k 3 CH 3 OCH 2 k 4 CH 3 CH 3 OCH 2 0
d CH 3 OCH 2
k 2 CH 3 CH 3 OCH 3 k 3 CH 3 OCH 2
dt
(3)
k 4 CH 3 CH 3 OCH 2 0
k 2 CH 2 CH 3 OCH 3
CH 3 OCH 2 (4)
k 3 k 4 CH 3
k1 CH 3OCH 3 k 2 CH 3 CH 3OCH 3
k 2 CH 3 CH 3OCH 3 k 4 CH 3 k 2 CH 3 CH 3OCH 3
k3 0
k 3 k 4 CH 3 k 3 k 4 CH 3
or
2
2k 2 k 4 CH 3 k 1 k 4 CH 3 k 1k 3 0
The terms k1k 4 CH 3 may be dropped because k1 and k4 are small compared to the
other k’s. Hence
k 1k 3
CH 3 (5)
2k 2 k 4
d CH 3OCH 3 k1k 3
k1 CH 3OCH 3 k2 CH 3OCH 3
dt 2k 2 k 4
d CH 3 OCH 3 k 1k 2 k 3
CH 3 OCH 3 (6)
dt 2k 4
This corresponds to n = 1.
k1k 2 k 3
ko
2k 4
1.11. K. Laidler and B. Wojciechowski [Proc. Roy. Soc., A260, 91 (1961)] provide the
following table of individual rate constants for ethane pyrolysis:
Reaction A0 E (Kcal/mol)
1 1.0 1017 85.0 1st order initiation
1a 2 (6.5) 1017 70.2 2nd order initiation
2 2.0 1011 10.4 hydrogen abstraction
3 3.0 1014 39.5 radical decomposition
4 3.4 1012 6.8 H C2H 6 H 2 C2H 5
5 1.6 1013 0 H C2H 5 termination
13
6 1.6 10 0 C2 H 5 C2 H 5 termination
(a) Derive the overall kinetic expressions for the four combinations of the two
possible initiation steps (1 or 1a) and the termination steps (5 or 6).
(b) Compare the overall rate constants at T = 837°K with the experimental
value of 8.4 10-4 s-1.
(c) Show that the ratio of the rates of reaction 5 and 6 is given by:
r5 k 3k 5 1
r6 k 4k 6 C 2 H 6
(d) Calculate the “transition pressure level” where terminations (5) and (6)
are equivalent (r5 = r6) at T = 640°C, and compare with the measured value of 60
mm Hg. At this point, the overall reaction is changing from 1 to 3/2 order.
Solution
k1
1. C 2 H 6 2CH 3
k1a
1a. Χ C2H6 2CH 3 Χ
k2
2. C 2 H 6 CH 3 CH 4 C2H5
k3
3. C 2 H 5 C2H 4 H
k4
4. C 2 H 6 H H2 C2H5
k5
5. C 2 H 5 H C2H6
k6
6. C 2 H 5 C2H5 C 4 H 10
d C2H6
k1 C 2 H 6 k 2 C 2 H 6 CH 3 k 4 C2H6 H
dt
(1)
k 5 C2H5 H
d CH 3
2k 1 C 2 H 6 k 2 C 2 H 6 CH 3 0 (2)
dt
d C2H5
k 2 C 2 H 6 CH 3 k 3 C2H5 k 4 C2H 6 H
dt
(3)
k 5 C2H5 H 0
dH
k 3 C2H5 k 4 C2H 6 H5 k 5 C2H5 H 0 (4)
dt
From (2)
2k 1
CH 3 (5)
k2
From (4)
k 4 C2H 6 H
C2H5 (6)
k3 k5 H
k 3k 4 C 2 H 6 H
C 2 H 6 2 k1 k 4 C2H 6 H
k3 k5 H
k 5 H k 4 C2H 6 H
0
k3 k5 H
d C2H6 k 1k 3 k 4
C2H6 (9)
dt k5
d C2H6 2
k 1a C 2 H 6 k 2 C 2 H 6 CH 3 k 4 C2H6 H
dt
(10)
k 5 C2H5 H
d CH 3 2
2k1a C 2 H 6 k 2 C 2 H 6 CH 3 0 (11)
dt
From (11):
2k 1a
CH 3 C2H6 (12)
k2
k 3k 4 C 2 H 6 H
C 2 H 6 2k1a C 2 H 6 k 4 C2H 6 H
k3 k5 H
k 5 H k 4 C2H 6 H
0
k3 k5 H
k 1a k 3
H C2H6 (13)
k 4k5
Substitution of (13) into (6):
k1a k 3k 4 32
C2H 6
k5
C2H5
k1a k 3k 5
k3 C2H 6
k4
or
k 1a k 4 3/ 2
C2H5 C2H6 (14)
k 3k 5
Substitution of (12), (13) and (14) into (10) and neglecting terms in k1 yields:
d C2H6 k 1a k 3 k 4 3/2
C2H6 (15)
dt k5
d C2H 6
k1 C 2 H 6 k 2 C 2 H 6 CH 3 k 4 C2H 6 H (16)
dt
d C2H5
k 2 C 2 H 6 CH 3 k 3 C 2 H 5 CH 3 k 4 C2H 6 H
dt
(17)
2
k 6 C2H5 0
dH
k 3 C2H5 k 4 C2H 6 H 0 (18)
dt
From (18):
k 3 C2H5
H (19)
k 4 C2H6
2k 1 1/ 2
C2H5 C2H6 (20)
k6
Hence
2k 1 k 3 1/ 2
H C2H6 (21)
k6 k4
d C2H6 2k 1 1/ 2
k3 C2H6 (22)
dt k6
d C2H6 2
k 1a C 2 H 6 k 2 C 2 H 6 CH 3 k 4 C2H6 H (23)
dt
d C2H5 dH
For and see equations (17) and (18).
dt dt
2k 1a
C2H5 C2H6 (24)
k6
k3 2k1a
H (25)
k4 k6
d C2H6 2 2 2k 1a
k 1a C 2 H 6 2k 1a C 2 H 6 k3 C2H6
dt k6
b)
k 1k 3 k 4
Case 1:
k5
k 1a k 3 k 4
Case 2:
k5
k 1k 3 k 4
Case 3:
k5
2k 1a
Case 4:
k6
With these individual rate constants, the overall rate constants become for:
r5 k 5 C2H5 H
(c) 2
r6 k 6 CH 5
k 1k 3
from (7): H
k 4k 5
k1k 3
from (8) : C2 H 5 C2H 6
k 4k 5
Hence:
r5 k 5k 3 1
r6 k 6k 4 C2H 6
Hence:
r5 k3 1
1
r6 k 4 C2H 6
1.05 105
C2H 6 1.31 10- 6 mol/cm³
8.01 1010
0.098 atm
74 mm Hg
Experimentally, 60 mm Hg is observed.
1.12. The overall reaction for the decomposition of nitrogen pentoxide can be written
as:
2N 2 O 5 4NO 2 O2
N 2O 5 NO 3 NO 2
NO 2 NO 3 N 2O 5
NO 2 NO 3 NO 2 O2 NO
NO NO 3 2NO 2
If the steady state approximation for the intermediates is assumed, prove that the
decomposition of N 2 O 5 is first order [Reference: R.A. Ogg, J. Ch. Phys., 15, 337
(1947)].
Solution
In steady state:
d NO3
r1 r2 r3 r4 0
dt
or
k1 N 2O5
NO 3 (1)
k2 k 3 NO 2 k 4 NO
d NO
r3 r4 k 3 NO 2 NO 3 k 4 NO NO 3 0
2dt
or
k3
NO NO 2 (2)
k4
k1 N 2O5
NO 3 (3)
k 2 2k 3 NO 2
d N 2O5
r1 r2 k1 N 2O5 k 2 NO 2 NO 3 (4)
dt
d N 2O5 2k 1 k 3
N 2O5 (5)
dt k 2 2k 3
1.13. The previous reaction was carried out in a constant volume and constant
temperature vessel, to allow the application of the “total pressure method”
outlined in Problem 1.4. There is one complication however: the dimerization
reaction 2NO 2 N 2 O 4 also occurs. It may be assumed that this additional
reaction immediately reaches equilibrium, the dimerization constant being given
by:
2866
logK p logT 9.132 (T in °K; Kp in mm-1)
T
The following data were obtained by F. Daniels and E.H. Johnson [J. Am. Chem.
Soc., 43, 53 (1921)] at 35°C, with an initial pressure of 308.2 mm Hg:
t (min) pt (mm Hg)
40 400.2
50 414.0
60 426.5
70 438.0
80 448.1
90 457.2
100 465.2
120 480.0
140 492.2
160 503.2
180 512.0
200 519.4
240 531.4
280 539.5
320 545.2
360 549.9
565.3
Determine the first order rate coefficient as a function of time. What is the
conclusion?
Solution
dp N 2O5
r kp N 2O5
dt
The solution is
0
p N 2O5 kt 1 p N 2O5
e or k ln (1)
p 0N 2O5 t p N 2O5
pt p NO 2 p NO p O2 p N 2O5 p N 2O 4 p NO3
From the apparent reaction, the terms pNO and pNO3 drop out. The complete structure reads
1
N 2O5 2NO 2 O2
2
N 2O4
Let α be the degree of dissociation of N 2 O 4 : when α = 0, no dissociation is taking place.
When α = 1, dissociation is complete. At time t, let the conversion of N2O5 be x. The
composition of the reacting mixture on the basis of one mole of N 2 O 5 is then:
N 2O5 1-x
NO 2 2α x
N 2O4 x(1-α )
O2 1/2x
1 α 1/2 x
1
pt 1 α x p 0N 2O5 (1)
2
By definition:
3 0
α p N 2O5 pt
2
p N 2O5 (3)
1
α
2
x 1 α p 0N 2 O 5
pt
p N 2O 4 1 a 1/2 x p 0N 2 O 5
Kp 2
p 2N 2 O 5 4x 2α 2
p 0N 2 O 5
2 2
p 2t
0
1 α 1/2 x p N 2O5
or
1 α
Kp (4)
4x α 2 p 0N 2 O 5
Substituting (2) in (4) and replacing p N 2O5 by (3) in the resulting equation yields:
1 α 1
Kp (5)
4α 2 0
α 3/2 p 0N 2 O 5 pt
p N 2O5
α 1/2
Further
2866
logK p logT 9.132
T
Kp 0.00484
Hence, for each t, the corresponding pt can be introduced in (6), giving the value of α ,
which in turn is substituted in (3) to give the actual pentoxide partial pressure .
t k t k
10 0.010670 120 0.008010
20 0.009618 140 0.007940
30 0.008980 160 0.007931
40 0.008622 180 0.007880
50 0.008460 200 0.007825
60 0.008360 240 0.007767
70 0.008308 280 0.007623
80 0.008235 320 0.007446
90 0.008166 360 0.007446
100 0.008080
Conclusion: k exhibits a trend as a function of time. Hence, the order of reaction is not
exactly 1. Mean value of k:
(1) is based on t = 0 as reference value. Any other value, t1 say, can evidently be used.
Writing (1) for two times t1 and t yields:
p 1 kt1
p kt
0
e and 0
e
p N 2O5 p N 2O5
Dividing
p1 k t1 t
e
p
1 p1
from which k ln .
t t1 p
The t1/p1 now serves as reference point. This possibility may be of interest when the initial
pressure is difficult to measure, due to temporary non stationarities, caused by inflow of
the reactant.
Graphical Solution
From (1), it is seen that the data can be plotted also in a graph
p 0N 2O5
ln t
p N 2O5
If the reaction is first order in N2O5, the graph should show a straight line with slope equal
to k.
1.14. Reconsider the data of Problem 1.13. Determine the order of reaction together
with the rate coefficient that best fits the data. Now recalculate the value of the
rate coefficient as a function of time.
Solution
dp N 2O5
rN 2 O 5 kp nN 2O5
dt
t p N 2O 5 t p N 2O 5
40 218.297 120 117.87
50 201.89 140 101.4
60 186.63 160 86.646
70 172.3 180 74.62
80 159.49 200 64.435
90 147.79 240 47.786
100 137.38 280 36.46
320 28.45
360 21.81
t Δ p N 2O 5 log rN 2O 5 p N 2O 5 log p N 2O 5
rN 2O 5
Δ t
50 1.583 0.1995 201.89 2.305
70 1.357 0.13258 172.3 2.236
90 1.1055 0.043559 147.79 2.1696
120 0.8995 -0.046 117.87 2.0714
160 0.6695 -0.174 86.646 1.9377
200 0.4472 -0.3495 64.435 1.8091
280 0.2417 -0.6167 36.46 1.5618
k = 4.71 10-3
n = 1.0985 ≈ 1.1
Using this value for n, point values for k can again be calculated by the integral method of
kinetic analysis:
dp N 2 O 5
k p nN 2 O 5
dt
dp N 2O5 1 1 n 1 n
kt n
p 0N 2O5 p N 2O5
p N 2O5 1 n
1 1 n
k p N 2O5 0.5638
0.1 t
This yields:
t k (min-1)
50 4.87 10-3
70 4.82 10-3
90 4.77 10-3
160 4.76 10-3
200 4.78 10-3
240 4.81 10-3
320 4.74 10-3
360 4.75 10-3
2.1 Derive the basic equation (2.3.1-7) for a single reversible catalytic reaction.
Solution
For the single reversible reaction A ð B , the following elementary steps can be written:
c
1) A l Al K1 K p c
A
A
Al
l
(1)
c
eq
2) Al Rl K2 K sr c Rl
Al
(2)
p c
eq
3) Rl ðR l K3
K
1
R
c
R
Rl
l
(3)
eq
c Al
- rate of adsorption: ra k A pAcl (4)
KA
k c
c Rl
- rate of surface reaction: rsr sr Al (5)
K sr
k
c
- rate of desorption: rd R
K
Rl
R
pR cl (6)
When adsorption, surface reaction and desorption are simultaneously rate determining, all
rates are identical:
ra rsr rd r (7)
KA
From (4): c Al r K A pAcl (8)
kA
KR
From (6): c Rl r K R pR cl (9)
kR
ct cl c Al c Rl (10)
Substitution of (8), (9) and (11) in the rate equation for the surface reaction and solving for r
yields:
pR %# "
k sr K A c t p A
K $ !
r
%# " %# "%## "
#$
k sr K A k sr K R pR K A K R
1
kA k R K sr !
1 K A p A K R p R k sr K A p A
K kA kR $ !$ !
Rearranging the denominator in a constant term, a term in p A and a term in p R leads to:
+) pR (&
*
k sr K A c t p A
K '
r
+) (& +) (&
)* &' )* &'
k sr K A k sr K R k sr K R k sr K R k sr K A k sr K A
1 KA 1 pA KR 1 pR
kA k R K sr k R K sr kR kA K sr k A
K A K sr
Or equivalently, since K
KR
1/ pR .,
0
ct pA
K -
r
1/ 1 ., 1/ 1 .,
/0 k K ,- /0 k K ,-
1 1 1 1 K sr 1 K sr
KA pA KR pR
k sr K A kA kRK sr A kRK sr A k A K sr
3
a) Derive the Langmuir-Hinshelwood-Hougen-Watson kinetic rate expression,
assuming that adsorption is rate controlling.
b) Compare the result of part (a) with that found from Yang and Hougen Table
2.3.1-1.
Solution
For the reversible reaction A B 4R S , the following elementary reactions can be written:
1) A l 5 Al K1 KA 6 pc c A
Al
l
(1)
2) B l 7 Bl K2 KB
c Bl
pB cl
(2)
3) Al Bl 8 Rl
c Rl c Sl
Sl K3 (3)
c Al c Bl
4) Rl 9 R l
1 pR cl
K4 (4)
KR c Rl
5) Sl : S l
1 pS cl
K5 (5)
KS c Sl
When the adsorption of A is rate controlling e.g., the reaction rate is given by:
@> =;
>? ;<
c Al
r k1 p A c l (6)
K1
Reactions 2-5 are assumed to reach chemical “equilibrium”, so that use can be made of the
corresponding equilibrium relations to determine the unmeasurable concentration of adsorbed
A:
K 2K 3K 4K 5 A
c Bl c Rl c Sl p R c l p S c l
p B c l c Al c Bl c Rl c Sl
A A
Hence, c Al
1 p R pS
K 2K 3K 4K 5 p B
cl B K A p R pS
K pB
cl since (7)
HF EC
FG CD
p R pS
r k1 p A cl (8)
Kp B
The unknown concentrations of adsorbed B, R, and S are solved from the equilibrium
relations (2), (4) and (5) respectively:
From (2): c Bl K Bp Bcl (10)
Substitution of (7) and (10) - (12) into (9), followed by solving (9) for c l yields:
ct
cl (13)
K A p R pS
1 K BpB K R pR K SpS
K pB
NL KI
LM IJ
p R pS
k 1c t p A
Kp B
rA
K A p R pS
1 K BpB K R pR K SpS
K pB
which is exactly the result found by Yang and Hougen and shown in Table 2.3.1-1.
H
O
C
C
C
C
C
H
O
5
2
5
2
L. H . Thaller and G. Thodos [AIChE J., 6, 369 (1960)] obtained data that
appeared to show two different steps controlling, depending on the temperature
level. At low temperatures, surface reaction was controlling, while at high
temperatures desorption of (perhaps) hydrogen seemed rate controlling. A
selection of their initial rate data is given in the table below.
a) Using the data at T = 371°C, determine the parameters of the appropriate
initial rate expression.
b) Using the data at T = 288°C and 302°C, again determine the parameters.
Solution
A PR S
Surface reaction controlling
A l P Al KA
C Al
Cl p A
Al l Q Rl R C RlCSl
Sl K sr
C AlCl
Rl Q R l
C Rl
KR
Cl p R
Sl S S l
CSl
KS
C l pS
Ct Cl C Al C Rl CSl
Cl (1 K A p A K R p R K S pS )
Then,
YW VT
rA rsr k sr
s
Ct WX
C AlCl
C RlCSl
K sr TU
_] \Z
k sr
s 2
Ct ]^
Cl K A p A
K R p R K S pS
K sr Z[
(p A p R pS /K)
k sr C t s K A 2
1 K A p A K R p R K S pS
Initial rate
pA
rA0 k sr K A 2
1 K ApA
K sr
C RlCSl
C AlCl
and K R ` CCp l
Rl
R
Then
K sr K A p A Cl
Ct Cl K A p A Cl K S p SC l
K S pS
and
fd C ca
rA rR kR de K Rl
Cl p R ab
lj K K p ig
R
k R Cl jk K K p
sr A A
pR gh
rp K p om
R S A
pq p A
pR mn
rp1 om
S
k R Ct
pq K ApA KRK
pA
pS
K S pS mn
For the initial rate, multiply through by p S , and let p R , p S s 0:
rA0
kR
KR
t
a) At high temperatures, if desorption controls, a plot of rA0 vs. p should give a
horizontal line, from which ( k R /K R ) can be determined:
rA0 (k R /K R )
From the data at 371°C, the plot on Fig. 2.3-1 shows random scatter about a
horizontal line, to give
(k R /K R ) 0.19
kmol
kg cat - h
u
Figure 2.3-1
b) At lower temperatures, with surface reaction control, a straight line should result
from plotting
p KA 1
p
rA0 k sr k sr K A
Then,
k sr v slope intercept w 1
KA (slope) / (intercept)
Figure 2.3-2 shows these plots for the two lower temperatures, with the results:
T = 302°C
k sr 0.113 kmol / kg cat h
KA 0.403 atm -1
T = 288°C
k sr 0.064 kmol / kg cat h
KA 0.299 atm -1
Figure 2.3-2
Note that K A increases with temperature, the reverse of the usual behavior of adsorption
equilibrium constants.
Finally, Fig. 2.3-3 shows the good agreement with the data of the surface reaction controlling
rate equations using the above values for the parameters.
Figure 2.3-3
2.4 The Michaelis-Menten mechanism in enzyme kinetics is based upon the following
reaction scheme between the reactant (substrate S), and the catalyst (enzyme E) to
give the product, P:
1 3
S E ES P E
2 4
a) Use the steady state hypothesis for the enzyme-substrate complex, ES, to derive
the Michaelis-Menten kinetic expression:
d(S)
k 3 (E 0 )
dt max
Solution
k1 k3
S E ES P E
k2 k4
a) Disappearance rate of S.
d(S)
k1 (S)(E) k 2 (ES) (1)
dt
d(ES)
k1 (S)(E) k 4 (P)(E) (k 2 k 3 )(ES) (2)
dt
d(ES)
0 (k1 (S) k 4 (P))(E) (k 2 k 3 )(ES) 0
dt
from which:
k 1 (S) k 4 (P)
(ES) (E) (3)
k2 k3
k1 (S) k 4 (P)
(E O ) (E) (ES) 1 (E)
k 2 k3
from which:
(E O )
(E) (5)
k1 (S) k 4 (P)
1
k 2 k3
d(S) k 3 (E O )(S) k 3 (E O )
dt K m (S) Km
1
(S)
This is maximum when the denominator is minimum or when (S) is maximum. In the
limit: (S) = ∞. Hence
d(S)
k 3 (E O )
dt max
2.5 (a) For the reaction in Problem 2.3, show that the initial rate expression,
assuming that both surface reaction and desorption of R are rate controlling, is
2 1/2
2 2
k 2R 1 K A p A k 2R 1 K A p A
rA0 kr kR k 2R
2k sr K Ap A 2k sr K Ap A
(b) Show that the result reduces to the proper Yang and Hougen Table 2.3.1-1
results for each of the special cases (k R /k sr ) and (k sr /k R ) .
(c) Using the combined results of Problem 2.3 and the above results, compare the
model with the data at the intermediate temperature level, T = 315.5°C. (See also
Shah and Davidson [1965] and R.W. Bradshaw and B. Davidson, Chem. Eng. Sci.,
24, 1519 [1969].)
Solution
A l R S
C Al
A l Al KA (1)
p A Cl
C RlCSl
Al l Rl Sl K sr (2)
C AlCl
C Rl
Rl R l KR (3)
p R Cl
CSl
Sl S l KS (4)
p SC l
s C RlCSl
rsr k sr C AlCl (5)
Ct K sr
C Rl
rdR kR p R Cl (6)
KR
Total sites
Ct Cl C Al C Rl CSl (7)
s C Rl K SpSCl
rsr k sr K A p A Cl2 (8)
Ct K sr
C t C Rl
Cl (9)
1 K A p A K S pS
2
s C t C Rl C Rl K SpS C t C Rl
rsr k sr K A p A (10)
Ct 1 K A p A K S pS K sr 1 K A p A K S pS
kR C t C Rl
rdR C Rl K R pR (11)
KR 1 K A p A K S pS
2
s C t C Rl C Rl K SpS C t C Rl
k sr K A p A
Ct 1 K A p A K S pS K sr 1 K A p A K S pS
(12)
kR C t C Rl
C Rl K R pR
KR 1 K A p A K S pS
kR k R C Rl
r0 rdR,0 C Rl
KR K R Ct
2
1 r0 K R /k R
k sr K A p A r0
1 K ApA
or
2 2
2 kR kR KR 1 K ApA kR
r 0 2 r0 0
KR k sr k sr K A p A KR
Solving,
2 2
kR kR KR 1 K ApA kR KR 1 K ApA
r0 1 1 1
KR k sr 2K A p A k sr 2K A p A
kR
(Note that the result in the book has further grouped k R ).
KR
b) Show that the result reduces to the proper Yang and Hougen Table 2.3.1-1 results for each
of the special cases.
kR KR
(i) For desorption control, 0.
k sr
Then the initial rate becomes:
kR 2 kR
r0 1 0 1 0 1
KR KR
k sr
(ii) For surface reaction control, 0 , and the initial rate expression must
kR KR
be rearranged by squaring within the radical:
2 2
kR k R K R 1 K ApA k R K R 1 K ApA k sr 2K A p A
r0 1 1 2 2
KR k sr 2K A p A k sr 2K A p A k R K R 1 K ApA
kR 1 k sr 2K A p A k sr K A p A
r0 (0) (both term, cancel) 2 2
KR 2 k R K R 1 K ApA 1 K ApA
c) Using the combined results of Problem 2.3 and the above results, compare the model with
the data at the intermediate temperature level, T = 315.5°C (also see Shah and Davidson
[1965] and R.W. Bradshaw and B. Davidson, Chem. Eng. Sci., 24, 1519 [1969].)
An Arrhenius plot of the rate coefficients found in Problems 2.3 is shown in Fig. 2.5-1. Only
k sr and K A are known at two temperatures, and the activation energy for k R K R cannot be
found. Thus, an assumption must be introduced for k R K R at 315.5°C. One possibility is to
assume E R 0 (merely for lack of information), which makes it equal to k sr at 315.5°C; in
this situation, both steps would surely be rate limiting. Another possibility is to assume the
activation energy for k R K R is similar to k sr K A , which leads to a smaller value at
315.5, and which is the same as that estimated by Shah and Davidson; however, their
activation energy was much smaller (and wouldn’t be at all correct at 317°C). Note that the
former value (0.192 = const.) is similar in value to k sr at 302°C, and only at 288°C is there an
order of magnitude difference. Therefore, probably both steps are still rate controlling at
302°C. The fact that a good surface reaction control only plot was obtained in Problem 2.3 is
possibly similar to the illustration of Bischoff and Froment [1965].
In any event, Fig. 2.5-2 shows the results of using the extrapolated rate parameter values in
the combined initial rate formula of part a), and it is seen that agreement is not obtained. The
even smaller value of k R K R would give worse agreement. However if the value of k sr =
0.35 is used, reasonable agreement with experiments is obtained. This extrapolated value at
315.5°C could have been obtained if the value at 302°C was 35% larger, as shown on the
Arrhenius plot. Since surface reaction was probably not truly rate controlling at 302°C, this
could be a reasonable value, as shown in the illustration of Bischoff and Froment [1965].
This problem illustrates the difficulties in using rate expressions with more than one rate
controlling step, even though meaningful kinetic parameters can only be found in this way.
When this situation occurs, precise data covering a large temperature range is essential in
elucidating the details and parameter values.
Figure 2.5-1
Figure 2.5-2
2.6 Consider the reaction A R S , occurring on dual sites. Determine the rate
equation in the case that all four elementary steps are simultaneously rate determining.
Solution
A R S
A l Al
Al l Rl Sl
Rl R l
Sl S l
Rate equations:
c Al
(1) ra k A c A cl
KA
c RlcSl
(2) rsr k sr c Alcl
K sr
c Rl
(3) rd1 kR c R cl
KR
cSl
(4) rd2 kS cSc l
KS
ct cl c Al c Rl cSl (5)
A possible procedure is as follows: cl , c Al , c Rl , cSl are calculated from (1), (3), (4) and (5) and
then substituted into (2).
(1) c Al K A c A cl rA k A
rA
(3) c Rl KR c R cl
kR
rA
(4) cSl KS cSc l
kS
(5) cl ct c Al c Rl cSl
KA K R KS
ct rA
kA k R kS ct MrA
cl
1 K AcA K R c R K ScS D
K A K R KS
where M
kA kR kS
D 1 K AcA K R cR K ScS
KA rA D
c Al c A c t c A MrA
D kA
KR rA D
c Rl c R c t c R MrA
D kR
KS rA D
cSl cSc t cS MrA
D kS
rA D
c t MrA K A c A c t c A MrA
k sr kA
rA
D2 K SK R rA D rA D
c R c t c R MrA cSc t cS MrA
K sr kR kS
or
K A MD K SK R 2 K SK R c
2
K A M 2c A M c R cS MD R
D rA kA k sr K sr kR
rA2
k sr K SK R c K SK R 2 1
MD S D
K sr kS K sr k R kS
K A Dc t K SK R
K A Mc A c t K A c A Mc t c R cSc t M
kA K sr
rA
K SK R c R c t K SK R K S K R cSc t
D c R cSc t M D
K sr k S K sr K sr k R
K SK R
K A c A c 2t cSc R c 2t
K sr
K R KS K SK R KA
whereby: A D2 MD k ScS k R cR
K sr k R k S K sr k R k S kA
1 K SK R KA c R cS
B ct D2 ct D k ScS k R cR 2c t K A M c A
k sr K sr k R k S kA K
c R cS
C c 2t K A c A
K
K A K sr
K is the overall equilibrium constant, .
K R KS
2.7 The following data were obtained by Sinfelt and co-workers [Sinfelt, J.H. et al., J.
Phys. Chem., 64, 1559 (1960)] for the dehydrogenation of methylcyclohexane to toluene.
In addition, they found that the product toluene had essentially no effect on the rate.
A l Al
Al Rl
Rl Q S l
The reaction
Solution
Since toluene and H2 have no effect on the rate, the final step is irreversible, and the
other steps possibly in quasi-equilibrium-thus try desorption control.
A l Al K1
Al Rl K2
Rl Q S l K3
Then
C Al K1p A Cl
C Rl K 2C Al K1K 2 p A Cl
and
Ct Cl C Al C Rl
C l 1 K1 1 K 2 p A
r k 3 C Rl K 3 k 3K1K 2 p A Cl K 3
k 3C t K1K 2 K 3 p A kp A
(1)
1 K1 1 K 2 p A 1 Kp A
Note that (1) has the features observed in part (a).
1 K 1 1
r k k pA
The plot shows that the slopes at all three temperatures have essentially the same
value, and so the “combined activation energy” E 3 Q1 Q 2 Q3 is zero. The rate
coefficient has a value k = 0.4 kmol/kgcat h atm. From the intercepts, the following
are found:
(c) Since the postulated kinetic scheme of irreversible desorption control reasonably fits
both the qualitative observations of the data, plus yields quantitative consistent
parameter estimate plots and activation energies, it will be accepted. The original
reference then uses this for further postulates about the catalyst behavior.
2.8 The isomerization of n-pentane was considered in the text, where several rate
expressions were stated. Derive the final result for desorption of i-pentene
controlling:
kK 5 K D K 6 p a p B K
r
p H2 K 5 K D 1 K 6 p A
Solution
When desorption of i-pentene is rate controlling, i.e., the 7-th reaction, the overall reaction
rate is given by:
p Ncσ
r k 7 c Nσ (1)
K7
From the equilibrium relations with respect to the fifth and sixth reactions:
c Nσ K 5K 6pMcσ
c Mσ K 5pMcσ (2)
ct cσ c Mσ c Nσ 1 K 5 1 K 6 pM cσ (3)
Hence:
pN
k 7ct K 5K 6 pM
KI
r (4)
1 k5 1 K6 pM
where K I is the equilibrium constant for M N on acid sites. The unmeasurable gas phase
partial pressures of the pentenes, pM and pN, are expressed as a function of the gas phase
partial pressures of the pentanes by making use of the assumption that the hydrogenation and
dehydrogenation stages are in equilibrium:
pH 2 pM pA
K1K 2 K 3K 4 KD pM KD (5)
pA pH 2
pB 1 pB
K 8 K 9 K 10 K 11 KH pN (6)
p H2 p N K H p H2
kK D K 5 K 6 p A p B K
r
p H2 K 5 K D 1 K 6 p A
where
K KDKIKH
k k 7 ct
2.9 For the isomerization of n-pentane, derive the rate expression if the surface
reaction step of the dehydrogenation reaction were rate controlling. Contrast this
with the correct rate of Problem 2.8, especially regarding variations with total
pressure.
Solution
c Ml c H 2 l
r k 2 c Al cl (1)
K2
From the equilibrium relations with respect to reaction(s):
By having considered reactions (4) - (11), c Ml is expressed directly in terms of the observable
partial pressures p B and p H 2 .
c t cl c Ml c Nl c Al c Bl cH 2l (5)
1
(11): c Bl p Bc l (6)
K11
1 pB
(9) - (11): c Nl cl (7)
K 9 K10 K11 p H 2
Hence:
1 pB 1 pB 1 1
ct 11
K1p A pB p H cl (8)
pH 2 K 9 K10 K11 p H 2 K11 K3 2
Ki
i 4
pB
k 2 K1 p A
K
r 2
1 1 pB 1 1
1 11
K1p A pB pH
K 9 K10 K11 pH 2 K11 K3 2
Ki
i 4
2.10 For the isomerization of n-pentane, the following experimental data were collected
by Hosten and Froment [1965]:
γ is the molar ratio H2/n-pentane. The pentane feed consisted of 92.65 mole % n-C5 and
6.37 mole % i-C5. The overall equilibrium constant is 2.07, while the selectivity for
isomerization is nearly constant and equal to 0.91. Estimate the parameters in the
adsorption model by means of the integral method of kinetic analysis. Both W/FA0 and x
can be used as dependent variable. Comment on this choice. Compare the results and
the computational effort for both cases.
Solution
The reaction network for the isomerization of n-pentane (A) into i-pentane (B), accompanied
by the cracking of the n-C5 into C1–C4 (C) to a small extent can be written:
B
A
C
When the adsorption of n-pentene is rate determining for the isomerization, the reaction rate
equation for isomerization is given by:
kK D p A pB K k pA pB K
rB (1)
1 1 p H2 K B p B
p H2 1 pB
K7KH K6
(It is assumed that the cracked products are not adsorbed on the acid sites). The integral
method of kinetic analysis makes use of the continuity equation for species B. For an ideal
tubular reactor with plug flow:
FA0 dx B rB dW (2)
(1) has to be substituted in (2), which is then integrated. This requires the expression of the
partial pressures as a function of xB. The feed contains P mol % n-pentane, Q mol % of i-
pentane and R mol % of an inert I, cyclopentane. The following balances can then be written:
100 Pγ 100 Pγ
It is hereby assumed that 1 cracked mole of A gives rise to two moles of cracked products C.
It is seen that cracking does not give rise to expansion or contraction.
Since the selectivity for isomerization, η x B x A , is constant, the partial pressures read:
P(1 x B /η η B Px B P γ - 1 η -1 xB
pA pt ; pB pt ; pH 2 pt (3)
100 Pγ 100 Pγ 100 Pγ
W Kη 1 KB
a c (4)
FA0 P(K η ) k k
in which:
η PK Q 1 1
a Pγ 1 ln u P 1 xB
K η η η
η PK Q
c Q ln u Px B
K η
PK η
u 1 xB
η PK Q
Parameters can now be estimated, using the given data pairs x | W/FA0, γ .
2
n
W Ŵ
Min (5)
i 1 FA0 i
FA0 i
Notice that (4) is linear in the groups 1/k and K B /k, so that linear regression will surface to
estimate these groups. Values of k and K B are unambiguously determined afterwards. If x B is
used as the dependent variable, the appropriate least squares criterion,
2
x Bi x̂ Bi Min (6)
requires non-linear regression. Moreover (4) is implicit in the conversion x B so that this
implicit equation has to be solved for x̂ Bi for each experiment. Since W and FA0 will
generally be precisely known, W/FA0 is likely to be considered as a discrete rather than a
random variable, so that criterion (5) seems to be inappropriate. The conversion on the other
hand seems to be the true observed variable, subject to experimental error and hence,
estimation should be based on criterion (6) indeed.
Results
Dependent variable
W/FA0 XB
k 0.89 0.89
KB 6.57 8.5
Both criteria yield estimates which agree very well. Clearly, required computational effort is
much higher when x B is the dependent variable.
2.11 A catalytic reaction A B is carried out in a fixed bed reactor. Comment on the
concentration profiles of adsorbed species as a function of bed depth for various
rate determining steps.
Solution
c Al
A l Al K1
p A cl
c Bl
Al Bl K2
c Al
p Bc l
Bl B l K3
c Bl
c Bl p Bcl
K 2 K3
c Al c Bl
or
1
c Al p Bc l (1)
K 2K 3
1
c Bl p Bc l (2)
K3
ct cl c Al c Bl
1 1 ct
1 pB p B cl cl (3)
K 2K 3 K3 1 1
1 1 pB
K2 K3
and
1 ct ct
c Al pB (4)
K 2K 3 1 1 K 2K 3
1 1 pB 1 K2
K2 K3 pB
(2) c
From , it follows Bl K 2 , or the ratio is constant.
(1) c Al
From an identical reasoning, the reverse is obtained for cl and c Al when the desorption is rate
determining.
c
The ratio Bl remains constant.
c Al
c Al =K1p A cl
1
c Bl p Bcl
K3
ct
cl =
1
1+K1p A + pB
K3
K1 p A c t
c Al =
1
1+K1p A + pB
K3
1 p Bc t
c Bl =
K 3 1+K p + 1 p
1 A B
K3
All kinds of profiles are possible. In the case that the denominator is nearly constant or, at
least, varies slower than p A , or p B , c Al is decreasing, c Bl increasing, and cl nearly constant
1
as a function of bed depth. Also with, strong product inhibition, this means that >>K1 ,cl
K3
will be decreasing. So will c Al at an even greater rate since not only the denominator
increases, but also the numerator decreases.
2.12 The dehydrogenation of ethanol was carried out in an integral reactor at 275°C
with the following results:
The overall equilibrium constant is 0.589. The feed consisted of the azeotropic mixture
ethanol-water, containing 13.5 mole % water. Water is not adsorbed on the catalyst.
Estimate the parameters of the adsorption, surface reaction, and desorption models,
using conversion as the regression variable. Comment on the feasibility for the
estimation of the parameters. Which model is the best? On what basis?
Solution
As shown in Chapter 2, the continuity equation (a) has to be integrated after substituting the
appropriate rate equation and expressing the partial pressures of the reaction partners as a
function of conversion and independent variables. The result is an expression of the form:
W 1
= D1 +D 2 +D3 (1)
F C
for all three rate equations with D1 ,D 2 ,D3 given in Chapter 2. The functional dependence for
C and A1 ,B1 ,C1 ,A 2 ,B2 ,C2 are different for each model, however. They are shown in Chapter 2
for the surface reaction controlling rate model. They are given below for the two other
models:
Adsorption controlling:
C=k
A1 = 1.334 A 2 = 1.155 p t
B1 = 2.31 + K R +K S p t B2 0.155p t
C1 1 K A p 2t /K (K R K S )p t C2 p t (1 p t /K )
Desorption controlling:
C = kK
A1 = 1.155 K R A 2 = 1.155
B1 = 1.155 + K A p t - 0.155 KK R B2 = - 0.155
C1 = 1 + K A p t - KK R + K S p t C2 = - 1+ p t K
The parameters are estimated in all three models by means of the least squares criterion based
on the conversion:
n
2
x i -xˆ i Min (2)
i=1
This again necessitates the solution of the implicit equation (1) for x̂ i for each experiment
and all models. The objective function (2) is minimized e.g., by means of the Marquardt
technique.
Results
The next table presents the point estimates for the parameters and their 95% confidence limits,
as well as the residual sum of squares.
Note that the parameters K R and K S can be estimated separately in the desorption model,
even when pure feed, i.e., containing no reaction products, is used. This is not possible in the
adsorption and surface reaction rate models: only their sum is estimable. Compared to the
differential method of kinetic analysis, discussed in Chapter 2 the estimation technique
discussed above is undoubtedly much more laborious.
From this analysis, it is clear that the surface reaction model is the best:
1) It is the best fitting model and has a residual sum of squares which is only ¼ of that of
the adsorption model.
2) All parameter estimates are positive and significantly different from zero.
3) The adsorption model fits much worse to the data and contains a significantly negative
parameter estimate; this is in conflict with thermodynamic requirements for adsorption
constants; hence the adsorption model must be discarded.
4) The desorption model fits relatively well to the data, but none of the parameter
estimates is significantly different from zero from the statistical point of view.
2.13 Boolean Relation Matrix and Label representation of molecules and ions.
a) Write the Boolean relation matrix and the label representation of
(i) 3-Me-pentane -2+ carbenium ion
(ii) Naphthalene
(iii) Cumene (i-Propylbenzene)
b) What are the Me-shift isomerizations and the β -scissions that the 3-Me-
pentane -2+ ion can undergo ? What are the products ? Hint: For the β -
scissions first construct the matrix M2-1 in order to determine the 3 -carbon
atoms.
Solution
2
1 2 3 2 1 1
8 8 8 8 8 8
0
3 2 2 2 2 3 2 2 2 2
1 4 4 4 4 1 4 4 4 4
0
3 2 2 2 2 2 3 1 1
4 4 4 4 4 4 8 8 8
CHAPTER 3
3.1 The cracking of cumene into benzene and propylene was carried out in a fixed bed
of zeolite particles at 262°C and atmospheric pressure, in the presence of a large
excess of nitrogen. At a point in the reactor where the cumene partial pressure was
0.0689 atm, a reaction rate of 0.153 kmol/kg cat. h was observed.
Show that, under these conditions, the partial pressure and temperature drops
over the external film surrounding the particles are negligible.
Solution
a) The partial pressure drop Δ pA over the external film is given by:
~ }{ zx 2/3
{| xy
rA M m p fA μ
Δ pA
a m G jD ρ g D Am
jD 1.68Re 0.51
(Re 190)
or jD = 7.50
p fA pt δ A
pA pt δ A pA Δ pA
p
pt δ ApA
ln
t δ A pA Δ pA
δ A q s ... a b ...
a
δ A 1 1 1
1
The pressure drop is calculated according to the iterative scheme presented in Chapter
3:
1) Assume Δ p A O p p δ p 1.0689fA t A A
or Δ p 3.836 10 atm
A
4
p fA p fA
1.06863
ln
1 0.0689
1 0.0689 Δ p A
This value is sufficiently close to the previous value, so that no further cycles are
required.
¡
Hence, δ p A 3.836 10 4 and Δ pA
pA
100 0.56% which is negligible.
Δ T ¢ ar C( Δ GH)j
A
m p H
pt
2/3
£ ( 41816) (0.846)
Hence
Δ T ¤ 45 £0.153
0.3342 £ 56.47 £ 5.49
2/3
= -1.228°C
and
Δ T
T
¦ ¥ 0.34% which is again negligible.
200
3.2 The solid density of an alumina particle is 3.8 g/cm³, the pellet density is 1.5 g/cm³,
and the internal surface is 200 m²/g. Compute the pore volume per gram, the
porosity, and the mean pore radius.
Solution
A catalyst pellet consists of the solid phase (catalytic material + support) and the void phase:
1 cm³ catalyst = X cm³ solid + (1 – X cm³) void
In weight :
1.5 g = X X 3.8 g + (1 – X) X 0 g
1.5
Hence X = = 0.395; 1 – X = 0.605
3.8
pore volume
¨ ¨ R 0.404 cm³/gcat
¨ §
0.404 10 6 m³
surface area 2 200 m²/g cat 200 m²
3.3 Turning to a general description of pore diffusion, the "dusty gas" theory of
Mason et al. [1969] utilizes the results from the formal kinetic theory of gases, with
one "species", the "dust", having a very large "molecular weight". Their final
results can be clearly visualized in the form utilized by Feng and Stewart [1973]:
Nj ª (diffusive flux) ( viscous flow flux )
(fluxes caused by other driving forces) (1)
ªN ( D)
j N (v)
j ...
N (jv ) ³ y ±¯°̄ RT
j
B p ®
² ¬¬«p
0 t
t (2)
with B0 = D'Arcy constant, a function of porous media geometry, = r 2/8 for a long
cylinder of radius r, and the diffusive flux is found from the extended Stefan-
Maxwell form
1
RT
pj µ ´¶ N
k 1 D
1
e, jk
( y k N (jD ) y jN ( D)
k )
N (jD )
De,Kj
(3)
Equations (1) to (3) can also be combined to give a single equation containing only
the total flux resulting from both diffusive and viscous flow mechanisms:
· ¿ À D1 ½» B p º·p
»¼ RT ¾ ¸¹̧
1 N Nj yj 0 t
pj ( yk N j y jNk ) t (4)
RT k 1 e, jk De,Kj De,Kj
Carefully watching how the various fluxes combine, derive (4) for the molar flux in
a porous medium.
Solution
The total mass flux is the sum of the diffusive and convective flows
Nj ÁN (D)
j N (v)
j (a)
N (v)
j à yj
Bo p t
RT μ
Âp t (b)
The diffusive flux driving force, the partial pressure gradient, is utilized by both bulk and
Knudsen diffusion:
1
RT
pj Å ÄÆ N
k 1 D
1
e, jk
y k N (D)
j y jN (D)
k
N (D)
j
D e,kj
(c)
N (D)
j ÇN j N (v)
j (1)
and N (v)
j Èy j (2)
Substituting (1) into (c) gives two parts to each of the terms on the RHS. The Stefan-Maxwell
term with the convective flow term is
k
N
Ê
1
1 D e, jk
yk y j y jyk É0
since diffusive intermingling of species is separate from convective motion. However,
convective and Knudsen flows are similar, and both terms remains. Thus, the final result is:
1
Ë Ò Ó D1 N Nj yj ÑÏ p B ÎÌËp
Ð RT μ Í
t o
pj yk N j y jNk t
RT k 1 e, jk D e,k j D e,k j
Solution
The first step is to estimate the bulk diffusivity. From Bird, Stewart, and Lightfoot [2] the
dense gas kinetic theory result for diffusivity is
1 1
T 3/2
D AB Õ 1.8583 Ô 10 3 MA M B cm²
p(atm)σ 2AB Ω D s
σ
AB Û 12 σ σ Û 12 5.25 2.92 Û 4.08 AÚ
A B
ε AB kÝ ε εA Bk Ý 447(38) Ý 130ÜK
Finally,
1 1
0.001858 (600) 3/2
D AB à 2
84
p (4.08) (0.84)
2
á 1.612
p
cm²/s
D AB â 1.612
30
â 0.0537 cm²/s (assuming ideal gas behavior at 30 atm!)
With this value, then,
r ä ρ 2ε S ä 1.402(180)
s (0.4)
4
å 31.8 Aæ å 3.18 nm
s g 10
D K,A ç 4
3
3.18 10 9
π
2 (8.314) 10 3 660
84
é è 0.865 10é 6
è
m²/s 0.865 10 2 cm²/s
D e,KA ë ετ D ë 0.346
τ
ê10
K, A
2
cm²/s
1
D eA
ó D1 e, AB
1
D e,KA
ó τ òïñ 0.677
1 1
0.00346
îì
í
or
1
D eA
ý D1 e, AB
1
D e,KA
ý τ üúû 0.0216
1 1
0.00346
ù÷
ø
or
Solution
The proper equation for steady counterdiffusion in a porous medium is to be used (Chapter 3),
with the flux ratio given by
NB MA
ð ;
NA MB
Thus,
An approximate solution is to use a mean value of the effective diffusivity for species ‘A’:
1 1 yA 1 MA MB 1
ln ave
D e,A ave
D e,AB D e,AB
dy A
NA D eA ave
Ct
dz
or
YAL YA0
N A C t D eA ave
L
For either approach, the bulk and Knudsen diffusivities must first be estimated.
From Bird, Stewart, and Lightfoot [23], the bulk diffusivity based on dense gas kinetic theory
is:
1 1
T 3/2
cm² MA MB
D AB 1.8583 10 3
s p (atm) σ AB Ω D
where the “collision diameter”, σ , and integral Ω D (which is a function of the “interaction
energy”, ε T/k) are found in tables: H2, σ
2.92 A , ε /k = 38°K; C 2 H 4 , σ 4.23 A , ε /k =
205°K. Then
1 1
σ AB σ A σ B 4 . 23 2.92 3 . 58 A
2 2
ε AB k ε A ε B k 205 (38) 88.3K
Then
ε T 298
3.38 Ω AB 0.92
k 88.3
Finally,
1 1
0.001858 (298) 3/2
28 2
D AB 2
p (3.58) (0.92)
0.593
cm²/s
p
(Note that diffusivities in hydrogen mixtures are about a factor of 5 higher than “normal larger
molecules.”)
Thus,
where τ has been arbitrarily taken to be 1.0; other values merely decrease the flux by τ 1 .
2ε s 2 (0.4) !
r 54.4 A 5.44 nm
ρ pSg 1.4 (105) 10 4
From (3.4-4)
4 2 (8.314) 10 3 (298)
D KA # (5.44 " 10 9 )
3 π 28
$ 1.722 % 10 m²/s $ 0.01722 cm²/s
6
ε
D e,KA & D KA & 0.4 (0.01722) & 0.00689 cm²/s
τ
Now the above formulas can be applied. (The remainder of this problem will be done using
S.I. units.)
p p p (bar) kmol
Ct ' ' '
RT . bar m³ + 24.78 m³
, 0.08314 ) (298(K)
- kmol (K *
It is seen that for large pressure, the maximum diffusion flux (bulk diffusion) is:
kmol
N A 8 3.445 7 10 5
ln (3.742) 8 4.54 7 10 -5
s m²
In general, it is useful to have the limiting forms for both high and low pressures. In the
former case, D e,AB D e,KA 9 0 , and
C t D e,AB 1 1 M A /M B YAL
NA : ln
L1 M A /M B 1 1 M A /M B YA0
C t D e,AB MB
NA = ln < fcn (p)
L1 MA MB MA
since
1
Ct De > p .
p
For very low pressures, careful expansion of the log terms by multiplying numerator and
denominator by D e,KA D e,AB leads to:
C t D e,AB C D e,KA @
NA D A 1 1 M A M B YAL 1 1 M A M B YA0 ?
L1 MA MB AB D e,AB ?
C t D e,KA
E YA0 YAL
L
Fp
which is pure Knudsen diffusion, and the various flux ratios relevant to bulk diffusion no
longer appear; the Knudsen flux of each species is independent.
These two limiting forms are useful bounds on the complete solution. The approximate model
becomes
J 10 5 (1.01 14.51 / p)
It is seen how the pressure dependency changes from Knudsen to bulk diffusion. Also, the
approximate model is very close to the exact complete results, except at high pressures in the
bulk diffusion range. The maximum flux is about 11% lower. This is caused by the very
arbitrary choice of YA ave K 0.5 ; the actual concentration profile is somewhat curved under
the straight line implicitly assumed by the simpler model. If a value of YA ave L 0.4 were
used, the two curves would essentially superimpose. In the Knudsen diffusion limiting
regime, the two formulas are identical.
Figure 3.5-1
3.6 The data given below on diffusion of nitrogen (A) and helium (B) in porous catalyst
pellets, have been provided by Henry, Cunningham, and Geankoplis [51], who
utilized the steady-state Wicke-Kallenback-Weisz technique. An alumina pellet
with the following properties was used:
Solution
a) From Chapter 3, (3.4-5), the theoretical expression for the ratio of fluxes in an
experiment with steady state counterdiffusion of two species (Wicke-Kallenbach-
Weisz technique) is:
N
NB M 28
N M M M M 2.646
A
N B 4
A
which is close to the experimental values: Avg = 2.365, S.D. = 0.27 (10%).
b) It is best to first plot the flux-pressure data in order to determine the likely diffusion
regime: bulk or Knudsen. This is shown in Figure 1, and the extremes of the data
range seem to essentially span the range. The diffusivity values are found using:
S Y1 N[ [ V P
[ Q1 W B N A T y AL D e,AB D e,KA O
C t D e,AB X U
NA Z
Y [ [ V ln QQ Y1 N[ [ V O
LW1 N B N A T 1 W N A T y A0 D e,AB D e,KA O
U QR O
B
X X U
which can be obtained for steady-state one-dimensional diffusion experiments, where
]N A \ 0 or NA = constant, after direct integration of N A _ DeA^C A between z = 0
and z = L [Satterfield, 1970].
Since D e,AB D e,KA ` P 1 , at high pressures D e,AB D e,KA aa 1 , and
f l1 Nn n i c
n d1 j B N A g y AL b
CD e,AB k h
NA m
l n n i ln dd l1 Nn n i bb
Lj1 N B N A g 1 j N A g y A0
h de h b
B
k k
The values of D e,AB and D e,KA must be used to check exactly what pressures allow
this approximation to be used. Also, at low pressures, D e,KA D e,AB aa 1 , and the
equation reduces to (with L’Hospital’s Rule):
r C D e,KA
NA q oy A0 y AL p
L
P p gmol
Ct t t 4.076 s 10 5 P (in atm)
RT { cm³ atm x cm³
yy 82.06 vv 298uK
z gmol uK w
0.5
Then, at the lowest pressure, P } } 6.579 | 10 4
atm
760
N AL (0.449 10 8 )(1.244)
D e,KA ~ ~ ~ 0.240 cm²/s
C y AB y AL (2.68 10 8 )(0.911 0.0407)
N AL 1 N B N A
(43.9 10 8 )(1.244)(1 - 2.86)
D e,AB 0.0516 cm²/s
c ln 1 (1 2.86)(0.146)
(3.218 10 ) ln
5
1 (1 2.86)(0.723)
Since D e,KA is independent of pressure, the use of the limiting form to calculate D e,AB
can be checked:
D e,AB 0.0516
0.215 ,
D e,KA 0.240
which is not really negligible with respect to unity. Therefore, the complete equation
must be used, which gives after two iterations,
At this point the other limiting approximation can be checked with D e,AB P 1 :
D e,KB 0.24 P
5.139 P
D e,AB 0.0592 0.790
5.139 (6.58 10 4 atm) 0.00338 1
Thus the value of D e,KA is correct (although more than one experimental point should
be used – the authors found an average of 0.027 cm²/s).
Next, the data at the second highest pressure is used with the complete equation to
obtain D e,AB at 0.3943 atm; after a few iterations:
The computations do not converge very well at the next lower pressures. However, to
estimate D eA P over the entire pressure range, the following equation can be used:
£ ¥ ¥
1 y A ¡1 N B N A
1
¤ ¢ 1
1 0.8 (1 2.646) 1
D eA D e,AB D e,KA D e,AB 0.24
Avg. y A0
or
The line on Figure 3.6-1 below was computed from this result:
Figure 3.6-1
c)
d) to be provided
e)
3.7 Derive (3.6.1-10) for the effectiveness factor for a first-order reaction in a spherical
catalyst pellet.
Solution
1 d 2 dC
De r k vC ¨ 0 (1)
r 2 dr dr
C(R) © C s (2)
dC(0)
ª0 (3)
dr
u
C« (4)
r
This is the same as the slab problem, and so the concentration profile can be immediately
found as
1
C A sinh k v D e r B cosh k v D e r (6)
r
Substituting into B.C. (3) gives B = 0, and into (2) gives A ® RC s sinh R k v D e
Thus,
C R sinh (h r/R)
¯ (7)
Cs r sinh (h)
where h ° R k v D e
¶ dC ³
4 π R 2 ´ De ±
η · µ dr ²
(9)
4
π R 3 k v Cs
3
3 De ½ h R º 1
¾ » cosh h ¸
R kv ¼ R R sinh h ¹ sinh h
2
3 h coth h 1
¿ (10)
h h
3.8 A series of experiments were performed using various sizes of crushed catalyst to
determine the importance of pore diffusion. The reaction may be assumed to be
first order and irreversible. The surface concentration of reactant was
C ss Á 2 À 10 4 mol/cm³ .
DATA:
Diameter of sphere (cm): 0.25 0.075 0.025 0.0075
r observed (mol/h cm³): 0.22 0.70 1.60 2.40
a) Determine the “true” rate constant k v and the effective diffusivity D e from the
above data.
b) Predict the effectiveness factor and the expected rate of reaction robs for a
commercial cylindrical catalyst pellet if dimensions 0.5 cm × 0.5 cm.
Solution
Vp R dp
a) Shape factor L Ã Â Â
Sx 3 6
Clearly, all the catalyst particle-sizes affect the rates; one approach is to check the
possible extreme values for large Φ (L):
Therefore, one suspects the larger particles are in the strong diffusion control regime.
For the smallest sizes
Therefore, these sizes have only modest diffusion control. The location of these data
on the E.F. chart will allow determination of k v and D e . The Figure shows a plot of
the data, along with the superimposed axes of the E.F. (---) graph, Fig. 3.6.2.A-1, with
the similar shape. Thus, the corresponding coordinate points are
Therefore:
kv k
1.0 Õ Φ Õ L Õ 0.0039 v
De De
and
robs 0.225
0.1 × η × ×
k v C obs k v (2 Ö 10 4 )
cm³
k v Ø 1.12 Ù 10 4 Ø 3.1 cm³/s cm³
h cm 3cat
D e Û 4.72 Ú 10 5 cm²/s (liquid?)
Also note that the smallest particle is almost in region of no diffusional effect
2.40
kv Ý Ý 1.2 Ü 10 4
2 Ü 10 -4
π 2
Vp dp Lp dp
b) For a finite cylinder, L Þ Þ 4 Þ
Sx π 2 4 2dp Lp
dp 2 dp
4
0.5 cm 3.1
▲ Lß ß 0.0833 cm and Φ ß 0.0833 ß 21.3
4 2 (l) 4.72 à 10 5
1 gmol
and η ~ â 0.046; robs â k v C obs â 0.046 (3.1) (2 á 10 4 ) â 3 á 10 5
Φ cm³s
Figure 3.8-1
3.9 The following rates were observed for a first order irreversible reaction, carried
out on a spherical catalyst:
Solution
robs1 η 1 rA (C SAs )
æ æ 2
robs2 η 2 rA (C SAs ) 1
The last equality holds in the region of strong pore diffusion limitation. An iterative cycle is
set up, in which use is made of Fig. 3.6.1-3:
robs1 robs1
From From Fig. 3.6.1-3 From
robs2 robs2
η 2 η 2 2 2 η 2
This cycle is continued until the value for 2 is converged. The following cycle is then
obtained:
η 2 0.64
To check for eventual pore diffusion at a particle diameter of 0.1 cm, the modulus is:
0.1
Φ 3 (1.22) 0.407
0.3
The reactant pressure is 1 bar, the temperature is 600 K, the molecular diffusivity is
D AR 0.10 cm²/s , and the reactant molecular weight is M A 60 . The catalyst pellets
have the following properties:
Radius of sphere R = 9 mm
Pellet density ρ S 1.2 g/cm³
Internal surface area S g 100 m²/g
Internal void fraction ε S 0.60
Solution
2ε 2 (0.60)
r S
10 6 cm 10 8 m ( 100 A)
ρ S Sg (1.2 g/cm³) (100 10 4 cm²/g)
1/2
ε 4 2 RT
D e,K r
τ 3 π MA
1/2
0.6 4 8 2 8.314 (600)
10 assume τ 3
3 3 π (60)
7
6.135 10 m²/s
also
ε 0.6
D e,AR D AR (0.1) 2 10 6 m²/s
τ 3
1 1
D e1 6 7
2 10 6.135 10
or
De 4.70 10 7 m²/s ←
n 1 k v C nA 1 R 3 k vCA
L
2 De 3 2 De
Then
3
9 10 3 (3.86) (0.0203)
1.50
3 2 4.70 10 7
Alternately, the value could be taken as an observed rate coefficient, and the extended
Weisz-Prater criterion for a second order reaction gives:
c) The most straightforward way to reduce pore diffusion limitations is to reduce the
pellet size – a factor of two or three should suffice from the numbers in part b.
3.11 A gas oil is cracked at 630°C and 1 atm by passing vaporized feed through a
packed bed of spheres of silica-alumina catalyst with radius = 0.088 cm. For a feed
rate of 60 cm³ liquid/cmr³.h, a 50 percent conversion is found. The following data
are also known:
Solution
cm³ g 1 mol
60 0.869 (0.5)
moles converted cm r ³ h cm³ 255 g
cat volume time s g cat 1 cm³ cat
3600 0.7
h cm r ³ 0.95 gcat
or
5 gmol
rA 3.85 10
cm³ cat s
2
L2 robs 0.088 3.85 10 5
Φ 6.90 (dimensionless) ←
CA De 3 (0.6 10 5 ) (8 10 4 )
1 1
η 0.1449
Φ
d) Then
rA
k (if first order)
η CA
3.85 10 5 1
44.3 s (or cm³/cm³p s)
0.1449 (0.6 10 5 )
4.1. Derive (4.2-3) by using simple geometric arguments. (Also see Kim and Smith [3]
and Wen [2]).
Solution
The solid concentration of species j is Cjs kmolj/mp³ (based on the total pellet volume—see the
notation), the molar volume is vjs mjs³/kmolj and the solid fraction is 1 ε S m 3solid /m 3p . Then
for the reaction A g Bs çPs Q g , the initial solid fraction is given by:
1è ε 0 è CB vB s0 s
C Is VIs (1)
where C Is represents the concentration of the inert solid material. At a given conversion level,
the solid fraction is:
1 é ε é CBs v Bs C Ps v Ps CI s v I s (2)
Thus,
ε s ε s0 ë1 ε s0 1 ε s
ë CB v B s0 s
CIs v Is C B s0 C I s v Ps (3)
ë CB v B s0 s
v Ps 1 C B s C B s0
With obvious change in notation, this is (4.2-6), but without the term 1 ε s 0 which would
actually only be needed if the reactive solids concentrations were based on the total solid
rather than total pellet volume.
4.2. Consider the general model with the reaction first-order in fluid phase
concentration:
c As
ε s ì De 2
C As akC As f C s
t
Cs
ì akC As f c s
t
where f(Cs) is the rate dependency on the solid reactant concentration; (e.g., a grain
model or mass action form). The simplest boundary conditions would be:
C As í 0
C s í C s 0 , at t í 0
and
t
Ψ x, t ï ak C As x, t' dt' (cumulative concentration)
0
Cs ò H s Ψ x, t ; C s 0
(b) Then, the new variable can be differentiated in space ( ), and these results
combined with the original mass balance differential equation to yield:
Ψ
εs ó De 2
Ψ ak Cs0 H s Ψ ; Cs 0
t
Ψ ô 0 at t = 0
Ψ õ aCsAs kt on the surface.
(d) The results of parts (b) and (c) show that the original two coupled partial
differential equations can be reduced to solving one diffusion type equation, with
a time-dependent boundary condition—a much simpler problem. For the special
case of rectangular (slab) geometry, and where the pseudo steady state
approximation is valid (gas-solid reaction), show that the mathematical problem
is reduced to:
2
Ψ
De ö ak Cs0 H s Ψ ; Cs 0
z2
with
and
Ψ
ø 0 at the centre, z = 0 (symmetry)
z
Thus notice that the results of Chapter 3 can be utilized to solve the transformed
problem.
For a zero order solid concentration f C s ù C S0 , show that the following results
are obtained:
cosh Φ z L akCS0
C As ú CsAs Φ ûL
cosh(Φ ) De
cosh Φ z L
Cs ü CS0 1 akCsAs t
cosh(Φ )
which are the type of results obtained by Ishida and Wen [9] in (4.2-13) and (4.2-
14).
(e) Finally, for the slab geometry of part (e), show that the conversion is given by
1
1ÿ
akC sAs t
ÿ
2
Solution
t
Ψ x , t ak C Asdt' (1)
~
0
If the left hand side of (2) can be integrated (e.g., if f(Cs) = Cs → ln (Cs/Cs0) then an
explicit expression can be found for Cs (e.g., Cs = Cs0 exp [−Ψ ]); this can always be done
in principle, even if only implicitly or numerically, to give H s [Ψ ( x , t); Cs 0 ] .
~
t
Ψ ak C As dt' (3)
0
t
2
Ψ ak 2
C Asdt'
0
t
1 C As
ak ε s akCAsf Cs dt'
0
De t'
(4)
ak Cs
ε s C As C As0 dt'
De t'
ak
ε s C As C As0 Cs Cs0
De
Ψ
akC As (5)
t
Ψ
ε s De 2
Ψ akε s C As0 ak Cs Cs0 (6)
t
Using the solution of (2) for Cs, H(Ψ ; Cs0), yields the final result from (6):
Ψ
ε s De 2
Ψ akCs0 H Ψ ; Cs0 ε s C As0
(7)
t
(c) The B.C. can be similarly transformed by using the definition (1) and the result (3):
● At the surface, C As C sAs
t
Ψ surface
ak CsAsdt akCsAs t (8)
0
● At the center, C As 0
t
Ψ center
ak (0)dt 0 (9)
0
Ψ ( x; 0) 0 (10)
~
(d) For pseudo steady state, the left side of (7) is taken to be zero, and if CAs0 = 0 and slab
geometry is used, (7) becomes
2
Ψ
De ak Cs0 H Ψ ; Cs 0 (11)
z2
For zero order solid reactions, the function H(Ψ ) can be found by using (2)
Cs
Ψ dC s' C s C S0
C s0
or
H Ψ ; Cs 0 Cs Cs0 Ψ (12)
2
Ψ
De akΨ ak' Cs0Ψ (13)
z2
which has precisely the form of a first order reaction diffusion problem, but with the
B.C. (8). Note that we have changed to the modified rate constant k’, k = k' Cs0 .
Ψ
akCAs ak' Cs0C As ;
t
Thus,
cosh z L
C As CsAs (15)
cosh(
cosh z L
Cs 1 ak' CsAs t Cs0 (16)
cosh(
These results are the same as those of Ishida and Wen, but for slab geometry.
(e) Since the entire problem is reduced, in general, to (11) with B.C. (8) (9), all the results
of Chapter 3 can be utilized with the "rate" being taken as Cs0 H Ψ ; Cs 0 ak . The
conversion is defined as
1 ' Cs $
L L
1
x! %%1 ""dz ! C s0 H dz
L 0 & C s0 # LC s0 0
(17)
L 2
De Ψ De Ψ
! 2
dz !
LakC s0 0 z LakC s0 z surface
where (11) was used as in Chapter 3. Next, (11) is partially solved as in Chapter 3:
1/2
Ψ * L
Ψ
-
*
De / .2 D e ak(C s0 HΨ )dΨ , (18)
z surface * Ψ Φ *
+
where Ψ Φ is the value of Ψ at the center of the pellet, which can be found for asymptotic
cases as in Chapter 3 (e.g., Ψ Φ ~ 0 for large Φ and irreversible reactions). Finally,
combining (17) and (18) and B.C. (8) gives:
1/2
10
ak' C sAs t
f Cs0 HΨ 3
0
x 6 42 1- dΨ 2 (19)
50 Cs0 Cs0 0
Ψ Φ 1
which is the (corrected) form of the result given in the text, with dimensionless
82 7 L2akf Cs0 /D e .
4.3. a) Derive the results of (4.2-13 to -15) by directly solving the appropriate differential
mass balances.
b) Compute the conversion-time results of Figs. 4.2-3 for φ = 2.0 (first stage only).
Solution
1 > 2 C As ;
0 ? De <r 9 ak' C AsCSo (1)
r2 r = r :
Cs
@ ak' C AsCSo (2)
r
The zero-order rate form permits the uncoupling of (1) from (2), and the standard
substitution of CAs = u/r leads to:
2
u G ak' CSo D
EE BBu A 0 (3)
r2 F De C
This equation is easily solved, as for slab geometry, and the result is:
A r B r
C As I sinh H cosh H (4)
r R r R
with
CSo
K2 J R 2ak'
De
R C O
Using the B.C. P r 2 As M L 0 , one readily finds B = 0. Then at r = R,
Q r Nr S0
Y sinh Z Z V Y A V
D e AW cosh Z T [ k g W C A sinh Z T
X R2 R 2
U X R U
From this, the constant A can be found and substituted back into (4), with the result:
C As 1 sinh \]
^ (5)
C A θ e ξ sinh \
where
f D c
ξ _ r/R and θ g 1 d e a ` coth ` 1
e dk Ra
e g b
Next, (2) is used to find the solid concentration, and by direct integration gives:
1
s C p 2
1
ξ sinh lξ θ
x m 3 qq1 nnξ dξ m 3 dξ
0r
CSo o 0
sinh l θ e
(7)
3 l
m l coth l 1
l 2
le
b) A few calculated values for t = 2.0 are given for the conversion (note that in Fig. 4.2-
t θ
3, t e = 1 and also that * u * ).
t θ
3
xv 2 coth 2 1 θ v 0.806 θ
(2) 2
4.4 The secondary steam reformer of an ammonia plant has to be opened to replace
the Ni/alumina catalyst. This requires the prior careful reoxidation of the
pyrophoric Ni-catalyst. Simulate the reoxidation by means of an oxygen/nitrogen
mixture containing 5 volume % oxygen. Use the general model of Section 4.2 to
calculate the evolution with time of the concentration profiles of oxygen (A) and
Ni (S) in the catalyst particle for various values of the rate parameters and for
conversions based on S of up to 50 %. The initial Ni content of the catalyst (CS0)
is 0.00624 kmol/kg cat.
The rate equation for ½ O2 + Ni into NiO is
KA = 0.305 exp(3070/T)
Solution
Atmospheric pressure is assumed. The density of the catalyst is 1515 kg/m 3 and the
catalyst particle diameter is 1.4 cm. Variations of the value of the diffusion coefficient by
a changing porosity do not have to be accounted for.
The molecular diffusion coefficient can be found in Perry et al. [1984] or can be
estimated from the Fuller, Schettler, and Giddings correlation also found in Perry et al.
[1984]:
1/ 2
3 1.75
M O2 M N2
10 T
M O2 M N 2
Dm ,O2 N2 w
1/ 3 1/ 3 2
p υ O2
υ N2
where T is in K, p is in atm, and D in cm2/s. The values of the atomic diffusion volumes
∑υ can be found in Perry et al. [1984], for O2, ∑υ = 16.6, for N2, ∑υ = 17.9. A value of
0.65 cm2/s is found.
The diffusion coefficient for Knudsen diffusion depends on the pore radius. For
macropores, a pore radius of 1 µm is considered (see Chapter 3). The diffusion
coefficient for Knudsen diffusion is then calculated from (3.4-4):
2r 8 R T
DK ,O2 x
3 π M O2
1
~ 1 1 {
De ,O2 ε |2 y
| Dm , O
s
DK ,O2 y
} 2 N2 z
Then, De ,O2 = 0.114 cm2/s, where the contribution of the Knudsen diffusion is minor in
this case with macropores only.
The species continuity equations to be solved are (4.2-9) and (4.2-2):
2
C O2 , s C O2 , s 2 C O2 , s
εs De ,O2 2
rO2 ρ s
t r r r
C Ni
rNi ρ s
t
with initial and boundary conditions (4.2-3)-(4.2-5):
t 0: C O2 , s C O2 , s , 0
C Ni C Ni , 0
C O2 , s
r 0: 0
r
r R: C O2 , s ( R) C O2 ( g )
Two results are shown in the figures hereafter: (1) for an initial oxygen partial
pressure of zero and (2) for an initial oxygen partial pressure equal to that in the gas
phase, i.e. corresponding to a 5 volume % oxygen content. Figures 4.4-1 and 4.4-2 show
the evolution during the first 10 seconds of the Ni concentration in the catalyst and the
partial pressure of oxygen in the catalyst pores, for the case where the initial oxygen
partial pressure is equal to that in the gas phase. Figures 4.4-3 and 4.4-4 show the
evolution during the first 10 seconds of the Ni concentration in the catalyst and the partial
pressure of oxygen in the catalyst pores, for the case where the initial oxygen partial
pressure is zero. The longer-term evolution is not shown here.
0s
CNi,s (mol/cm3 cat)
10 s
Center Solid
r (cm) surface
Figure 4.4-1. Evolution during the first 10 seconds of the Ni concentration in the catalyst.
The initial oxygen partial pressure is equal to that in the gas phase.
0s
0.1 s
pO2 (bar)
10 s
Center Solid
r (cm) surface
Figures 4.4-2. Evolution during the first 10 seconds of the partial pressure of oxygen in
the catalyst pores. The initial oxygen partial pressure is equal to that in the gas phase.
0s
CNi,s (mol/cm3 cat)
10 s
Center Solid
r (cm) surface
Figure 4.4-3. Evolution during the first 10 seconds of the Ni concentration in the catalyst.
The initial oxygen partial pressure is zero.
pO2 (bar)
10 s
0.1 s
0s
Center Solid
r (cm) surface
Figures 4.4-4. Evolution during the first 10 seconds of the partial pressure of oxygen in
the catalyst pores. The initial oxygen partial pressure is zero.
Chapter 5
5.1. For shell progressive poisoning, the “shrinking core” model of Chapter 4 was
utilized to derive the time rate of change of poison deposition, (5.2.3-6); complete the
steps leading to this result.
Solution
Equation (5.2.3-6) is obtained by elimination of C cPs and C sPs from the set of equations
(5.2.3-1) – (5.2.3-4):
d 4
C Ps π R 3 rc3 ρ s 4π R 2 k gP C P CsPs (1)
dt 3
4π D eP s CcPs
C Ps (2)
1 1 β
rc R
2 C cPs
4π r k rp
c (3)
β
d 4
Setting C Ps π R 3 rc3 ρ s x , (3) yields:
dt 3
CcPs x
β 4π rc2 k rP
4π D eP s x
x C Ps
1 1 4π rc k rP
2
rc R
from which :
«1 1¨ ¥ ¢
©© ¦¦ £
CsPs ª rc R § x £1 D eP 1
4π D eP £ « 1 1 ¨ rc2 k rP
£ ©© ¦¦
£¤ r
ª c R § ¡
or
d½ 4 º 4π R 2 k gP C P
x » C PsÅ Ä π R 3 rc3 ρ
½ º
s
dt ¼ 3 ¹̧
» ¸
Ã1 1 À 2 k gP » D eP ¸
1 ÁÁ ¾R 1
 rc R ¾¿ D eP » à 1 1 ¸À
» rc k rP ÁÁ ¾¾ ¸
2
»¼ r
 c R ¿ ¸¹
Ì 4 É 4 Ó1 1Ð 11 ξ Ù rc Ö
With ÊC PsÍ Æ π R 3 rc3 Ç C Ps Æ π R 3 and ÑÑ Î ×ξ Ô
Ë 3 È 3 Ò rc R ÎÏ R ξ Ø RÕ
This equation is transformed into
3k gP
CP
d R
C Ps ρ
dt
S
R k gP 1 ξ ß D eP R 1 ξ Ü
1 1
D eP ξ ÝÞ k rP rc2 1 ξ ÚÛ
or
3D eP 1 C Ps
à
d æ C Ps ã R 2 ρ s C Psç
ä á
dt äå C Psç áâ D eP 1 ξ 1
2
R k gP ξ Daξ
with Da k rP R D eP
Sh' P k gP R D eP
5.2. The effect on the reaction rate for shell-progressive poisoning is based on (5.2.3-8), (-
9) and (-10). Use these to derive the effectiveness factor relationship (5.2.3-11).
Solution
Derive:
1
ñ C í 3Q 2
η îî Ps ëë (5.2.3-12)
ï C Psò ì 1 1 ξ 1
Sh'A ξ ξ è3êξ coth 3êξ 1é
1
rc ø C Ps õ 3
where ξ ö1 ó
R ÷ C Psù ô
Sh' A k rA R D 'eA
R
ú k rA D eA
3
R
û' k rA D 'eA
3
1 d 2 dC 'A þ
Poisoned Shell: D 'eA ÿr ü 0, rc r R (5.2.3-8)
r 2 dr ÿð dr üý
1 d 2 dC As
Unpoisoned Core D eA r k rA C As , 0 r rc (5.2.3-9)
r 2 dr dr
Boundary conditions :
dC 'As
D 'eA k gA C A C sAs @r R (5.2.3-10a)
dr
dC As dC sAs
CA C 'As D eA D 'eA @r rc (5.2.3-10b)
dr dr
C As finite @r 0 (5.2.3-10c)
from (5.2.3-8)
d 2 dC sAs
r 0
dr
dr
dC 'As C1
dr r2
C1
C 'As C2 (d)
r
dC 'As
D 'eA k gA C A C sAs @r R
dr
k gA
C1 '
R 2 CA C sAs (e)
D eA
using B.C. (5.2.3-10b) with (c), (d), and (e)
B k gA R 2
sinh k rA D eA rc '
CA CsAs C2 (f)
rc D r
eA c
also,
B k rA B k rA k rA k gA R 2
D eA 2
sinh r cosh r D 'eA
CA C sAs (g)
r D eA r D eA D eA r rc
D 'eA r
From (g)
2
$R!
k gA "" CA C sAs
# rC
B
1 k rA k rA 1 k rA
D eA cosh rc 2
sinh rc
rc D eA D eA rc D eA
k gA R 2 C A C sAs
B
k rA * k rA k rA '
D eA sinh rc ( rc coth rc 1%
D eA () D eA D eA %
&
but,
k rA R k rA rc
rc , , 3 3+ξ
DeA 3 DeA R
so,
k gA R 2 C A CsAs
B (h)
D eAsinh 3/ξ -3/ξ coth 3/ξ 1.
From (f)
B k gA R 2
C2 sinh 39ξ CA Csas
rc D 'eA rc
k gA R 2 C A CsAs k gA R 2
CA Csas (i)
D eA 8 rc 039ξ coth 39ξ 11 D 'eA rc
s
7
2 k gA R 2 1 42
CA C as 6 '
8 3
5 D eA rc 039ξ
2 coth 39ξ 11 Sh A ξ 2
Combining (c) and (h)
k gA R 2 C A CsAs 1 k rA
C As <
sinh r (j)
DeAsinh 3=ξ :3=ξ coth 3=ξ 1; r DeA
2
E
@ k gA R K1 r HB@
C'As CA CsAs D Sh 'A II FA (k)
C D eA rc >(3Lξ ) coth
@ 3Lξ 1? Jξ r FG@
dC'As
4π R 2 D 'eA
dr r R
η (l)
4
π R 3k rA C A
3
4π R 2 k gA C A C sAs 3 k gA R C sAs O
η P1 M (m)
4 R k rA PQ C A MN
π R 3 k rA C A
3
2
s s
E
@ k gA R K1 HB
@
C As CA C As D Sh 'A II 1FFA
C D eA rc >(3Lξ ) coth
@ 3Lξ 1? Jξ G@
k gA R
Rewriting: Sh 'A
D eA
2
3 k D 1 3 D 'eA
1
then, gA eA
R k rA k gA R 3 R k rA
3 '
2
2
R k rA
k gA R 2 3 2
D 'eA RD 'eA 1 D eA 1
and
D eA rc k gA R rc D eA ξ R k rA
2
ξ '
3 D 'eA
1
2
3 '
η 2
1 1 ξ ¥¢ 1
££
Sh 'A 1 ¤ ' ¡ ξ (3ξ ) coth 3ξ 1
1
2
3 ©'
η (5.2.3-12)
1 1 ξ 1
Sh 'A 1 ξ §(3©ξ ) coth 3©ξ 1¨
5.3. Obtain a plot of the deactivation function Φ vs. dimensionless time ω for the shell
progressive model:
For Da ¹ ¸ and Sh 'p » º , the dimensionless time is found by integrating the results
of Problem 5.1 (or (5.2.3-7)):
1
2
Á1 '
Cp ¾
ω ¿ Ns t ¼
À¿
3 C ps B ½¼
1
2
È Î 2
3 ËÅ
Ã1 Ì Ô C ps
Ò
Ñ
Ï
3Î Ô C ps
Ò
ÑË
ÏÉ
3 ÉÃ
Ç Ì1 Ä
Ì ÒC Ï ÒC Ï 2 ÉÃ
Ã3 Ì Ó psÕ Ð
2 ÍÌ Ó psÕ ÐÊÉ
É
Æ Í Ê
1
2
Ú1 à 3 3 2 3 Ý×
Ù Þ ξ 1 ξ Ö
Ø3 ß 2 2 ÛÜ
1
2
å 1 ëò 3 3 2 1 îè â
ä éï ξ ξ ì á (B)
ã 3 êñ 2 2 íæç
ó 0 3 10 100
η 0 1 0.67 0.27 0.03
C ps
(1) Pick value of (0 to 10 by 0.1 increments)
C ps ô
1
ú 3÷
ð C ps ý
(2) Determine ξ ø1 þ û õ
ø þC û õ
øù ÿ ps ü õö
5.4. Derive (5.2.4-5) and (-7) for poisoning effects with consecutive reactions.
Solution
SLAB
1 2
A
R
S
Unpoisoned Poisoned
(Both Rxn’s Poisoned)
zone zone
O Zc L
Boundary conditions
@ Z = Zc
BC(7) C 'As C As
'
BC(8) C Rs C Rs
'
BC(9) C Ss C Ss
'
C As C As
BC(10) D'eA DeA
Z Z
'
C Rs C Rs
BC(11) D 'eR D eR
Z Z
'
C CSs
BC(12) D 'eS Ss
D eS
Z Z
Differential Eqs.
2
C'As
1. D 'eA 2
0
Z
2 '
' C Rs
2. D eR 2
0 (Poisoned Zone)
Z
2 '
CSs
3. D'eS 2
0
Z
2
C As
4. D eA 2
k1C As
Z
2
C Rs
5. D eR 2
k1C As k 2C Rs
Z
2
CSs
6. D eS 2
k 2C Rs
Z
Boundary conditions
@ Z =L
'
C As
BC(1) D 'eA k g A CA C'As
Z L
'
C
BC(2) D 'eR Rs
k g R CR C'Rs
Z L
'
C
BC(3) D 'eS Ss '
k gS CS CSs
Z L
@ Z =0
C As
BC(4) 0
Z
C Rs
BC(5) 0
Z
CSs
BC(6) 0
Z
k gA L k1 Zc
Let Sh 'A '
D 'eA D eA1 l ξ
D eA D eA L
k gR L k2
Sh 'R '
D 'eR D eR 2 L
D eR D eA
k gS L
Sh S' '
D 'eS D eS
D eS
1A C 'As A BZ
2A C 'Rs C DZ
'
3A C Ss E FZ
4A C As G sinh 1 Z L H cosh 1 Z L
C Rs ?
These are complicated.
C Ss ?
Z
1B C'As A Sh 'A C A C'As
L L
Z
2B C'Rs C Sh 'R C R C'Rs
L L
' Z
3B CSs E Sh S' CS '
CSs
L L
Thus @ Z = L
A Sh 'A C A
C'As A Sh 'A CS C'Ss C 'As
L L L 1 Sh 'A C A
C Sh 'R C R
Similarly: C 'Rs
L 1 Sh 'R C R
' E Sh S' C S
C Ss
L 1 Sh S' C S
Sh 'A Z
1C C'As A C A A
1 Sh 'A L
Sh 'R Z
2C C'Rs C C R C
1 Sh 'R L
' Sh S' Z
3C CSs E !CS E"
1 Sh S' L
#C As
0 only when G = 0
#Z 0
* Z'
$ 4C C As H cosh( +1 %
) L&
Substitute 4C into 5
2
9 C Rs k1 1 7 Z 4. k2
/H cosh5 81 2 C Rs
9Z
2
D eR 0 6 L 3,- D eR
2 2 2
A
C Rs ? @2 < ? @1 < DeA ? Z<
5A 2 = : C Rs = : H cosh= @1 :
AZ > L; >L; DeR > L;
G
ZD G ZD G ZD G ZD
5B C Rs I sinhE H1B J coshE H1 B S sinh E H1 B T coshE H1 B
F LC F LC F LC F LC
General solution Particular solution
Inserting 5B into 5A and equate cosh (by inspection-only the particular solution need be
substituted).
2 2 2
N O1 K N ZK N O1 K N ZK N O1 K U N ZK N Z KR
SL I sinh L O1 I TL I cosh L O1 I L I SS sinh L O1 I T coshL O1 I
MLJ M LJ MLJ M LJ MLJ T M LJ M L JPQ
2
N O1 K D eA N ZK
L I H coshL O1 I
MLJ D eR M LJ
[ ZX
Equating coefficients sinh Y \1 V terms: S = 0
Z LW
2
b Z_ T 2 2 d1D eA
cosh` c1 ] terms: 2 d1 d2 2
a L^ L L D eR
2
e1 D eA
T 2 2
H
e1 e2 D eR
mC Rs
0 when I = 0
mZ 0
2
t Zq u1 D eA t Zq
n 5C C Rs J coshr u2 o 2 2
H coshr u1 o
s Lp u1 u2 D eR s Lp
Substitute 5C into 6
2
2
CSs k2 { Z~ 1 D eA Z ~x
2 yJ cosh 2 | 2 2
H cosh 1 |v
Z D eS z L} 1 2 D eR L }w
2 2
CSs 2
2 D eR Z 1 D eA Z
6A 2 J cosh 2 2 2
H cosh 1
Z L D eS L 1 2 D eR L
The solution is
Z Z Z Z
6B CSs M Nz θ sinh 2
U cosh 2 P sinh 1 V cosh 1
L L L L
General solution Particular solution
2 2
¤¥ ¡ ¤ Z¡ ¤ ¥1 ¡ ¤ Z¡
U¢ 2 cosh¢ ¥2 V¢ cosh¢ ¥ 2
£ L £ L £L £ L
2 2
¤ ¥2 ¡ D eR ¤ Z¡ ¥1 D eA ¤ Z ¡
¢ J cosh¢ ¥ 2 2 2
H cosh¢ ¥1
£ L D eS £ L ¥1 ¥2 D eR £ L
equating coefficients
2 2
¬ Z© ³ ´2 ° ³ ´2 ° D eR D eR
sinh ª 2 §: U± ® ± ® J µU J
« L¨ ² L¯ ² L¯ D eS D eS
2 2 2 2
» Z¸ ý À à ½2 À DeA ½1 D eR u1
cosh¹ ¼1 ¶ : VÁ 1¾ Á ¾ H ÄV H
º L· ÂL¿ Â L¿ DeS ½12 ½2 2 D eS u12 u2 2
ÌCSs
0 when N = 0
ÌZ 0
2
D eR Ó Z Ð D eA Ô1 Ó ZÐ
Í 6C CSs M J cosh Ñ Ô2 Î 2 2
H coshÑ Ô 2 Î
D eS Ò L Ï D eS Ô1 Ô 2 Ò LÏ
Summarizing
Sh 'A Z
1C C 'As A ÕC A AÖ
1 Sh 'A L
Sh 'R Z
2C C 'Rs C ÕC R CÖ
1 Sh 'R L
' Sh S' Z
3C C Ss E ×C S EØ
1 Sh S' L
Þ ZÛ
4C C As H coshÜ ß1 Ù
Ý LÚ
2
Ê ZÇ D eA Ë1 Ê ZÇ
5C C Rs J coshÈ Ë2 Å 2 2
H coshÈ Ë1 Å
É LÆ D eR Ë1 Ë2 É LÆ
2
D eR Ê ZÇ D eA Ë1 Ê ZÇ
6C CSs M J coshÈ Ë 2 Å 2 2
H coshÈ Ë1 Å
D eS É LÆ D eS Ë1 Ë 2 É LÆ
There are six unknowns and six remaining BCs ( BC(7) à BC(12) ).
'
åC As åC As Sh 'A áC A A â ã1
ä H sinh ã1ξ (7)
åZ Zc
åZ Zc 1 Sh 'A L L
Sh 'A
C'As C As Zc é A æC A A çξ H cosh è1ξ (8)
Zc 1 Sh 'A
CA
H
ú 1 ÷
1 øø1 ξ õô1tanh ô1ξ
ù Sh 'A õö
'
ûC Rs ûC Rs
B.C.(11)
ûZ Zc
ûZ Zc
C 'Rs C Rs Zc
B.C.( 8)
Zc
1 Sh 'R D eA þ12
C R ü1 þ 2ξ tanh þ 2ξ ý Hüþ1sinh þ1ξ þ 2cosh þ1ξ tanh þ2ξ ý
Sh 'R D eR þ12 þ 22
C
1
1 1 ξ þ 2 tanh þ 2ξ
Sh 'R
D eA þ12 1
C R H cosh þ1ξ þ1 1 ξ sinh þ1ξ tanh þ 2ξ
D eR þ12 þ22 Sh 'R
J
1 ð
1 1 ξ þ tanh þ 2ξ ÿsinh þ2ξ
' 2
Sh R
Finally using
C Ss
'
C Ss
Z Zc
Z Zc
'
C Ss C Ss Zc
Zc
6.1 Derive the rate equation for a reversible first order gas-liquid reaction
A P
dCp
B.C. y = 0: CA = C Ai and =0
dy
y = y1: CA = CAb and Cp = KC Ab
k L C A i - C Ab 1+ K
Show that NA = '
tanhγ
1+ K
γ '
k 1 1 + K DA
where γ '=
k L2 K
Solution
% C &
The rate equation of a reversible first order gas-liquid reaction reads r=k1 ' CA - P (.
) K *
The continuity equations for species A and P are
d 2CA + C ,
DA 2
=k1 - CA - P . (1)
dy / K0
1 C 2
2
d CP
DP 2
=-k1 3 CA - P 4 (2)
dy 5 K 6
d2
Since D A =D P , D A 2 CA +CP =0 (3)
dy
d dC -N A
CA +CP = A = (4)
dy dy y=0
DA
D A k 1 (K 1)
where @' ?
k 2L K
-N A
P= '
(8)
k L K+1 γ
NA
Q= +CAb (9)
k L K+1
Accounting for the boundary conditions permits the determination of the integration constants
A1 and A 2 .
NA
For y = 0 CAi =A1 +CAb +
K+1 k L
NA
A1 =CAi -CAn - (10)
K+1 k L
NA NA
For y = yL CAb =A1coshγ ' +A 2sinhγ ' - + +C Ab
K+1 k L K+1 k L
A1
A2 B
tanh A '
C NA DE C ' y D 1 C y DF NA C y D
CA = G CAi -Cb - HH I cosh G γ H- sinh G γ ' HJ - G -1 H +C Ab
G y L L tanhγ '
K K+1 k L LM K K y L L N K+1 k L K y L L
The rate of the overall phenomenon follows from the application of Fick’s law:
dCA
N A =-D A
dy y=0
Solution
dCBb
= - k1C Bb C A (1)
dt
dCRb
= - k1C Bb C A - k 2 C Rb C A (2)
dt
dCRb k 2 CRb
= 1 (3)
dCBb k1 CBb
k2
Let = a , CRb = x and CBb = y.
k1
dx x
(3) becomes = a -1 (4)
dy y
B.C.: x = 0 for y- y0
x dx dz
The transformation = z leads to = y +z (5)
y dy dy
dx
and (4) becomes = az-1 (6)
dy
dy dz
(5) and (6) - = (7)
y 1- a-1 z
with B.C.: z = 0 at y P y0
y 1
ln = ln Q1- a-1 z RT
y0 1- a S
or
a
U y V y x
W X = - a-1
Y y0 Z y0 y0
k2
[ CBb \ k1 CB [ k 2 \ CRb
] ^ - = ] 1- ^
_ CB0 ` CB0 _ k1 ` CB0
6.3 A gas is being absorbed into a liquid in which the concentration of the reactive
component B is 0.1 M. The reaction between the gaseous component A and the
component B is extremely fast. The conditions are such that CAi = 0.1M . Further,
DA = 10-5 cm 2 /s . Compare the enhancement factors based upon the film theory and
1
the surface renewal theory for the cases that a) DA = DB ; b) DB = DA ; c)
2
DB = 2DA .
Solution
1) Film theory
a D B CBb
FA = 1+
b D A C Ai
a) FA = 2
b) FA = 1.5
c) FA = 3
β 2 2
g β h b CBb β
D B DA g β h
e erfc i
DB
j= e erf i j
i D j a CA DA i D j
k B l i k A l
a) FA = 2
b) FA = 1.83
c) FA = 2.3
6.4 Consider the absorption of gaseous CO2 by a NaOH solution. The stoichiometry is as
follows:
CO 2 + 2NaOH = Na 2CO 3 + H 2O
1) Can the reaction be considered as being of the pseudo first order when the
gas-liquid contact time is 0.01s and when
a) The partial pressure of CO2 is 0.1 bar and the concentration of NaOH
1 mol/l?
b) The partial pressure of CO2 is 1 bar and the concentration of NaOH
1M?
2) When the gas-liquid contact time is 0.1s and the NaOH concentration is 3
mol/l, what is the partial pressure of CO2 above which the reaction is no
longer pseudo first order. Take k’= 107 cm³/mol s and H = 25.10³ cm³
bar/mol.
Solution
N A =k L CAi
DA
N A =2CAi
π t
So that k L can be related to the contact time by
DA
k L =2
π t
kD A π
and γ = = kt with k=k 'C NaOH
kL 4
π
Finally, γ = 104 C NaOH t (with NaOH in mol/l)
4
a D B CBb C
=12.5 NaOH
b D A C Ai PCO2
π a D B CBb
1. a) for γ = 104 x1x0.01 m 785 and =125
4 b D A C Ai
a D B CBb
b) for γ n 78.5 and =12,5 it is not
b D A C Ai
C NaOH
2. when γ n 50 12.5 has to be larger than 200 so that p CO 2 should not exceed
PCO2
0.2 bar.
CO 2 + 2R 2 NH → ® R 2 NCOO - + R 2 NH 2+
The rate of absorption at these conditions is found to be 3.26∙ 10-4 mol/s. What is the
value of the rate coefficient neglecting the gas phase resistance and considering the
reaction to obey pseudo first order behavior?
Additional data are: DA = 1.4∙ 10-5 cm²/s; DB = 0.77∙ 10 -5 cm²/s; Henry’ constant, H =
29.8∙ 10³ atm cm³/mol .
Solution
The solution is obtained from (6.5.4-3) or from the two simplified formulae derived from it—
for short contact times (6.5.4-4) and for long contact times (6.5.4-5).
Q 3.26 o 10 4
First calculate N A p p p 1.73 o 10 6
mol/cm²s
t 188.5
q 1 r
Then, from (6.5.4-5), N A =CAi D A k 'CB s1+ ' t
u 2k CB t v
2
0.1atm 5 cm mol
NA x 3
1.4 w 10 k' 2.5 w 10 3 3
atm cm s cm
29.8 w 103
mol
~ 1 {
|1 3 y
} 2k'0.2 2.5 10 z
from which:
By repeating this calculation on the basis of (6.5.4-4) it is seen that k 'CB t largely exceeds the
value for which this formula is valid.
Chapter 7
7.1. Write (7.3.1.1-6) in terms of ξ 'i , the extent of the i-th reaction per unit mass of the
reaction mixture, defined by
ξ i Cj
ξ '
i (kmol/kg)
N j0
ρ f 0
Solution
(7.3.1.1-6) reads:
x j x j x j x j ρ f
ρ f ux j ρ f D e, x ρ f D e, y ρ f D e,z R
t x x y y z z C
j 0
M
Starting from: N j N j0 α ij ξ i
i
N j0 Nj
and xj
N j0
1 ρ
we get: xj i α ij ξ α ij ξ i' f
N j0
i C
j 0
Further
M
R j α ij ri
i
r j i α ij ri
Substituting the above relations into (7.3.1.1-6), we get for the ith reaction:
ρ £ξ i'
ρ f f α
ij u¥ξ i'
C
j 0 £t
ρ f ¢ £ £ξ i' £ £ξ ' £ £ξ ' ρ f
¤ α ij ρ f D e, y i ρ f D e,z i α ij ri
C £x f e, x £x
ρ D
£y £y £z £z C
j 0 ¡ j 0
or
« ¬ξ i' ¨ ¬ « ¬ξ i' ¨ ¬ « ¬ξ i' ¨ ¬ « ¬ξ i' ¨
ρ f ©© u®ξ ¦¦
'
©© ρ f D e,x ¦ © ρ f D e, y ¦ © ρ f D e,z ¦ ri
ª ¬t § ¬x ª ¬x ¦§ ¬y ©ª ¬y ¦§ ¬z ©ª ¬z ¦§
i
7.2. Derive the steady state continuity and energy equations and appropriate boundary
conditions for the tubular reactor with turbulent flow, corresponding to the various
situations represented in the figure below. The continuity equation for the first case
is given by (in cylindrical coordinates):
µC j µ 2C j 1´ µ µC j ±
ur ¶ D e,z r ² rD e,r r ¯ Rj
µz µz 2 r ³ µr µr °
·C j 0, r
with B.C. u r C j0 ¸ u r C j 0, r D e,z r
·z
ºC j
z=L ¹ 0 , all r
ºz
ºC j
z=0 ¹ 0 , all z
ºr
ºC j
z = Rt ¹ 0 , all z
ºr
Solution
ÂT Â 2T 1Á Â ÂT ¾
ρ f Cpu z Ãλ r rλ r » Δ H i ri
Âz r ¿À Âr Âr ¼½
e, z e, r
Âz 2
B.C.
Çno radial dispersion
Ä
a) entrance: z = 0 Æ
Äno reaction
Å
ÊT 0, r
ρ f C p u r ÈT0 T 0, r É Ë λ r
Êz
e, z
ÍT
b) z = L Ì0 all r
Íz
ÍT
c) r = 0 Ì0 all z
Ír
ÏT
d) r = Rt λ e, r Î U Tr TR
Ïr r Ð R t
2. λ e, z λ e, r
cst and
D e,z D e,r
×C j × 2C j D e,r Ö × ×C j Ó
ur Ø D e,z Ô r Ñ Rj
×z ×z 2 r Õ ×r ×r Ò
B.C.:
ÙC j 0, r
a) u r C j0 Ú u r C j 0, r D e,z
Ùz
conditions for: z = L
r = 0 as in case 1
r = Rt
Energy equation:
ÙT Ù 2T λ á Ù ç ÙT äÞ
Úλ
e, r
ρ f Cpu r r år â Û Δ H i ri
Ùz r ßà Ùr æ Ùr ãÜÝ
e, z
Ùz 2
B.C.:
êT
a) ρ f C p u r èT0 T 0, r é ë λ 0, r
êz
e, z
b), c) as in case 1
ÙT
d) r = Rt λ Ú U Tr TR
Ùr r ì R t
e, r
D e,z ñ D e,a ñ
í í
3. For a flat velocity profile, u(r) = constant and ï become ï corresponding to a
λ e,z íî λ e,a íî
uniform velocity profile
Continuity equation:
ÙC j Ù 2C j D e,r á Ù ÙD j Þ
u Ú D e,z ß r Ü Rj
Ùz Ùz 2 r à Ù r Ùr Ý
B.C.:
òC j 0, r
uC j0 ó uC j 0, r D e,a
òr
Energy equation:
T 2
T λ ú ð T ý÷
ρ f Cp u λ e, r
þr û ô Δ H i ri
r øù r ÿ r üõö
e, z
z z2
B.C.:
T
ρ f C p uT0 T 0, r λ
z
e, z
C j
Flat concentration profile 0
r
T
Flat temperature profile 0
r
Continuity equation:
dC j d 2C j
u
D e, a Rj
dz dz 2
B.C.:
dC
uC j0 uC j z 0 D e, a j
dz
z 0
dC j
z = L: 0
dz
C j
Since 0 , the other B.C.’s don’t need to be considered.
r
Energy equation:
dT d 2T 4U
ρ f Cp u λ e, a Tr Δ H i ri T
dz dz 2 dt
4 surface
in the last term comes from
dt volume
π d dz 4
t
2 dt
π dt
dz
4
B.C.:
dT
ρ f C p uT0 Tz 0 λ e, a
dz z 0
5. No dispersion in axial direction D e,a ! 0
Continuity equation:
dC j
u " Rj
dz
B.C.:
C j0 # C j z # 0
Energy equation:
dT 4U
ρ f Cp u $% Δ H i ri Tr T
dz dt
B.C.:
T0 & T z & 0
8.1 The esterification of butanol with acetic acid, using sulfuric acid as a catalyst, was
studied in a batch reactor:
C 4 H 9 OH CH 3 COOH ,H, ,- C 4 H 9 - O - C - CH 3
2 SO 4
The reaction was carried out with an excess of butanol. The following data were
collected [C.E. Lejes and D.F. Othmer, I&EC, 36, 968 (1945)].
Solution
A plot of 1/CA vs t yields a straight line. Hence the reaction is second order. The slope of the
line is the reaction rate coefficient and equals 0.9 liter/(g mole h). Point values for k are also
obtained from the integrated continuity equation:
dCA
rA = - = kCA2
dt
or
1 1 .1
- =k
CA CA0 t
8.2 The following data on the conversion of hydroxyvaleric acid into valerolacetone
were collected
Time (min) 0 48 76 124 204 238 289
Acid concentration (gmole/l) 19.04 17.6 16.9 15.8 14.41 13.94 13.37
Determine a suitable kinetic model by means of both the differential and integral
method of kinetic analysis.
Solution
Differential method:
t Δ t CA Δ CA Δ CA/Δ t CA ln C A
0 19.04
48 1.44 0.03 18.32 2.908
48 17.6
28 0.7 0.025 17.25 2.848
76 16.9
48 1.1 0.0229 16.35 2.794
124 15.8
80 1.39 0.0174 15.11 2.715
204 14.41
34 0.47 0.0138 14.18 2.651
238 13.94
51 0.57 0.0112 13.66 2.414
289 13.37
rA = k C An
ln rA = ln k + n ln C A
Hence
rA = k C3A
A plot of rA vs C3A should give a straight line, the slope of which is k. It follows:
k 5 / 10 6
l 2 /g mole 2 min
Integral method:
dC A
rA = - = k C3A
dt
from which
C1/2 1/2
A - C A0 = 2 kt
C1/2
A C1/2
A0
2t k
4.698×10-4 96 4.89×10-6
7.428 152 4.89
12.47 248 5.03
20.57 408 5.04
23.88 476 5.02
28.36 578 4.91
was carried out in a 200 ml reactor at 26°C. The initial concentrations of both
reactants were 0.051 N.
a) From the following time versus concentration data, determine the specific rate
and tabulate as a function of composition of the reacting mixture.
Solution
Time (sec) NaOH (gmole/liter) Δ t (sec) -Δ C (gmole/liter) -Δ C/Δ t
0 0.0510
30 0.0081 0.000270
30 0.0429
60 0.0089 0.000148
90 0.0340
60 0.0058 0.0000967
150 0.0282
60 0.0042 0.00007
210 0.0240
60 0.0031 0.0000517
270 0.0209
120 0.0045 0.0000375
390 0.0164
240 0.0046 0.0000192
630 0.0118
480 0.0051 0.0000106
1110 0.0067
Figure 8.3-1
- rA = k C A C B
Δ ( rA ) 10 5 10 5
1 liter
k 10
Δ (C A C B ) 10 5 10 4
gmoles 4 sec.
Integral method:
dCA 2
- rA = - = k CA C B =kCA2 =kC A0
2
1-x
dt
dCA -d CA0 1-x dx 2
- = =CA0 = k C2A0 1-x
dt dt dt
x t
dx
2
= k CA0 dt = k C A0 t
0 1-x 0
x
= k CA0 t
1-x
4.5
Slope: k CA0 = = 0.00529
850
8.4 A daily production of 50,000 kg (50 tons metric) of ethyl acetate is to be produced
in a batch reactor from ethanol and acetic acid:
C 2 H 5 OH CH 3 COOH 7 CH 3 COOC 2 H 5 H 2O
(A) (B) (R) (S)
rA k (C A C B C R CS K )
At 100°C
k 7.93 8 10 6 m³/kmols
K 2.93
Solution
The conversion will be based on CH 3 COOH (B)
χ Bf 0.35
dχ 3.91 dχ
θ C B0 A
7270 s 9 2h.
0
rB χ B 7.93 : 10 6
0 CACB
1
C R CS
2.93
24 hr
8 batches
2 1 hr
The daily production rate per m³ reactor volume is used to find the necessary volume:
50,000 kg R
V 52 m³
kmol R ; kg ;
8 batches 1.37 per batch 88
m³ kmol
10,000 =
k 1014 exp h 1
Solution
For the reaction A > R S , in the gas phase, the general batch reactor design equation is
(8.1-4):
χ Af
dχ A
θ N A0
0
V rA χ A
The rate equation given contains species concentrations, which in general are given by (8.1-
8):
1 χ A z 0 T0 p t ?
CA C A0
1 ε A χ A z T p t0
Therefore, in general the mode of operation must be chosen – i.e., constant volume (where the
simpler equation (8.1-5) is used), constant pressure p t p t0 , or other conditions. However,
for the special case of first order reactions, this choice is not necessary, since the mass
balance requires VrA :
VrA VkC A kN A kN A0 (1 χ A )
χ Af
dχ A
θ
0
k T 1- χ A
a) Isothermal operation T A T0
Here,
χ Af
1 dχ A 1
θ ln 1 χ A
k T0 0
1 χ A k T0
with
dT
mtcp V Δ H rA Q
dθ
Δ H k N A0 1 χ A Q
For part a) with isothermal conditions,
dT
D0
dθ
k T0 θ
Qθ Δ H k T0 N A0 1 χ A Δ H k T0 N A0 e
kcal E 1
1500 0.334 h 0.1016 kmol 1 χ A
kmol
kcal
50.9 1 χ A
h
b) For adiabatic operation the temperatures (for substitution into the rate coefficient)
must first be determined with the heat balance:
dT dχ A
m t cp Δ H N A0 Q (adiabatic => Q → 0)
dθ dθ
JN ~ NR ~ NS ~
mtcp N t H A Cp A Cp R Cp S N A0 F 1 χ A 30 χ A 25 χ A 20 G
I Nt Nt Nt
N A0 30 15χ A L 40 N A0 4.064 kcal/KC
Δ H N A0
T T0 χ A
mtcp
Δ H O 15
T T0 ln M1 χ A
15 N 30
O ~ ~ ~
Δ H Cp R Cp S Cp A P
T0 ~ ~ ~ ln M1 χ A ~
Cp R Cp S Cp A MN Cp A
( 1500)
T 300QK χ A 300 37.5 χ A
40
Tad 300 37.5 (1) 337.5; 340.6RK, exact
χ Af
dχ A
θ
U 10,000
0
1014 exp S 1 χ A
T 300 37.5χ A
Figure 8.5-1
2 X
1 P
A
3 Y
Discuss qualitatively the optimum temperature profile for the two cases: (a) E 2 > E3
> E1; (b) E2 > E1 > E3. Describe your reasoning carefully.
Solution
a) E2 > E3 > E1
The temperature should be high at the beginning of the reaction to speed up reaction 1;
reactions 2 and 3 are not yet important then. Later in the reaction, T should be decreased
to decrease the P lost to X and Y.
Therefore, the profile should be rather sharply decreasing.
b) E2 > E1 > E3
Again start with high temperature and decrease with time. However, the profile should
not be as steep to avoid excessive loss of P to Y.
8.7 One method of decreasing the large initial heat release in a batch reaction is to utilize
“semibatch” operation. Here, the reactor initially contains no reactant and is filled up with
the reacting liquid-thus, there is an inflow but no outflow, and the reacting volume
continuously changes. The mass balances are:
Total:
dV
F0'
dt
Reactant A:
d
VC A F0' C A0 kVCA
dt
(a) Show that the reactant concentration at any time is, with isothermal operation,
CA F0' 1 e kt
C A0 k V0 F0' t
(b) Derive an expression for the rate of heat release and sketch the curve.
Solution
a) Mass balance
dV
Total: F0V
dt
Integrating
V V0 F0Wt (1)
d
Reactant A: VC A F0X C A0 kVC A
dt
dC A dV
or V CA F0Y C A0 kVC A (2)
dt dt
dC A
V0 F0Z t C A F0Z F0Z C A0 k V0 F0Z t C A
dt
dC A ^ F0[ F0[C A0
\k CA (3)
dt ] V0 F0[ t V0 F0[ t
Integrating factor
F0b c dt
a b b `
e _kt
k
F0Y t e kt
V0 F0 t ln V0 F0 t
e V0
F0dC A0 F0dC A0 kt
V0 F0dt e kt C A V0 F0dt e kt dt e C
V0 F0dt k
F0e C A0 const. kt
CA e (4)
k V0 F0e t V0 F0e t
F0fC A0 const.
0
kV0 V0
F0gC A0
Const.
k
F0e C A0 F0e C A0 . kt
CA e
k V0 F0e t k V0 F0e t
CA F0h 1 e kt
(5)
C A0 k V0 F0ht
dT
b) MC p Δ H rA V Q
dt
Q Δ H rA V Δ H kC A V
C A0 F0i 1 e kt
Q Δ Hk V0 F0i t Δ H C A0 F0i 1 e kt
k V0 F0i t
or
Q kt
1 e (6)
Δ H C A0 F0j
Figure 8.7-1
rA = kC A
with
7900 −1
k = 4 × 10 6 exp − s
T
The initial temperature T0 of the reaction mixture is 20°C and the maximum
allowable reaction temperature is 95°C. The reactor contains a heat exchanger
with area A k = 3.3 m 2 , and it can be operated with steam ( Tr = 120°C ,
U = 1360 W / m 2 °C ) or with cooling water ( Tr = 15°C , U = 1180 W / m 2 °C ).
The times required for filling and emptying the reactor are 10 and 15 min,
respectively. Other physicochemical data are : ∆H = −1670 kJ / kg ;
ρc p = 4.2 × 10 6 J / m 3 °C ; M A = 100 kg / kmol ; C A 0 = 1 kmol / m 3 .
The desired conversion is x Af ≥ 0.9 , and the batch reaction and complete
reaction cycle times along the steam and water consumption rates are to be
determined for the following policies of operation:
(a) Preheat to 55°C, let the reaction proceed adiabatically, start cooling when
either T = 95°C or x A = 0.9 occurs, and cool down to 45°C.
(b) Heat to 95°C, let the reaction proceed isothermally until x A = 0.9 occurs,
cool down to 45°C. [See H. Kramers and K.R. Westerterp, Elements of
Chemical Reactor Design and Operation, Academic Press, New-York
(1963).]
Solution
(a) The complete reaction cycle time can be divided into the time required for heating
from 20 to 55°C, the time required to reach T 95kC or x A 0.9 , the time required to
cool down to 45°C, and the time required for filling and emptying the reactor.
- The time required to heat up adiabatically from 20 to 55°C can be calculated from an
energy equation
UA k t l
T 55 C
dT dT
UA k (Tr T) Vmc p n dt
dt Vmc p 0 l (Tr
T0 20 C
T)
Integrating yields
Vpc p Tr T o
tH ln 2016 s 33.6 min
UA k Tr T0
- To know whether T 95kC or x A 0.9 is reached first, the temperature when reaching
x A 0.9 is calculated, again with from an energy equation based on adiabatic operation
x Af 0.9
dT dC A dx A T
( sH ) C A 0
Vrc p V ( sH ) u V( sH)C A 0 t dT dx A
dt dt dt T0 55q C
rc p xA0 0
Integrating
( wH)C A 0
T T0 x af 90.78vC 95vC
mc p
This shows x A 0.9 is reached before T 95kC . The time required to obtain a 0.9
conversion is calculated from
0.9 0.9
dx A dx A
tR C A0
kC A0 (1 x A ) 7900 x
0 0
4 y 10 6 exp (1 x A )
T(x A )
0.9
dx A
0 x
7900
4 y 10 6 exp (1 x A )
( Δ H)C A0
T0 xA
ρ cp
- The time required to cool down from 90.78°C to 45°C is found in the same way as the
time to heat up
V{c p Tr T z
tC ln 4997 s 83.3 min
UA k Tr T0
The complete cycle time is then found from a summation including the time required for
filling and emptying the reactor.
(b) The complete reaction cycle time can be divided into the time required for heating up
from 20 to 95°C, the time required to reach x A 0.9 , the time required for cooling down
to 45°C, and the time required for filling and emptying the reactor.
- The time required to heat up from 20 to 95°C can be calculated in the same way as in (a)
UA k t |
T 95 C
dT dT
UA k (Tr T) V}c p ~ dt
dt V}c p 0 | (Tr
T0 20 C
T)
Integrating yields
Vc p Tr T
tH ln 6487 s 108.1 min
UA k Tr T0
Vc p Tr T
tC ln 5290 s 88.2 min
UA k Tr T0
The complete cycle time is then found from a summation, including the time required for
filling and emptying the reactor.
1
8.9 A
R
2
Solution
a)
E2
α 2
E1
From Fig. 8.4.2.A-2, β 0.08 for x rf 0.8
From Fig. 8.4.2.A-1, u 2 .2
θ f A2
β 2
eq. (8.4.2.A-c)
θ f , A1
1 A2 1 5000
θ f, opt 1276 sec 21.3 min
β A12 0.08 49
E1
Topt eq. (8.4.2.A-e)
R ln θ f A1 u
10000 kcal/kmole
Topt
kcal (1.276 sec) (7 sec 1 )
1.987 ln
kmole K 2.2
dT
mt Cp Δ H V rA Q (8.2-1)
dθ
Q dT
ρ F cp Δ H rA
V dθ
dT
For isothermal operation, 0
dθ
1000 kg/m³
Also, C A0 8.33 kmol/m³
100 20 kg/kmol
Δ H E1 E2 10000 kcal/kmol
Q E1/RT E1/RT
Then, Δ H A1 e 1 xA A2 e x A C A0
V
10000/R (607.5) 20000/R (607.5)
(10000) (8.3) 7 e 1 xA 5000 e xA
The reaction times are found from the integrated mass balances:
1 1
x eq 1 β uα 1
1 0.08 (2.2)1 0.8503 (8.4.2.A-g)
θ x eq 1
τ ln 1 x/x eq (8.4.2.A-f)
θ f u
0.8503 1
or θ (21.3 min) ln 1 x A /0.8503
2.2
xA 0.8
B3end 4.0
1 xA 0.2
A2 E2 (5000) (20,000)
B2 1428.6
A1 E1 (7) (10,000)
E1 E 2 10,000 kcal/kmole
B1 5032.7K (8.4.2-4)
R 1.987 kcal/kmole K
B2 B3 end 5714.4 1 ok
1
Topt1 ln B2 B3
B1
Topt 581.8K at x rf 0.8
1
(800K) 1
ln (1428.6) B3
5032.7K
x Ac
and B3 0.3777
1 x Ac
and x Ac 0.274
0.274 xA 0.8 :
1 xA
Topt1 ln 1429 B 3 , B3
5033 1 xA
xA B3 Topt (°K)
0.3 0.429 784
0.4 0.667 734
0.5 1.00 693
0.6 1.50 656
0.7 2.333 620
xA
dx
θ opt C A0 (8.4.2-5)
r ( x, Topt )
x Ac A
xA
dx
E1/RTopt E 2 /RTopt
x Ac A 1e 1 xA A 2e xA
Note that
Ei E i ln B 2 B 3 Ei
exp exp B 2 B3 E1 E 2
R Topt R B1
Thus
1
xA ¡ 1 1 x¢ 1 1 x¢
2 xA
x dx
θ A1 1 x A2 x dx (408 sec) 2
x Ac B2 x B2 x x Ac 1- x
Integrating:
xA
¥ xA
θ 408 £ln 1 x A
¤ 1 xA x Ac
¨ xA
θ 408 ¦ln 1 x A 0.058 sec .
§ 1 xA
x Ac
dx A
θ
0
E1 E2
A1 exp « 1 xA A 2 exp « xA
¬ RTmax ¬ RTmax
x Ac
dx 1
ln 1 2.308 x A sec .
0
0.03x 0.013 0.03
Use Simpson’s rule to evaluate the integral.
Table 8.9-2
xA θ (sec)
opt T opt (°K)
0 0 800
0.05 4.05 800
0.1 8.71 800
0.2 20.6 800
0.274 33.3 800 From Table 1
0.3 39.4 784.1
0.4 73.6 733.7
0.5 135.2 692.8
0.6 248.2 656.2
0.7 470.8 620.4
0.8 985.4 581.8
c) To determine the heat exchange requirements, use the same heat balance as in part a)
θ kcal/s ® dT
ρ ccp Δ H γ A
V m³ dθ
dT ± ± 5032.7 ± 10065
1000 83000 ¯7 exp ¯ 1 xA 5000 exp ¯ xA
dθ ¯° ¯° Topt ¯° Topt
Figure 8.9-1
xA Topt (°K) dT/dθ (Fig. 6) -(Q/V) kcal/m³ s θ opt (sec.)
0 800 0 1077 0
0.05 800 0 953 4.05
0.1 800 0 827 8.71
0.2 800 0 576 20.6
0.274 800 -0.461 1157 33.3
0.3 784 -1.82 3353 39.4
0.4 734 -0.952 1760 73.6
0.5 693 -0.471 883 135.2
0.6 656 -0.235 445 248.2
0.7 620 -0.125 234 470.8
0.8 582 -0.05 93 985.4
Note the sudden jump in cooling requirements when the optimal decreasing
temperature profile demands cooling of the reacting mixture. The requirements are
also much more severe for the single temperature case.
Figure 8.9-2
8.10 In Example 8.4.2.B, the dimensionless equations for a parallel reaction were
derived:
1 Q (desired)
A
2 S
Solution
dx A
u β uα 1 xA
dτ
u β uα τ
1 xA e
dx Q u β uα τ
u 1 xA ue
dτ
u u β uα τ
or xQ 1 e
u β uα
dx Q
0
dτ τ 1
1 1 µ
1 u , σ ´ u β uα
u 1 α β uα 1
e σ
1
The value of u that satisfies this relation leads to the optimal temperature level.
b) For α 2, β 1/2 :
1 1 ¶ 1 2
1 σ σ
, σ u u
u 1 u e 1 2
Δ H 25000 kcal/kmol
V 1 m³ constant
C pm 0.59 kcal/kg ¹K
mt 950 kg
N A0 10.2 kmol
10000 2
ln k 5 k in m³/kmol A /s
RT
Solution
x x0 λ T T0
T0 400ºC
m t Cp 950 » 0.59
where λ 0.0022
Δ H N A0 25000 » 10.2
Hence,
dN A
rA V
dθ
dN A
θ
rA V
NA N A0 1 x C A0 V 1 x
x x
dx dx
θ C A0 C A0 3
r
x0 A x0 kC 3A0 1 x
x
dx
θ C1/2
A0 3
(2)
x0 k1 x
Changing variables in (2):
673
310000/2T -5
θ C1/2
A0 dt
400
[0.9 0.0022 (673 T)3 ]
Hence
1.427 ¼ 106
θ 2
13700 s 3.8 h .
10.2
Chapter 9
9.1. A gas phase reaction, A ½ 2R , is carried out in a tubular plug flow reactor at T =
60°C and pt = 4.75 atm. The feed consists of 50 mol% A and 50 mol% inert at a rate
of 4000 kg/h. The molecular weights of A and inert are 40 and 20, respectively, and
the rate coefficient is k = 2000 h-1. Determine the reactor size for 35% conversion of
A.
Solution
pA p
rA ¾ kC A ¾ k ¾ ky A t
RT RT
¿2 À2 x
1 x kp Ç 1 x Ä
Hence, y A Á and rA È t Å Â
2 x RT Æ 2 x Ã
x
RTFA0 2 x
or VÊ
kp t 0
1 x dx
After integration:
RTFA0
VÍ Ë 3ln 1 x x Ì
kp t
4000 200
FA0 Î Î kmol A/h
M A M inert 3
Hence:
Calculate the length of the tube to maximize the yield of B in the cases:
a) k 2 Ô k 1 /2
b) k 2 Õ k 1 .
Solution
A ÖÖ×
k1
B ÖÖ×
k2
R
ÛrA Ü k 1C A
Ø
Ø
Ø
ÚrB Ü k 2 C B k 1C A
Ø
Ø
Ø
ÙC R Ü C A0 C B C B
F0' dC A Ý rA Ω dz
Ω k1z/F0'
C A Ý C A0 e
F0' dC B Ý rB Ω dz
Ω k1z/F0'
ÝΩ k 2 C B - k 1C A0 e dz
k 1C A0 Ω k1z/F0' Ω k 2 z/F0'
ß CB Þ e e
k 2 k1
dC B
The maximum of CB/2 is found from à 0:
dz
F0' k1
zx á ln
Ω k1 k2 k2
1) 2k 2 â k 1 ã z â 0.603 m
F0'
2) k 2 å k 1 ä By the l'Hôpital’s rule, it follows: æ 0.435 m
Ω k1
Exit concentrations
1)
Ω k1z/F0'
C A ç C A0 e ç 0.0125 Kmol/m³
k 1C A0 Ω k1z/F0' Ω k 2 z/F0'
CB ç e e ç 0.025 Kmol/m³
k 2 k1
2)
C A è 0.0184 Kmol/m³
Ω z k 1Ω z/F0'
C B ëé éê k1C A0
l' Hôp.
e è 0.0184 Kmol/m³
F0'
C R è 0.0132 Kmol/m³
9.3. a) Repeat the derivations of Section 9.3-1, but for a zeroth order reaction
b) Given the data
Calculate the reactor volume and exit temperature when the reaction is of
zeroth order.
c) Compare with the volume required when the reaction is carried out
isothermally α ) at T = T0; β ) at T = (T0 + Te)/2 where Te is the exit temperature
of the adiabatic reactor.
Solution
a) Energy equation
FA0 dx Δ H ÷ mC p dT
x ÷ x0 λ T T0
mC p
λ ÷
FA0 Δ H
Continuity equation
x
v dx
ø
FA0 x 0 k
x
dx
ø
k e E/RT
x0 0
T
λ
ø ø e E/RT dT
k 0 T0
E 1 E
ù u ú dT ù u
RT u2 R
u
v λ E eu
ú ù du
FA0 k 0 R u 0 u 2
u
eu
u
ð eu ý u
eu
The integral can be solved as du þ du
u0
u2 ÿ u ûü u u0
u
0
Ei u Ei u 0
mC p 1000 0.5
b) λ 0.0025
FA0 Δ H 20 10000
x x0 1
Δ T 400K
λ 0.0025
E 9000
u 6.4
RT 2 700
E 9000
u0 15
RT0 600
λ E 0.0025
9000
3.44 10 6
k 0R 3.27 106
2
e u 6.4
FA0
20 V
6.88 10 5
E i 6.4 E i 15
u 15
1.17 m³
V x FA0 e E/RT
V x
FA0 k 0 e E/RT k0
x at T0 = 300°K : V = 20 m³
9.4. Prove that the curve x/(V/Ft0 ) , where x is the conversion, V is the total reactor
volume and Ft0 the total molar inlet flow rate of reactant plus inert diluent, is
independent of the dilution ratio for a reversible reaction where both forward and
reverse reactions are of first order only.
Solution
dx $ pB !
% r % k" p A (1)
d
V # K
F0
&1 γ &1 γ
1 x x
from which p A ' p t and p B ( pt (2)
1 γ 1 γ
1 dx k / x,
0 -1 x * pt
1 γ d V 1 γ . K+
Ft0
9.5 Derivation of a rate equation for the thermal cracking of acetone from
nonisothermal data:
When submitted to thermal cracking conditions, acetone decomposes according
to the overall reaction
It can be seen how the curves do not extrapolate through the origin. This results
from the fact that not all of the volume accounted for is at the reference
temperature considered.
(a) Use the equivalent reactor volume concept to reduce the data to
"isothermal" conditions. Use the short-cut method to estimate the
Figure 1
Acetone cracking. Conversion versus space-time diagram at 750°C. From Froment et
al. [1961a and b].
Figure 2
Acetone cracking. Short-cut method for estimation of activation energy. From
Froment et al. [1985a and b].
Figure 3
Acetone cracking. Temperature profiles for calculation of equivalent reactor volume.
From Froment et al. [1961a and b].
activation energy. Figs. 2 and 3 are given. In Fig. 2 xK and pA are plotted
versus log FA' 0 for two series of experiments, one at 750°C, the other at
710°C. Verify if the conditions for a satisfactory estimate of E are fulfilled.
Fig. 3 shows the temperature profiles, allowing to obtain the equivalent
reactor volumes. Show that, after accounting for the equivalent reactor
volumes, the curves xK versus VR/FA0 extrapolate through the origin.
(b) Use the corrected conversion versus space-time curves to derive a rate
equation. Postulate the form
rA 2 k p An
Apply the differential and integral methods of kinetic analysis (see Chapter
2) to determine the rate coefficients and order at the different
temperatures. To work out the integral method of kinetic analysis, it is
necessary to express pA as a function of xk. A rigorous expression would
only be possible if all reactions taking place were exactly known. Therefore,
undertake an empirical fit of this function.
Solution
(a) The short-cut method is used to estimate the activation energy. In Fig. 2, the two xK lines
are parallel, while although side reactions do occur, equal values of pA correspond very nearly
to equal xK. The conditions for a satisfactory estimate of E are fulfilled. The horizontal
distance between the two parallel xK lines leads to a value of 216,900 kJ/kmol. This value
looks quite plausible. E for the cracking of diethyl ether is 223,000 kJ/kmol, for dimethyl
ether 196,800 kJ/kmol.
With this value of E and the temperature profiles, the equivalent reactor volumes may
be obtained as shown in Fig. 3. The curve xK versus VR/FA0 is shown in Fig. 4. The curves
now extrapolate through the origin. With such a diagram the derivation of a rate equation may
now be undertaken.
Figure 4
Acetone cracking. Corrected conversion versus space-time curves. From Froment et al.
[1961a and -b].
rA 3 kp nA (a)
is postulated, the continuity equation for acetone reacting into ketene becomes
VR 1 x dx k
4 (b)
FA 0 k 0 p nA
The differential method is based on (a), the integral on (b).
p A 5 (1 1.05x K ) 2
Figure 5
Acetone cracking. Determination of the order of the reaction at 750°C. From Froment et al.
[1961a and -b].
Figure 6
Acetone cracking. Arrhenius diagram. From Froment et al. [1961a and -b].
Equation (b) then becomes
It follows that, when the values of xK and VR/FA0 corresponding to the different experiments
are substituted in (c) or (d), k becomes a function of n only for each experiment. The point of
intersection of the k-versus-n curves should give the value of k at the temperature considered
and the unique value of n. This is shown in Fig. 5 for 750°C. The order is found to be 1.5, also
at 730° and 710°C. This order is quite plausible on the basis of radical mechanisms for the
reaction. The values of k are given in Table 1. The Arrhenius diagram for k is shown in Fig. 6.
A value for E = 221,500 kJ/kmol is obtained, very close to that obtained by the short-
cut method, 216,900 kJ/kmol, so that no iteration is required.
The rate equation for the ketene formation from acetone may therefore be written
C 26,600 @ 1.5
rA D expA 22.780 > pA
B T ?
a
Units m3/kmol s; for first order s−1. bFrom Sundaram and Froment [1977].
TABLE 2
MATRIX OF STOICHIOMETRIC COEFFICIENTSa
a
From Sundaram and Froment [1977].
The following heat flux profile was generated from uncoupled simulations of
the heat transfer in the furnace firebox: first tube: 96 kJ/m2s; second tube: 84;
third: 80; fourth: 71; fifth: 63; seventh, eighth, ninth, and tenth tubes: 59.
Calculate the profiles of ethane conversion, temperature and pressure
(smoothed) in the coil. The ethane conversion is limited to 60 % to limit the coke
formation.
Solution
Use (9.3.2-1) to (9.3.2-7) and the equations for the pressure drop in straight tubes and in
bends given in Chapter 9. The set of equations can be integrated by means of Runge-Kutta
routines or, in case of an extreme stiff set of equations, the Gear routine [1971].
Figure 9.6-2
Ethane cracking. Product distribution versus conversion.
9.7 Consider the following data for the enzymatic hydrolysis of n-benzoyl 1-arginine
ethyl ester (BAEE) by trypsin bound to particles of porous glass in a fixed bed
reactor:
CA0 = 0.5 mM
xV/F0' min F0' G FA0 /C A0
0.438 5.90×10-2
0.590 8.03
0.670 9.58
0.687 9.46
0.910 14.72
0.972 18.00
1
a) For Michaelis-Menten kinetics, show that a plot of 1/C A0 x A ln 1 x A
versus V/FA0 x A should give a straight line, from which the constants can be
determined.
Solution
a) According to the Michaelis-Menten theory for enzymatic processes, the mechanism of the
enzymatic hydrolysis of BAEE to glass particles might be based upon the following reaction
scheme:
1 3
S+E SE P+E
2
dHSI
J k1HSIHE I k 2 HSE I
dt
dNSO
P k1NSO k 2 NEO k 2 E (1)
dt
Also,
dQPR
S k 3 QSE R S k 3 E kQER (2)
dt
On assumption of steady state conditions, (1) and (2) are equal. Hence:
k2 k3 E
TE U V (3)
k 1 TSU k 2 k 3
dWSX k 3 E WSX
Y
dt K M WSX
k2 k3
where K M Z is the Michaelis-Menten constant.
k1
k 1' C A
rA [ (4)
k '2 C A
aC A b \BAEE] b \S]
^^
where `k 1' b k 3 E
^
^_k '2 b K M
dV FA0 c dx rA
x
V k' C A0 1 x
d 2' dx
FA0 0 k 1 C A0 1 x
1
V k ' ln 1 x x
or e 2'
FA0 k 1 C A0 k 1'
Hence:
V k ' k ln 1 x 1
h x
l 2' i f '
xFA0 k 1 j xC A0 g k1
v r ln 1 x 1
o
This equation represents a straight line for vs. p m
xFA0 q xC A0 n
FA0 s C A0 F0' and C A0 s 0.5 t 10 3 kmol/m³
v
u min/kmol m³v | ln 1 x 1
y
xFA0 z w
{ xC A0 x
269.41 2631.29
272.20 3022.37
285.97 3309.44
275.40 3381.52
323.52 5292.19
370.37 7357.10
k '2
} k ' 0.0219
} 1
Linear regression yields:
} 1 208.1129
}k'
~ 1
K M 1.05 10- 4 kmol/m³ 0.105 mM
Hence:
k E 4.81 10-3 kmol/m³ min 4.81 mM/min
3
Chapter 10
10.1. Kermode and Stevens [1965] studied the reaction of ammonia and for maldehyde
to make hexamine:
4NH 3 6HCHO (CH 2 ) 6 N 4 6H 2 O
(A) (B)
The continuous flow reactor was a 490-cm3 baffled stainless steel tank stirred at
1800 rpm, with several precautions to ensure almost perfect mixing. The overall
reaction had a rate
rA kC A C B2 mol A/l s
with k = 1.42 × 103 exp(-3090/T). The reactants were fed in streams of 1.50 cm3/s,
with the ammonia concentration 4.06 mol/l and the formaldehyde concentration
6.32 mol/l. the temperature in the reactor was 36°C. Calculate CA and CB, the
concentrations in the reactor and in the effluent.
Solution
To be provided.
10.2. A perfectly mixed flow reactor is to be used to carry out the reaction A R . The
rate is given by
rA kC A kmol/m³ s
with
8000
k 4 10 6 exp 1
T(K)
s
At a temperature of 100°C and desired production rate of 0.4 kg/s, determine (a) the
reactor volume required at a conversion of 70 percent; (b) the heat exchange
requirement.
Solution
At 70% conversion:
4 10 -3 kmol
FA0 5.71 10 -3
0.7 s
Also,
FA0 5.71 10 -3 m³
F '
0 3
kmol/s 5.7 10 -3
C A0 1 kmol/m s
a) At T = 100°C = 373°K
8000
k 4 10 6 exp 1.938 10 3 s 1
373
Thus,
FA0 x A 4 § 10 3 kmol/s
V 6.88 m³
kC A0 1 x A 1 ¦ kmol £
(1.938 § 10 s ) ¤1 3 ¡ (1 0.7)
3
¥ m ¢
τ rA
0 ¨ T0 T Qr
λ C A0
Then,
and
rA 6.88 m³
τ « x A « 0.7 τ k 1 x A « 1.938 ª10 -3 s 1
1 0.7
C A0 5.7 ª10 m³/s
-3
In dimensional terms:
µ kcal ²µ m³ ²
Q ® ρ C p F0' Q r ® ³1000 °³ 5.7 ¶10 -3 ° 28¯C
´ m³¯C ±´ s ±
Q ® 160 kcal/s
The stability of the design point should also be checked, with (10.4.1-8) and (10.4.2-12):
½ UA k º 1 E kτ
1. 1 kτ »1 ¸·
» ρ c p F0' ¸ λ RT² 1 kτ necessary but not sufficient
¼ ¹
Ä UA k Á 1 E kτ
Â1 ¿
2. 1 kτ
 ρ c p F0' ¿ ¾ λ RT² 1 kτ
à W Ì BTU É kcal
U Æ 1000 Ê Í 175 Ç Æ 0.239
m²K Ë h ft² ÅF È s m² ÅK
1 E kτ 8000 2.339
Î 40 Î 1.611
λ RT² 1 kτ (373) 2 1 2.339
Ö UA k Ó 0.239 20
Ô ÑÏ Ï 0.838
Ô ρ c p F0 Ñ 1000 5.7 Ð10
' 3
Õ Ò
Then,
1
A R
2
is carried out in a constant-volume perfectly mixed flow reactor. The feed
contains only A, at a concentration of CA0, and all initial concentrations are zero.
CA 1 k 2τ k2 k 1e 1 k 1τ k 2 τ t τ
Ý e t τ
C A0 1 k 1 τ k 2 τ k1 k2 k 1 k 2 1 k 1τ k 2τ
b) Find C A /C A0 at steady state, and also show that for very rapid reactions,
k 1 , k 2 à ß , the equilibrium concentration is
CA 1 k
â Ká 1
C A0 1 K k2
t
CA 1 1
ã e τ
C A0 1 K 1 K
and explain how this can be physically interpreted as the final steady-state
equilibrium minus the equilibrium “washout”.
Solution
dC A
V ä F' C A0 CA V k 1C A k 2CR
dt
dC R
V ä F' 0 C R V k 1C A k 2CR
dt
d
τ CA C R å C A0 CA CR
dt
This standard form differential equation has the solution (with zero initial concentrations):
t
C R ç e æ e t' /æ C A0
t/ dt'
CA
0
τ
ç C A0 1 e t/æ
Then, the mass balance for species “A” becomes:
dC A
τ 1 k1τ k 2 τ C A è C A0 C A0k 2 τ 1 e t τ
dt
t
dt'
CA é e 1 k1τ k2τ t τ
e1 k1τ k 2 τ t' τ
C A0 C A0k 2 τ 1 e t' τ
0
τ
or
CA 1 k 2τ k2 k1e 1 k 1 τ k 2 τ t τ
ê e t τ
C A0 1 k1τ k 2 τ k1 k2 k1 k 2 1 k1τ k 2τ
CA 1 k 2τ
í
C A0 1 k1τ k 2 τ
CA 1
ï
C A0 1 k 1 τ
For very rapid reactions, k1τ , k 2 τ ññ 1 , the steady state result becomes
CA k2τ 1 k
ó ó ,K ò 1
C A0 k 1 τ k 2 τ 1 K k2
c) For very rapid reactions, k 1 τ , k 2 τ ôô 1 , but for finite times t/τ ~ 1.0, the last term of part a) is
very small, but the others become (as in part b)):
CA 1 1
õ e t/τ
C A0 1 K 1 K
Note that CA (t = 0) = 0, the correct initial state, but that the empty contents are “washed out”
to lead to the final ( t ì ë ) equilibrium steady state; the second term is similar to a physical
wash out.
10.4. For a first order reaction, the conversion to be expected in as series of n stirred
tanks can be formed from Fig. 10.2.2-1. Alternatively, at a given conversion level,
and for a given rate coefficient and mean residence time, kτ , the total volume
required to carry out the reaction can be determined.
a) With this basis, plot Vtotal Vplug flow versus the fraction of unreacted reactant,
1 x A , for varies values of n = 1, 2, 5, 10, 40. Study the effect of utilizing several
stirred tank reactors in series compared to a plug flow reactor.
b) Add further lines of constant values of the dimensionless group kτ total to the
plot. These are convenient for reactor design calculations.
Solution
The conversion to be expected for n-stirred tanks in series is given by (10.2.2-7); when
rearranged, this is:
ü k nV ù ö n 1 x
ú ÷
1/ n
A 1 (or utilize Fig. 10.2.2-1)
û F' ø
VPF
k ð ÿ lný 1 x A þ
F'
1/ n
nV n 1 xA 1
VPF k, F' const.
1
ln
1 xA
For example, with n = 5, at a conversion level of xA = 0.9, Fig. 10.2.2-1 gives nVk / F' 2.9 ;
Thus:
1 3
A R S
2 4
taking place in a steady state , constant-volume perfectly mixed reactor, show
that the concentration of R, when the feed contains only A at concentration CA0,
is:
k 1τ k 2τ
1
1 k 1τ Kb
CR
C A0 k 1τ 1
k 2τ
1 1 k 2τ
1 k τ Ka Kb
1
where
k1
Ka
= equilibrium constant for the first equation
k2
k
Kb 3
k4
b) For both reactions irreversible, show that the results of part (a) reduce to the
equation given in Section 10.3.
Solution
1
F' C A0 F' C A Vk1 C A C R (1)
Ka
# 1 # 1
F' C R0 $ F' C R Vk1 !! CR C A Vk 3 !! C R CS (2)
" Ka " K b
* 1 '
F' CS0 + F' CS Vk 3 (( CS C R %% (3)
) K b &
Adding:
CS . C A0 CA CR (5)
5 1 2
1 6 xA τ k1 33 x A x R 00 (6)
4 Ka 1
< 1 9 < 1 9
0 = xR τ k1 :: xR x A 77 τ k 3 :: x R 1 xA xR 7
7
(7)
; Ka 8 ; Kb 8
Solving (6)
τ k1
x A 1 τ k1 >1 xR (8)
Ka
τ k1 K τ k 3 H
I1 F
1 τ k 1 IJ K b FG
xR L (9)
K τ k1 1 HK τ k3 H
I 1FFII1 F τ k3
I1 τ k1 K a K b FG
J GJ
Then
τ k1 1
xR P (10)
1 τ k1 1 τ k 3
c) Another interesting limiting case is when k 1 , k 2 RQ, but KA is finite; then the general
equation (9) reduces to
X τ k3 U
V1 S
V K b ST
W
xR Y (11)
X 1 UX τ k3 U
V 1SSVV1 S τ k3
VK K b ST
W a TW
In this situation, reaction "a" is in quasi equilibrium, and reaction b is the rate limiting one;
this is the reactor analogue of similar situations in Chapters 1 and 2.
f 1 c
1 g xA xR τ k 3 dd x R 1 xA xR a
a
e Kb b
m 1 j m 1 mk m 1 jjj
or 1 n x R kk 1hh τ k 3 k x R k
1 x R kk 1hh hh h
k h
l Ka i l
Kb l l Ka iii
t τ k3 q
r1 o
r K b op
s
or xR u (12)
t 1 qt τ k3 q
r 1oorr1 o τ k3
rK K b op
s a ps
(12) is identical to (11), but was found without first having a general solution, (9). Thus, for a
rapid reaction in a sequence, a more direct derivation of concentrations is possible, a possible
great advantage for reactions other than first-first order.
10.6 Consider the startup of a perfectly mixed flow reactor containing a suspended solid
catalyst. For a first-order reaction, rA v kC A , and assuming constant volume, show that
the outlet concentration of reactant A is
C A (t) 1 C A (0) 1 | (1 } ε )V y Fz
~ } exp } {1 ~ k w t
C A0 | (1 } ε )V C A0 | (1 } ε )V Fz xε V
{1 ~ k {1 ~ k
Fz Fz
where
C A (0) = initial concentration
C Ai = feed concentration
ε = void fraction, not occupied by solids
εV = fluid volume
Note that the steady state (t → ∞) result depends only on the group (1 ε )Vk/F , the solid
catalyst inverse space velocity-rate coefficient group, but the transient effects also require
knowledge of (F /εV) 1 , or the fluid mean residence time.
Solution
It is assumed that the flows entering and leaving the reactor containing the catalyst slurry are
only fluid (e.g., filters); other situations would be more common, but the internal catalyst
amount (“hold-up”) need not be the same as in the feed (or product) as discussed for actual
reactors in Chap. 14, and only this simplest of cases will be considered here. The mass balance
then is, with units for each term:
dC A
V F(C AO
C A )
V (1
) kC A
dt
m 3f kmol m f kmol
3
M 3c m 3c kmol
m3 m 3
m3 m 3f s s m 3f m 3 m 3cs m 3f
εV dC A V 1 ε k
1 CA C AO
F dt F
Then,
¡¦ V 1 ¢ k F£ t
¤ 1§ t
CA F£ ¢V C A (O) t F
e ¥ e e t dt
C AO C AO V
O
C (O) 1 e t
e t A
C AO V1 k
1
F
which can be further rearranged into the text result. Again note the transient vs. steady-state
variables.
where f(V) (in m3 side feed/ h m3 reactor volume) is the distribution of side feed
additions along the reactor length (volume) to be determined. Assuming the reactor to
be plug flow, derive the following mass balances:
dF ¬
Total: « f(V)
dV
d 2
A: F ±C A ® ° C AW f V ® ¯ k 1C A C B ¯ k 2C A
dV
d
B: F ±C B ® ° ¯k 1C A C B
dV
c) As an approximate optimal design, the conditions will be used that the side feed be
adjusted to main CA = constant (i.e., CA = CAO = CAL). Also, a high conversion of A is
desired, and to simplify the calculations, it will be assumed that the side feed
concentration is high, CAW >> CA = CAO = CAL. For these special conditions, show that
the three mass balances become
F ´ µ constant ³ FO´
2
O ³ C AW f(V) ² k 1C AL C B ² k 2 C AL
dC B
F´ ³ ²k 1 C AL C B
dV
d) Using the simplified balances, determine the total reactor volume required as a
function of FO’, CA1, CBO, and CBL.
e) Show that the side feed distribution as a function of reactor length, to maintain the
above condition of constant CA, is given by:
C AL
f(V) ¸ k 2 C AL · k 1C B
O
e ¶k 1C AL V/FO'
C AW
f) As a final condition, equal stoichiometric feeds of A and B are to be used:
VL
FO ' C BO º FO ' C AO ¹ C AW f(V)dV
O
Show for this case that the relationship between the outlet levels of A and B is;
C BL
C AL ¼
k 2 C BL
1» ln
k 1 C BO
Note:
This problem was first solved by van de Vusse and Voetter (1961), who also considered
more general cases and a true mathematically optimal profile, f(V). These latter results
were rather close to the approximately optimal basis of CA = constant. Finally, such an
ideal scheme might be implemented in practice by using a series of stirred tank reactors
with intermediate feed additions of A.
Solution
CA
Thus to have a high Á, should be as small as possible, which means C B Â CA .
CB
b) A total mass balance over ÃV yields:
(F' C A ) | V Ë (F' C A ) | V Ï ÎV Ì C AW f ( V ) ÍV Ì rA ÍV Ë O
(F' C A ) | V Ï ÎV Ê(F' C A ) | V
Ë C AW f ( V ) Ì rA
ÍV
d
(F' C A ) Ë C AW f (V ) Ê k 1C A C B Ê k 2 C A 2
dV
A balance on B yields:
(F' C B ) | V Ñ (F' C B ) | V Õ ÔV Ó rB ÒV Ñ O
d
(F' C B ) Ñ rB Ñ Ð k 1C A C B
dV
c) Special restrictions:
CA = const. = CAO = CAL
CAW >> CA = CAO = CAL = small number
With these restrictions, very little side feed quantity need be added to maintain a constant
Ú CA
CA = CAL; i.e., f(V) Û FOÖ ØØ ×× FOÖ × FÖ . Therefore, the total balance becomes:
Ù C AW
V
FÝ à FO
Ý ß f (V Ý)dV Ý
O
V
FÝ f (V Ý)
ß 1Þ dV Ý Ü 1
Ý
FO Ý
FO
O
d 2
(FåC A ) ä O ä C AW f(V) ã k 1C AL C B ã k 2 C AL
dV
remembering CA = CAL = const.
d dC
(FåC B ) ä Få B ä ã k 1C AL C B
dV dV
d) Integrating the B-component balance
CB V
FOæ dC æB
é ç dV
k 1 C AL C BO C æB O
FOæ C ê
Vç ln BO è CB ç C BO e ë k1C AL V / FO
k 1 C AL CB
or
FOæ C
VL ç ln BO
k 1 C AL C BL
now,
VL VL
C AL û k1C AL V / FOú ö from
f (V)dV ù k 2 C AL ø k 1 C BO e dV ÷ ô
ô part (e)
O C AW O õ
ð
1 þ e k 1C AL VL / FO
C AL ý C BO FO
ük C V ÿ
C AW 2 AL L C AL
C AL ý k 2 C ð
C BO FO C BL
ü ð ln BO
FO ÿ 1 þ from part (d)
C
C AW ü k1 C BL C AL BO
C AL ý k 2 C BO C BO þ C BL
ð
FO ü ln ÿ
C AW k1 C BL C AL
Thus
k C C C BL
C BO FO C AL FO C AL 2 ln BO BO
FO
k1 C BL C AL
k C
C BO C AL 1 2 ln BO C BO C BL
k1 C BL
or,
k 2 C BL C
ln 1 BL
k1 C BO C AL
C BL
C AL
k C
1 2 ln BL
k1 C BO
C
R 21 BL 2 B
C BO
We need B in terms of A
A in A out B in A out C BO C AL C
A 1 AL
A in B in C BO C BO
C BL / C BO (1 ! B )
A " 1! " 1! where: (1 B ) C BL / C BO
k 2 C BL k2
1! ln 1! ln(1 ! B )
k1 C BO k1
1% $B $ % ln(1 % $ B ) (1 % $ B ) ln(1 % $ B )
$A & 1% & B & $B %
1 % ln(1 % $ B ) 1 % ln(1 % $ B ) 1 % ln(1 % $ B )
+ (C AO * C AL ) ) (k1C AL C BL ( k 2 C AL 2 )V
Mass Balance A: FO
. (C BO - C BL ) , k1C AL C BL V
Mass Balance B: FO
1 C AO 0 A / (k1C AL C BL 2 k 2 C AL 2 )V
writing in terms A : FO
of conversion B : FO 1 C BO 0 B / k1C AL C BL V
0 A C BO 5 k 2 C AL C BO 5 k 2 C AO (1 6 0 A )
taking ratio: / 31 2 / 31 2
0 B C AO 34 k1 C BL C AO 34 k1C BO (1 6 0 A )
Since C AO 7 C BO 8 k1 # k 2
:A 1< :A
9 1; = : B 2 < 2: B ; : A 9 O
:B 1< :B
A > A @ 2> B ? > B 2 PMR
Plug Flow (no side streams)
dC A
rA C C Bk1C A C B B k 2 C A 2
dt
dC B
rB C C B k1C A C B
dt
1st order linear DE
dC A k 2 C A k1 H k 2 dC C
taking ratio: E D 1 FF FFG A E A D 1
dC B k1 C B dC B C B
The solution is:
CA C C
J ln C B I const ; with B.C.@ C B K C BO , A L AO
CB C B C BO
CA C
O N ln B M 1
CB C BO
In terms of conversion
1E PA
D ln(1 E P B ) Q 1 G P A D P B E (1 E P B ) ln(1 E P B )
1E PB
Plug flow with no side streams
Summarizing:
yield of R L SR L 2R B
T A V T B U (1 U T B ) ln(1 U T B )
Perfectly Mixed Reactor
W A Y 2W B X W B 2
10.8 A perfectly mixed reactor is to be used for the hydrogenation of olefins and will be
operated isothermally. The reactor is 10 m3 in size, and the feed rate is 0.2 m3/s, with a
concentration of CA0 = 13 kmol/m3. For the conditions in the reactor, the rate expression is
CA kmol
rA \
(1 [ C A ) m 3 Z s
2
It is suspected that this nonlinear rate form, which has a maximum value, may cause
certain regions of unstable operation with multiple steady states.
a) From the reactor mass balance, determine if this is the case by plotting rA and
(1/τ 1/τ AO ] C A ) on the same graph
b) To what concentration(s) should the feed be changed to avoid this problem?
Note:
This problem was investigated by Matsuura and Kato [Chem. Eng. Sci., 22, 17 (1967)], and
general stability criteria are provided by Luss [Chem. Eng. Sci., 26, 1713 (1970)].
Solution
This can be solved for CA by plotting the LHS and RHS vs. CA –see the figure.
a) Note that there are three possible steady state solutions; again, it can be shown that the
center one is unstable; the slope of the loss of “A” by reaction-curve is steeper than the net
supply of “A” by the flow streams-line.
b) This problem can be avoided by either 1) decreasing CAO < ~ 12 kmol/m3, or 2) increasing
CAO > ~ 13.6 kmol/m3 (but at a very low conversion). Then, for the given τ and kinetics,
there will be unique steady states. (Alternatively, τ could be changed!)
A criterion that guarantees stability, for any value of τ , was provided by Luss (1970):
n d
m(C AO k C A ) ln rA (C A ) l k1
dC A S
Applying this gives CAO < 8 kmol/m3 – it seems from the figure that indeed only one
intersection is then ever possible. However, for τ = 50 s, this is a very conservative criterion (8 <
12).
Figure 10.8-1
10.9 Using the expressions for the necessary and sufficient conditions for stability of a stirred
tank chemical reactor as derived in Chapter 10,
a) Show that for a single endothermic reaction the steady state is always stable.
b) Show that for an adiabatic reactor the slope condition
p τ s trA s s dQ H p τ s trA
o1 w qq q1 v q uo q
q r dT
o C AO r tχ A r S o λ C AO r tT S
Solution:
and
Q T
with f c p / C AO (H)
Now, for endothermic rxn, Δ H > 0, λ < 0
Thus, need to determine the signs of the other parts of the expression.
rA
For most rxn, O.
T
eg., simple 1st order rA A O e
E / RT C (1 )
AO A
¢rA ¡E
A O e £ E / RT 2 C AO (1 A )
E
kC A O .
¢T RT RT 2
¦rA
Also, for most rxn, ¤O (But NOT autocatalytic forms, in Prob. 10.8!)
¦¥ A
ªrA
eg. 1st order: ¨ kC AO (§1)
ª© A
¬Q H
Also, «O
¬T
UA K
e.g., for Q H ° (T Tr )
¯ f c p FO®
QH UA K
´ ±O
²
dT ³ f c p FO
Thus,
·
¶ µ O always (except special cases)
¸
»
º ¹O
Q
¾
½ ¼ O (because of λ < O)
T
and so for any values of the parameters
À À À
¿ ¿ Á¿
à Q T
À À À
¿ ¿ Á¿
à Q T
The criteria are always satisfied.
An alternative way to illustrate this is based on the S.S. equation:
1 Ç
rA (É A , T) È [T Å TO Ä Q H (T)]
C AO Æ
The slope of the RHS is
Ð Ë dQ H ÐË UA K
Ê1Î Ñ eg. Ê1 Î
Ï dT Ï Ê Í f c p FOÌ
and is negative for λ < O (endothermic). Thus, the figure has the appearance:
It is seen that there is only one possible intersection (no multiple S.S.) for most rate
expressions, and QG-curves. However, recall the above restrictions, which mean here that
certain rate forms could have QG-curves leading to multiple S.S.
b) For adiabatic reactions, QH Ò O , and so
Õ
Ô Ó1
Q
The “slope” criterion then becomes
× × ×
Ö Ö ØÖ
Ù 1 Q T
or
Û Û
Ú ÜÚ
Ý T
If this is true, the “dynamic” criterion
Û Û
Ú Þ1 Ü Ú
Ý T
is certainly also true. Thus, for an adiabatic reactor, the “slope” criterion is necessary and
sufficient.
c) The heat removal term is given as
Q H (ß A , T ) ã Q H (T ) â á(ß A à ß A, S )
with å ä O (for ç A è ç A, S æ O , cool it)
The linearized Taylor-series expression then becomes
ñ òQ H ñ òQ H
Q H ó Q H ,S í îî y í îî ì é new term ê
ï òT S ï òì A S
ñ òQ
ó Q H,S í îî H y í ëì
ï òT S
When substituted into the linearized heat balance, it becomes
dy ö ý ù úr A ö ý ù úrA ù úQ
ý õ ÷÷ þ ð ÿ þ õ1 þ ÷÷ û ÷÷ H
dt õ üC AO ø úÿ A S õ üC AO ø úT S ø úT S r
ô
New term
Assuming solutions of the form
, y e mt /
the eqn. becomes
r A
r A
Q
m 1 r yO
C AO
A S C AO
T S
T S
Which together with the corresponding equation leads to the following determinant for n:
rA rA
m 1
C AO A S C AO T S
O
rA rA Q
m 1 r
C AO A S C AO T S T S
or m 2 a 1m a O O
with
" * % )rA " % )Q " * % )rA
a 1 - !1 ' # + !1 + # H '! #
! C AO #$ ), A S ! $ )T S ! (C AO $ )T S
" * % )rA " % )Q H " * % )rA %1
a O - !1 ' # !1 + # '! # # '&
! C AO #$ ), A S ! $ )T S ! C AO $ )T S$ (
NEW
Thus, here the “dynamic” criterion (a1 > 0) remains identical to the case with no
concentration control:
/ / /
. 1. 0.
2 Q T
However, the “slope” criterion (aO > 0) becomes:
: : :
9 9 ;9 31 8 67 4
< Q T
5
new
Therefore, the “slope” criterion becomes easier to satisfy (the R.H.S. is smaller), but this is
only a necessary condition. The overall control of the reactor may, or may not, actually be
significantly improved. This is in contrast to the temperature control strategy discussed in
the text, which always (at least in principle) can improve the control.
10.10 Show that recycling the effluent of a CSTR reactor has no effect on the conversion.
Solution:
10.11 Consider two CSTR reactors in series. For a given total volume, determine the optimal
distribution of the subvolumes for a) first order reaction; b) second order reaction.
Solution:
2
b q b
t A1 s 1 r n oo r1 n1 (4)
2V1 p 2V1
Second reactor:
V2
u A 2 x u A 1 w kC 2A (1 v u A 2 ) 2
O FA O
or
b b2 b2 2b b { b
A2 ~ 1 | } | | yy1 | (5)
2V2 V22 2V1V2 V2 4V1 z 4V1
In terms of V2 and the given volume V (V1 = V - V2):
b b2 b
A2 1 4b(V V2 ) b 2
2V2 V2 2V2 (V V2 )
2
2b 1 2b 2 Vb 2 2b 2 V2 2bV2 Vb
0 2 3 4b(V V2 ) b 2
V2 2 V2 2V2 (V V2 )
2 2
2V22 (V V2 ) 2
b2
V2 (V V2 ) 4b(V V2 ) b 2
1
*
b2 b2 b
4b(V V2 ) b 2
V22 2V2 (V V2 ) 2V2 (V V2 )
This equation should be solved numerically.
CHAPTER 11
dx kK A (p A p R p S /K)
r (1)
W (1 K A p A K R p R K S p S ) 2
d
FA 0
The reaction is carried out isothermally in a packed bed reactor with plug flow at
275°C. The feed contains 0.155 moles water per mole of reactant. Water is not
adsorbed on the catalyst and acts purely as an inert diluent. Given the following
data
ρ b = 1500 kg/m3
b) Suppose the reaction is carried out under the same conditions in a multitubular
reactor. The tube length is 3 meters. The total feed per tube is 4 kmoles/h. An
annual production of 20,000 metric tons of product is required. The molecular
weight of the product is 44. One year on stream is equivalent to 8000 hours.
Determine the number of tubes required to meet the production.
Solution
a.α . To relate the conversion x vs. W/FA0, the continuity equation (1) has to be
integrated. This requires the partial pressures to be expressed as a function of the
conversion and total pressure
R 0 x
S 0 x
x
pR = pS = pt (2)
1.155 x
2
1 x x
1 KA K R KS pt
W 1 1.155 x p t 1.155 x
d dx
1 x
2
FA0 kK A 1 x
pt p 2
1.155 x K 1.155 x
t
or
W 1 (A1 B1 x C1 x 2 )dx
FA0 kK A A 2 B2 x C2 x 2
Upon integration
W 1
(D1 D 2 D 3 ) (3)
FA0 kK A
where
A1 2C 2 x B 2 B 22 4A 2 C 2 B 2 B 22 4A 2 C 2
D1 log log
B 22 4A 2 C 2 2C 2 x B 2 B 22 4A 2 C 2 B 2 B 22 4A 2 C 2
B1 D
D2 log(A 2 B 2 x C 2 x 2 ) logA 2 B 2 1
2C 2 A1
x B B 2 2A 2 C 2 D1
D3 C1 22 [log(A 2 B 2 x C 2 x 2 ) logA 2 ] 2 x
C 2 2C 2 2C 22 A1
The desired conversion is substituted into the RHS of (3), and the corresponding W/FA0
value is calculated. The following table summarizes the results for a few values of x.
x W/FA0
_______________________________________
0.10 0.1309
0.15 0.2357
0.20 0.3812
0.25 0.5885
0.30 0.9006
0.35 1.4304
___________ _____________
0.40 2.7266
W π d 2t b
L 2.7266
FA0 4FA0
2.7266 4 4.2
Hence L = = 3.366 m
(0.05) 2 1500 1.155
a.β . Solution is not possible, since the required conversion is far beyond the equilibrium
conversion corresponding to the operating conditions.
π d 2t
Lρ b
W 4 π ¡ (0.05) 2 ¡ 3 ¡ 1500 ¡ 1.155
2.551
FA0 Ft0 4¡ 4
1.155
From a linear interpolation between the values of the last rows of the Table of Problem
11.1.a, it follows that x ¢ 0.393. Hence the production per tube amounts to:
4
£ 0.393 1.361 kmol R/h
1.155
20000000 ¤ 56.818
41.75 42 tubes.
44 ¤ 8000 ¤ 1.361
a) The relation conversion vs. reactor length is linear for a zero order reaction
without heat effect carried out in an adiabatic reactor;
b) In an adiabatic reactor the relation temperature vs. conversion is a straight line
for first order reactions only.
c) Optimization of a multibed adiabatic reactor turns out to be roughly equivalent
with distributing the catalyst in equal amounts over the different beds.
Solution
a) Correct
b) Wrong
c) Wrong
11.3
a) Consider an isothermal fixed bed reactor with axial mixing superposed on plug
flow conditions, in which an irreversible first order reaction takes place. Show that,
for a given set of operating variables, the effect of axial diffusion decreases with
increasing reactor length.
b) Given the values
Solution
d 2CA dC
εD ea 2
¥ u s A ¥ rA ρ B 0
dz dz
d 2CA dC
or 2
¦ α ’ A ¦ β ’C A 0 (first order reaction)
dz dz
us kρ B
with α ’ and β ' ; α ’ and β ’ > 0
εD ea εD ea
dC A
z 0 α ’(C A0 § C A ) §
dz
Boundary conditions:
dC A
z L 0
dz
Integration yields:
CA = Ae(α +β )z
+ Be(α –β )z
¨' 1
with ¨ ; β α ' 2 © 4β ' (1)
2 2
¬ dCA
x A(α « β )e(α ® β )L « B(α ª β )e(α β )L 0
dz z L
° ² ± 2¯ L
³B A e
±§°
´ · ¶ 2 ¸ L ¹¸ z
CA Ae ºz e ¸z · e e
¶µ´
dC A
xz = 0 2¼ C A 0 » C A »
dz
½ ¾ Á À 2Â L
2¾ C A 0 ¿ A 1 Á e
À¿¾
Ä Æ Ã 2Ç L Ä Æ Ã 2Ç L
Å AÄ 1 Æ e ÅA ÃÅ Ãe
ÃÅÄ ÃÅÄ
2ÉC A 0
A
È É Ì Ë 2ÍL È É Ì Ë 2ÍL È É Ì Ë 2Í L
2É 1 Ì e Ê É 1Ì e Ê Ë 1Ê e
ËÊÉ ËÊÉ ËÊÉ
Î ° ² ± 2¯L Î ° ² ± 2¯L
Denominator: ° 1 ² e § ± 1² e
±§° ±§°
° ± § ° ² ° ° ² ± e 2¯ L § ± ± § ° ² ± ° ² ± e 2 ¯ L
1
±§°
Ï Ò Ñ 2 e 2Ó L Ð Ñ Ð Ï
1 2
ÑÐÏ
2ÕC A 0 × Ö Õ e Üz Ô Ú z Õ Ø × 2 Ú L ÛÚ z
Ù CA e Ø e e
ÕØ× e Ú Ö ×ÖÕ
2 2 L 2
×ÖÕ
It follows from this formula that C A(z) is only a function of the reactor length L if all
other operating variables are fixed (including particle size). Differentiation with respect
to L yields:
dC A 2ÞC A 0 (à ß Þ)e åz â (Þ á à) 2 â 2à e 2ãL Ý ãz Þ á à 2ãL äãz
ß e á e e
(Þ á à) 2 e 2ãL ß (à ß Þ ) 2 àßÞ
2
dL
2éC A 0 (ë ê é)e èz é ì ë 2 æ L çæ z
ì 2 2æ L
í 2ë e e
(é ì ë) e ê (ë ê é) 2
ëêé
2ÞC A 0 (à ß Þ )e åz 2(Þ á à)
ß 2à(Þ á à) 2 e ãz e 2ãL ß 2à(Þ á à) e 4ã L e ä ã z
(Þ á à) e ã ß (à ß Þ ) 2 àßÞ
2 2 L 2
ñ ò î 2óL ôóz
ò 2ñ e e ((î ò ñ) 2 e 2óL ï (ñ ï î) 2 )
ñïî
2øC A 0 (ú ù ø )e ÷z e 2õL
ù 2ú(ø û ú) 2 e õz ù 2ú(ú û ø )(ú ù ø)e öõz
(ø û ú) e õ ù (ú ù ø ) 2
2 2 L 2
ß 4Þà C A 0 (à 2 ß Þ 2 )e åz e 2ãL
(Þ á à)e ãz á (à ß Þ )e äãz
2 2ã L 2 2
(Þ á à) e ß (à ß Þ )
It is easily seen that this expression has always a negative value (see also (1): β > α ).
This means that increasing the reactor length tends to decrease the concentration of A
(in other words: increase the conversion) in each point of the reactor and thus diminishes
the influence of axial mixing.
c) In this case it is sufficient because the difference between the CA/CA values calculated
with the two models is only of the order of 8.55 % at 10 dp, and of the order of 0.35 %
at 50 dp.
11.4 Calculate the heat transfer parameters of the two dimensional pseudo
homogeneous models for the design of the reactor for hydrocarbon oxidation of
Section 11.7.3, using the correlations given in Section 11.7.1. Compare the values of
0
λ er calculated from the expressions given by a) Kunii and Smith and b) Zehner and
Schlünder. Determine their sensitivity with respect to the solid conductivity.
Additional data: λ s = 1 kcal/m.h.°C = 1.163.10-3 kJ/m s °K
λ g = 0.0429 kcal/m h °C = 4.99 10-5 kJ/m s °K
P = 0.8
β = 0.95
dp = 0.003 m
dt = 0.0254 m
Tm = 382°C
ε = 0.38
Solution
1) Static contribution ü er
Kunii and Smith:
ð
3
0.1952 þ 655 kcal
m 2 ýC h
rv
0.38 .2 100
1ÿ
2.0.64 .8
= 0.1813 × 218.0114
= 50.95
rs 0.1952
.8 655
3
1.2 100
= 36.56
0.216
2 1
0.26
2
0.043
s 1
as 23.3 0.08
g 2 0.125
1 d (1 )
0
er rv p
1
1 d
g g
p
rs g
g s
50.95 0.003
0.95 0.62
2 03.0429
0.38 1 .95
0.0429 1
1
0.003 36.56
0.08 0.0429
= 1.6662 + 6.199
= 7.8652
0
er 0.3374 kcal/m °C h
1 10 / 9
B 2 .5
4.307
) 25..4307
007
(2.557 ( 4.307)
-
0
* + , + 1 + (2.55662.* 4.62.307)0.0429
-
er
(1 .62 )(1 0.38 2.557)
g
/
0.2126 1.9717 8.4702 . 8.8894
0 0
0
er
0.3814 kcal/m °C h
g
2) Dynamic contribution 1 er
3 2 Re Pr
t
3
er
6 .14
1 5 46
4 dp 2
dt
7 0.0853
9t
er
0.0853 121 0.6918 8
g
; 0.0429 : 7.1301
t
er 0.3059
Wall coefficient:
Scatters: 8 D F E d D 20
W P
H W
G
8 0.0429
114.4
0.003
K J 20 I0.0003
W
.0429
= 286.0
or 114.4 ≤ α W ≤ 286.0 NM W L
134 kcal / m 2 h C
(article)
but De Wasch & Froment
α W P O 0.0115
0
W
d
d
Re t
R Q 11.781 mkcalh SC
0
W 2
if T 0
W 70
V 81.8 mkcalh UC
0
W 2
1
hw
1
X
Y 8W
d t
w er
1
hw 80.66 (K & S)
1
134
[ Z 0.0254
8 0.6433
1
hw 82.77 (Z & S)
[ Z 1
134
0.0254
8 0.6873
Sensitivity of \ for ] 0
er s (K & S)
] = .8 Kcal/m∙ h°C
^
s
18.65 ` _
^
s
1 0.048
ba
g
0.084
c 2 0.13
d 0
f e
50.95 0.003
f e
0.95 0.62
d f ee
er
0.38(1 .95 )
0.0429 1 2 0.0429
g
1
f e
0.003 36.56 3 0.8
0.084 0.0429
= 1.6662 + 5.615
= 7.281
i
0
0.3124 kcal / m C h h g 20 % decrease of ]
7.4 % decrease of \
er s
0
l kj
er
1.2 kcal / m h C
^
s
^
s
24.4 nm 1 0.041
ba
g
0.076
c 2 0.13
o 0
q p
0.95 0.62
o q pp
er
1.6662
1 2 0.0429
g
1
q p
0.003 36.56 3 1.2
0.076 0.0429
= 1.6662 + 6.7278
= 8.394
r 0
0.3601 kcal / m C h t s 20 % decrease of u
6.7 % decrease of v
er s
0
er
Sensitivity of v0
er for u s
u = .8
s
B = 4.307
xd
w
rs p
2.557
p
4.666
0.8211
ln 4.9234 3.6495 1.0782
9.0590 3.645 1.0782
4.3314
0
2 .62
er
1 .62 1 0.38 2.557
g 1 2.557 4.307 0.0429
.8
= 0.4192 + 7.5275
= 7.9467
0
0.3409 kcal / m C h 20 % decrease of u
v
er s
0
results in 10.62 % decrease of er
s 1.2 Kcal / m h C
1 2.557 1 0.10429 4.307
1 2.557
0.0429
.2
ln 1 .2 3.307
5.1739 ln 7.0882 3.5277 1.0782
10.1327 3.5277 1.0782 5.5268
0
2 .93.62
er
0.4192 0.4192 9.2845 9.7037
g ...
0
0.4163 kcal / m C h 20 % increase of results in
er s
0
9.15 % increase of er
11.5 Check whether multiple steady states can occur in the case of the case of the
hydrocarbon oxidation of Section 11.7.3, but considering only the reaction A → B.
Required data:
Tf = 655°K
De = 5 10-4 m2/h
Solution
E
RTf
27000
1.987 655
20.75
¥ (¤£¢H)TD C ¡ ¡
307000 5 10 4 0.4145 10 3
e f 5
9.7 10
s f 1 655
so that β γ = 0.002, which is less than 1 and less than 4(1 + β ) = 4.0004. Hence, only
one steady state is possible.
11.6 A tubular, fixed bed catalytic reactor is to be used for a highly exothermic
reaction, and the preliminary design must consider the possibility of a hot spot.
The following parameters have been established in the initial design estimates:
§ ¦TT as 600
400
1.5 dimensionless adiabatic temperature rise
Re f
ª RTE 32000
2 400 © ¨
40 dimensionless activation energy
ref
k BC A0 V
3 reaction rate group or the number of reactor units
FA 0
UA
«
F' c p
22.5 number of heat transfer units
a) Will there be an excessive hot spot for the set of parameters given in the preliminary
design ?
b) An obvious (if expensive) way to overcome a hot spot problem is to add diluent to
the reactor feed. What must the dilution be to achieve a design 10 percent safer than
the hot spot minimum dilution ?
c) Indicate how the two parameters of the hot spot analysis are altered by the following
design choices:
d) The reactor designed in part (b) is expected to undergo two changes during extended
operation: the catalyst activity will decrease by 30 percent and the heat transfer
coefficient will decrease by 20 percent. The loss in catalyst activity will be
compensated by raising the reactor temperature enough to keep kB constant.
Investigate the probability of developing a hot spot in the reactor under the revised
conditions.
Solution
a) These values of (S, N/S) are far into the “Runaway” region.
´T ( µ ´H ) C
³C
A0
ad
g P
Thus, the parameter S will decrease, N will remain ~ constant, and N/S will
increase:
S new
60
6.0,
¶N 10(0.125) 1.25
10 S new
·T
ad const.
S new S
¸ T0
2
5.5
¸ 400 2
5.8
T0,new 390
k v ,new
kV
exp ¹ 16000¸ 390
1
¹ 400
1
0.359
º» T 400
»
0 , new
1.0256
0 gas
Tnew 390
7.5
N new 20.37
(1.0256)(0.359)
S = const. = 5.5
N new N
¼ Rt 7 .5
9.38
R t ,new 0 .8
3. No effect.
cal
4. Lower activation energy by 40 %: Enew = 19200.
gmol
S new S
½E new
5.5 (0.6) 3.3
E
If rate constant kr0 unchanged, N = const. = 7.5
Less sensitive.
Find
T0,new = 403.6
As in part (c.1)
S new S
¾ T0
2
5.5
¾ 400 2
5.40
T0,new 403.6
(a) Introduction
Styrene is produced by catalytic dehydrogenation of ethylbenzene on an iron catalyst. The
reaction is endothermic and reversible and takes place with an increase in the number of mole.
Consequently, styrene conversion is favored by high temperatures, low pressures, and dilution
of the feed by means of an inert component, such as benzene or, more generally, steam. The
steam also serves as a heat carrier, reducing the temperature drop in adiabatic operation.
(b) Reactor
Operating conditions
Molar feed rates:
Ethylbenzene: 707 kmol/h
Styrene: 7.104 kmol/h
Benzene: 0.293 kmol/h
Toluene: 4.968 kmol/h
Steam: 7777 kmol/h
Inlet temperature of the mixture: T0 = 620°C
Inlet pressure: 2.37 bar
Reactor dimensions
Inner diameter: 7 m
0
( W / FEB ) total = 62 kg cat. h/kmol
Additional data
Catalyst equivalent diameter: dp = 0.0055 m
Catalyst internal void fraction: ε s = 0.4
Tortuosity of the catalyst: τ = 3
Catalyst density: ρ s = 2500 kg/m3 cat.
Void fraction of the bed: ε B = 0.4312
Bulk density of the catalyst bed: ρ B = 1422 kg/m³
(c) Kinetics
The main reaction is:
The following rate expressions were proposed for the above catalytic (rcj) and thermal (rtj)
reactions [Lee, W.J., Froment, G.F., Ind. Eng. Chem. Res., 47, 9183 (2008)]:
Á p Kp
k 1 K EB p EB ST H2
eq
rc1
À
1 K EB p EB ÀK p ÀK H2 H2 ST p ST
2
k 2 K EB p EB
rc 2
Â
1 K EB p EB ÂK H2 p H2 ÂK ST p ST
2
k 3 K EB p EB K H 2 p H 2
rc3
Ã
1 K EB p EB ÃK H2 p H2 ÃK ST p ST
2
k 4 K ST p ST K H 2 p H 2
rc 4
 ÂK
1 K EB p EB H2 p H2 ÂK ST p ST
2
rt1
Ä p p
k p Å ST H2
t1 EB
K eq
rt 2 k t 2 p EB
rt 3 k t 3 p EB
where
ki A i exp
ÆÇ E i
RT
k ti A ti exp
ÈÉ E ti
RT
Kj A j exp
Ê Ì ËH j
RT
The rate parameters are given in Table 1, the thermodynamic parameters in Table 2.
TABLE 1
RATE PARAMETERS
TABLE 2
THERMODYNAMIC PARAMETERS
K exp
Í Ï ÎG o
RT
and
K eq Ñ
K (P o ) Ð
where Po is the standard state pressure (1 bar) and Ó i
Ò , with α
i i the stoichiometric
coefficients.
ÔG Ô H Õ TÔS
o o o
with
ÖH Ö H o o
298.15 × T
298.15
ÖC dT o
p
ØS ØS o o
298.15 Ù T
298.15
ØC o
p
dT
T
The heat capacities are calculated in the form of cubic functions of T.
C pj aj Úb TÚc T Úd T
j j
2
j
3
The coefficients are given in Table 3 [Reid, R.C., Prausnitz, J.M., and Sherwood, T.K., The
Properties of Gases and Liquids, 3rd ed., McGraw Hill, New York (1977)].
TABLE 3
COEFFICIENTS IN THE CUBIC HEAT CAPACITY EQUATION AND STANDARD
HEATS AND GIBBS FREE ENERGIES OF FORMATION
The mixture viscosity can be calculated using Wilke's approximation. The viscosities of
ethylbenzene, styrene, benzene, and toluene can be calculated using the corresponding-states
method of Thodos [Perry, R.H., Green, D.W., Perry's Chemical Engineers' Handbook, 7th ed.,
McGraw-Hill (1997)]. The viscosities of hydrogen and steam can be calculated using the
Chapman-Enskog equation.
The inert steam being largely present, Wilke's equation can be used for the calculation of the
diffusion coefficients of the different species in the gas mixture. The binary diffusion
coefficients can be calculated from the atomic diffusion volumes, according to:
0.00143 T 1.75
D AB
PM 1AB2 [( Û Ü Û)
)1A3 ( 13
B ]
(f) Simulation
Simulate the profiles of conversion into styrene, benzene, and toluene, and the temperature and
pressure profiles in the reactor.
Solution
Conversion of ethylbenzene: x EB
0
FEB FEB Ý
0
FEB
dx ST
0
d ( W / FEB )
è r é è r ç r æ äå
1 c1 4 c4 t1
B
(b)
b
dx BZ
0
d ( W / FEB )
î r í r ì êë
2 c2 t2
B
(c)
b
dx H 2
d ( W / FEB0
)
õ r ó õ r ó 2õ r ô (r ó r ) ò ïñ
1 c1 3 c3 4 c4 t1 t3
B
(d)
b
The other conversions, xTO, xCH4, and xC2H4 can be solved from algebraic equations which are found by
combining (a) to (d):
x TO x EB öx öx
ST BZ
x CH 4 x TO and x C2H 4 x BZ
ýüH ) ÷ û r ú r øù
6 4
dT 0 B
m j c pj 0
FEB ( ri i ci ti
j 1 d ( W / FEB ) i 1 B
with j: EB, ST, BZ, TO, H2, and H2O. Because of their limited concentrations in the reactor, CH4 and
C2H4 are neglected.
The mass flow rates of the different components can be expressed in terms of the corresponding
conversions:
For EB: m EB 0
M EB FEB (1 x EB ) þ
For the other species j: m j M j (Fj0 ÿF 0
EB x j)
TABLE 4
MOLAR MASS
The heats of reaction i can be calculated from:
bi 2
H ri H 0298 a i T ð 298.15 T ð 298.15 2
2
ci 3 di 4
T ð 298.15 3 T ð 298.15 4
3 4
The required data are shown in Table 5.
TABLE 5
DATA FOR THE CALCULATION OF THE HEATS OF REACTION
1 B 1 B
f ab
3
B Re
1
k Mj
jk 12
Mj
8 1
Mk
The viscosities of EB, ST, BZ, and TO are calculated from the corresponding-states method from
Thodos:
Tc1 6 M 1 2 Pc 2 3
T
Tr
Tc
in P
M in kg/kmol, Pc in atm, and T and Tc in K.
MT
26.69
2
with σ the hard sphere diameter in Å, the collision integral, and μ in μ P.
A
C exp(DT*) E exp( FT*)
T *B
where
!
T* T
0.2" 2
(Stockmayer) (Lennard $ Jones) #
T*
The values of the required properties are listed in Tables 6 and 7.
TABLE 6
PROPERTIES FOR THE CALCULATION OF THE VISCOSITY FOR EB, ST, BZ, AND TO
TABLE 7
PROPERTIES FOR THE CALCULATION OF THE VISCOSITY FOR H2 AND H2O
Effectiveness factors
The effectiveness factors can be calculated from
1 d . 2 dPs ,EB RT
r )- s rc1 + rc 2 + rc3 + , s rt1 + rt 2 + rt 3 *
r 2 dr dr D e,EB
1 d 5 2 dPs ,ST RT
r 3 /4 s rc1 3 rc 4 2 1 s rt1 0
r 2 dr dr D e,ST
1 d C 2 dPs ,TO RT
r B =A s rc3 @ rc 4 @ ? s rt 4 >
r 2 dr dr D e,TO
1 d J 2 dPs ,H 2 RT
r F DI s rc1 F rc3 F 2rc 4 H G s rt1 F rt 3 E
r 2 dr dr D e,H 2
1 d Q 2 dPs ,CH 4 RT
r P KO s rc3 N rc 4 N M s rt 4 L
r 2 dr dr D e,CH 4
1 d X 2 dPs ,C 2 H 4 RT
r W RV s rc 2 U T s rt 2 S
r 2 dr dr D e ,C 2 H 4
p s,H 2O (r ) p H 2 O (const.)
The presence of inert steam allows the use of Wilke's equation for diffusion through stagnant
components for the calculation of the diffusion coefficients of the species in the gas mixture:
N
1 1 yk
D jm 1Y yj k 1 D jk
The binary diffusion coefficients can be calculated from the atomic diffusion volumes according to:
0.00143 T 1.75
D AB
PM 1AB2 [( Z )1A3 [ ( Z)1B3 ]
with
DAB in cm2/s
T in K
\1
1 1
M AB 2 ]
MA MB
MA and MB in kg/kmol
^ j
is calculated by summing the atomic diffusion volumes.
The properties required for the calculation of the binary diffusion coefficients are listed in Table 8.
TABLE 8
PROPERTIES FOR THE CALCULATION OF THE BINARY DIFFUSION COEFFICIENTS
` s D jm
D e, j
_
Integrate numerically.
Figures 11.7-1 and 11.7-2 show the different conversion profiles, the temperature and pressure
0
profiles, and the profiles of the effectiveness factors as a function of ( W / FEB ).
The parametric sensitivity for the inlet temperature and concentration can be verified.
Figure 11.7-1
Ethylbenzene dehydrogenation into styrene. Conversion versus (W/FEB0) profiles.
Figure 11.7-2
Ethylbenzene dehydrogenation into styrene. Profiles of the temperature, pressure, and effectiveness
factors as a function of (W/FEB0).
11.8 Determine the units of the rate coefficients k1, k2, k3, and of the adsorption coefficients in
the rate equations of Example 11.9.1.A, Table 11.9.1.A-2.
Solution
To be provided.
11.9 (a) Repeat the calculation of the primary methane steam reformer presented in Example
11.9.1.A. Assume constant effectiveness factors based on the calculations shown in Figure
11.9.1.A-7.
(b) Repeat the calculation as in (a), but using the 2-dimensional reactor model of Section
11.10. Verify the radial temperature uniformity in the reactor.
Solution
To be provided.
CHAPTER 12
12.1 (a) Starting from the Navier-Stokes equations (12.3-1)-(12.3-5), derive the Reynolds-
averaged Navier-Stokes equations.
(b) Calculate the Reynolds-averaged reaction rate for a second-order reaction: r =
kCACB. Consider the extreme cases of no and complete micro-mixing.
Solution
To be provided.
Solution
Figure 12.2-1
Cold-shot cooling in a fixed bed ammonia synthesis reactor. Quench zone geometry and grid. In blue: different
inlets; in red: outlet.
Verify the grid independency of the simulation results by repeating the calculations on a finer
grid.
Simulation model
Use the Reynolds-averaged Navier-Stokes equations. Account for the effects of turbulence via
the turbulent viscosity and conductivity and using the standard k-ε model and wall functions.
Boundary conditions
Depending on the CFD solver used, the inlet mass flow rates can be directly imposed or an inlet
velocity has to be calculated and imposed.
For a constant gas density of 50 kg/m3, the inlet velocity at the top of the quench zone, that is, at
the exit of the first bed, can be calculated to be 0.18 m/s. The cold-shot inlet velocities can be
calculated to be 1 m/s.
Simulation results
Figure 12.2-2 shows the temperature profile in an axial cross section through 3 of the cold-shot
tubes. The temperature is seen to become quite uniform when approaching the exit of the quench
zone, that is, the inlet of the second bed. A more detailed picture of a radial cross section at the
inlet of the second bed is given in Fig. 12.2-3. Two radial temperature profiles at the exit of the
quench zone are shown in Fig. 12.2-4. The maximum temperature difference at the inlet of the
second bed is seen to amount to 5°C.
Figure 12.2-2
Cold-shot cooling in a fixed bed ammonia synthesis reactor. Quench zone. Temperature profile in an axial cross
section through 3 of the cold-shot tubes.
Figure 12.2-3
Cold-shot cooling in a fixed bed ammonia synthesis reactor. Quench zone. Temperature profile in a radial cross
section at the exit of the quench zone (inlet second bed).
Figure 12.2-4
Cold-shot cooling in a fixed bed ammonia synthesis reactor. Quench zone. Radial temperature profiles at the exit of
the quench zone (inlet second bed). Red curve: below a line of 3 cold-shot tubes; Black curve: line rotated 45° with
respect to the line corresponding to the red curve.
The uniformity in the velocity field can also be studied. Figure 12.1-5 and -6 show respectively a
vector plot of the velocity in an axial cross section through 3 of the cold-shot inlet tubes colored
by the velocity magnitude and a radial profile of the velocity magnitude at the exit of the quench
zone (inlet of the second bed). Some non-uniformity in the velocity profile is observed. The
latter will be reduced when entering the second bed.
Figure 12.2-5
Cold-shot cooling in a fixed bed ammonia synthesis reactor. Quench zone. Velocity vector profile colored by the
velocity magnitude in an axial cross section through 3 of the cold-shot tubes.
Figure 12.2-6
Cold-shot cooling in a fixed bed ammonia synthesis reactor. Quench zone. Velocity magnitude profile in a radial
cross section at the exit of the quench zone (inlet second bed).
where a fraction α of the flow passes through the second tank V2.
a) For an impulse function input to tank V1, derive the RTD for the complete system that would
be measured at C(t).
V2
ba
V1 V2
The overall RTD becomes as for a single, perfectly mixed region!
Note that this example illustrates that overall perfect mixing, as measured by RTD, need not mean that the
specific details of the flow system are a simple perfect mixer. Further discussion is provided by T.
Fitzgerald, Chem. Eng. Sci., 29, 1019 (1974).
Solution:
C( t ) d (1 c)C1 ( t ) cC 2 ( t )
The mass balances for C1 and C2 are:
dC1
V1 g M 0 h( t ) FeC1
dt
dC 2
V2 g fFeC1 fFeC 2
dt
M 0 Fit / V
C1 j e 1
V1
Then
mFl mFl M o
e Fkt / V1
dC 2
C2 n
dt V2 V2 V1
and
0
V2 V1
q M0 1 o pFot / V
r e F t / V1
e 2
V2 V1 q 1
V2 V1
Finally
y v
M w z t
C( t ) { 0 w(1 z )e F|t / V1 e F |t / V1 }F|t / V2
1
e t
V1 w V2 1 1 t
wx V2 zV1 tu
V2 V1
b) For the special case ~ ,1
V1 V2 V1 V2
M 0 V1
e Ft / V1 e Ft / V1 e Ft /( V1 V2 )
V1
C( t )
V1 V1 V2 V1 V2
e Ft /( V1 V2 )
M0
V1 V2
This is the RTD for a perfectly mixed reactor with total volume (V1+V2)!
12.4 Find the mean and variance for the RTD of Fig. 12.6.4.A-1.
Solution:
1 )e ( 1 ) / 2
1
The RTD is: E () U (
2
Then the moments about the origin are:
1 e /
( ) /
1/ 2
0 U( 1 )e d 1 2
e d 2
0 2
2 0
e
1
2
2
e / e 2 /
1
1/ 2 1/ 2
1 e d 2
2e 2
1
2 1
2
2
1 2 (total sum of for each reactor)
e e 3 / 2
1
2 /
1/ 2 1/ 2
2 e d 2
2e 2 2 2
2
2 1
2 2 2
2
1 212 222
2 2 12 2 22
Thus, the total variance for the system is that of the perfectly mixed reactor alone; this is because the plug
flow reactor response has 12 0 . The more general situation is given in Chapter 12.
12.5 Derive equations (12.6.4.B-d), (12.6.4.B-e), and (12.6.4.B-f). It might be helpful to first derive
the first-order reactions results.
Solution:
The results for plug flow (PF) and perfectly mixed (PM) reactors are:
¡ e k 1
CA CA
PF £ (1 kC AO ¢1 ) 1
C AO C AO
(Table Chapter 1)
CA 1 CA 1 4kC AO ¦ 2
PM ¥ §
C AO 1 k¤ 2 C AO 2kC AO ¦ 2
PF +PM PM+PF
¡ e k 1
C A1 C A1 1
¥
C AO C AO 1 k¤ 2
« e kª1
CA 1 CA
©
C A1 1 k¨ 2 C A1
CA C A C A1 e ¯
k 1
CA e ±
k 1
® ¡ ¡ (b) ° ¥ (b)
C AO C A1 C AO 1 k¬ 2 CAO 1 k¤ 2
PF+PM
CA1 1
³
CAO 1 kCAO²1
CA 1 1 4kCA1² 2
³
CA1 2kCA1² 2
CA 1 1 4kCAO² 2 (1 kCAO²1 ) 1
´ ³
CAO 2kCAO²2
PM+PF
CA1 1 1 4kCAOµ2
¶
CAO 2kCAOµ2
CA 1
¶
CA1 1 kCA1µ1
CA 1 1 4kCAO µ2
· ¶
CAO 2kCAOµ2 kCAOµ1 1 1 4kCAOµ2
If the total volume V = V1+V2 and the ratio V1/V2 are imposed, what should be the ratio of the
volumes V1/V2 in the second configuration to obtain the same exit conversion, XA2 for a first order
reaction? For a second order reaction?
Solution:
1.
kC A V1
O
Hence,
FA
O
xA
1
º1 e
or
C A V1
x A1 ¼ 1 e k» 1
, where ¾1 ½ O
FA
O
V2
xA
2
¸ rA xA
1
FA
O
1 e k¿1
V2
¸ kC A O (1 x A 2 )
FA
O
e kÂ1
or xA Á 1
2 1 kÀ 2
C A V2
where Ä2 Ã O
FA
O
1
Hence, x A È1
1 kC A
O
Ç1
or
1 Ð 4kÑ 2 C A Í
xA Ò1 Î1 1 Ë 0
(2)
2 2kÑ 2 C A Î 1 kC A Ñ1 Ë
0 Ï 0 Ì
2.
V2Ô
x ÔA Õ rA
1 FA
0
kÖ×2
or x ×A Ø rA
1 1 kÖ×2
FA O dxÙA1 Ú rA dV1Ù
dx ÛA dV1Û
Ü CA k
10 x ÛA FA 0
0
1 xàA1
Hence ß e kÝÞ 1
1 xàA1
After substitution of x áA
1
e åæ
k
xãA 2
1
ä1 (3)
1 kâã2
b) Second order reaction:
V2è
x èA é rA
1 FA
0
x êA ë k (1 x êA1 ) 2 C 2A V2ê / FA 0
1 0
1
or x íA î1 1 4kìí2 C A 1
1 kìí2 C A 0
0
dxïA1 dV1ï
ñ
kC 1 xïA
2 2
A0
FA 0
Hence
ú 1 1 ÷
ø õ ô kC A 0 ò1ó
øù1 x óA1 1 x óA 2 õö
1 1 4kC A 0 ûè2
xèA 2 é1 (4)
2kC A 0 ûè2 kC A 0 û1è 1 1 4kC A 0 ûè2
Equations (1) and (3) are identical so that the ratio V1/V2 must be the same in both configurations to
obtain the same exit conversion for a first order reaction.
For the second order reaction, equating the RHS’s of (2) and (4) yields
1 4ýV2 1 1 4ýV2ü C 2A
1 1 ÿ þ1 ; k 0
(5)
2ýV2 1 ýV1 ð 2ýV2ü ýV1ü 1 1 4ýV2ü FA
0
This relation is now written as a function of the total volume V and the ratio of the volumes V 1/V2 =,
respectively V’1/V’2 =’. Therefore the set of equations (6) is first solved for V1 and V2.
V
V V1 V2 V1
1
V1 (6) → (7)
V
V V2
2 1
and similarly for the second configuration. Substituting (7) into (5) yields
4 V 1
(1 ) 1 1
1 V 1
1 4V 2
1
1
or
1 A
!" 2
A 2 V(A 2) A
12.7 Calculate the effect of recycle upon the conversion in tubular reactors with plug flow.
Solution:
rA dV $ (1 # ) FA dx A
0
(1 x A ) n kC nA dV & (1 % ) FA dx A
0 0
dx A kC nA
0
( dV
(1 x A )n (1 ' ) FA
0
xA
VkC nA 2
dx A
0
) (1)
(1 * ) FA
0 xA
(1 x A ) n
1
+x A FA FA x A , (1 +) x A FA
2 0 0 0 1 0
-x A
2
Hence, x A . (2)
1 1 -
Vk xA
2
From (1): 0 xA xA 0
(1 / )FA 2 1 1 /
0
Vk
xA 1
2 FA
0
x A1
VkC 2A 0 dx A 1 xA2 1 x A1
From (1): 2 2 ln 2 ln (4)
(1 3 ) FA x A2
(1 x A ) 1 x A1 1 xA2
0
or
VkC A 1
0
=
FA 1 <
e 0
xA ;1 (5)
2 9 VkC A 1 6
0
7 =
FA 1 <4
1 : 71 e 0 4
7 4
7 4
8 5
VkC A
0
FA
1) α → 0 xA >1 e 0
2
This is indeed the equation for the tubular reactor with plug flow.
VkC A / FA
0 0
2) α → ∞ xA ?
2 1 VkC A / FA
0 0
This is indeed the equation for the perfectly mixed continuous reactor.
12.8 Suppose a reactor system consists of many piston flow reactors in parallel:
From Chapter 9 (or 1), the exit concentration in any one of them is, with a first-order reaction,
C A ( L) AkL / F @
B e
C A0
R 1
Pa 1M LR H LE
f ( L) Q N K exp F (I 1)
O L L J (I 1) G L CD
x
where L S mean length S Lf (L)dL (check this)
0
x
C C A ( L)
^ f (L)dL
CA0 C A0
0
(T 1)
Z L \k W
^ XX1 U
Y ] 1 F[ UV
b) For the special case of α = 0, the exponential distribution, the result of part (a) becomes
1
C d Lfk a
g bb1 _
CA0 c Fe _`
which is the result for a single perfectly mixed reactor (Chapter 10). Discuss this result in view of
reactor flow models.
Solution:
h i 1
C kkL / F j w x 1t Li q Ln
| e u r exp o (x 1) dL
CA0 v L s { (x 1) p L lm
0
i 1 h
wx 1t 1 q w zk x 1 tn
|u r Li exp o u r l dL
v L s { (x 1) p v Fy L sm
0
}
(z) ~ e ax a z x z 1dx
0
k 1
Identifying x ↔ L, z ↔ α +1, a ↔ , the integral is evaluated as
F
1 ( 1)
C 1 1 k 1
( 1)
CA 0 L ( 1) F L
( 1)
L k
1
1 F
1 1
C Lk Vk
1 1
CA0 F F
This result, that for a perfectly mixed reactor, is because the distribution average is identical to
segregated flow with an exponential distribution of residence times; the two are identical for first
order reactions.
12.9 Derive (12.7.2-11) and plot a few curves for various values of the parameters.
Solution:
1 d 2C dC
k¡C 0 (1)
Pe a dz 2 dx
1 dC
1 ¢ C( O ) (O ) (2)
Pe a dx
dC
(1 ) £ 0 (3)
dx
P P
(1 a ) z (1 a ) z
C ¤ Ae 2 Be 2 (4)
with
a ¦ 1 4k¥ / Pe a
Now
1 1
dC Pe a (1 a ) z Pe (1 a ) z
¤A (1 a )e 2 B a (1 a )e 2 (5)
dz 2 2
B 1 a Pe a a
§ e (6)
a 1 a
1
1 a Pe a a 1 a ª
A ® 1
«
e 1 e Pe a a ¨
¬ 1 a 2 ©
Pe a P
(1 a ) z 1 a Pe a 2 (1 a ) z
e 2 e e
C¤ 1 a (7)
1 a (1 a ) 2 Pe a a
e
2 2(1 a )
2a Pe a / 2 Pe a a / 2
e e
1 a
12.10 Show that for an axial dispersion flow system with variable density, area, velocity, and
dispersion coefficients between two adjacent sections, equating total fluxes leads to the boundary
condition.
µ C1 ² d µ C1 ² µ C 2 ² d µ C2 ²
³ ° D1 ³ °·³ ° D ³ °
³¶ ° dz ³´ ¶1 °± ³´ ¶ 2 °± 2
dz ³´ ¶ 2 °±
´ 1 ±
Solution:
The proper balance at a boundary surface between two regions is based on the mass (moles) of species A
per time being conserved:
¸1 N A1 ¹ ¸ 2 N A 2 (1)
Now
N A1 Á u1C A1 J A1
d ¿ C A1 ¼ (2)
Á u1C A1 À1D1 ½ º
dz ½¾ À1 º»
Thus
d Ç C A1 Ä d Ç C A2 Ä
É1u1C A1 É1È1D1 Å ÂÊÉ u C É 2È 2 D 2 Å Â (3)
dz ÅÆ È1 ÂÃ 2 2 A2
dz ÅÆ È 2 ÂÃ
Ì1u1Ë1 Í constant Í Ì 2 u 2Ë 2
C A1 D1 d µ C A1 ² C A 2 D 2 d µ C A2 ²
³ °· ³ ° (4)
¶1 u1 dz ³´ ¶1 °± ¶2 u 2 dz ³´ ¶ 2 °±
13.1 A 0.1 m column is loaded with 5 kg of sand. The size distribution is as follows
The density of the sand by displacement methods was measured to be 2600 kg/m3. The
sand is to be fluidized with air at 100°C. Atmospheric pressure is 772 mm Hg. Estimate
the minimum fluidization velocity. Calculate the composite particle diameter by means of
1
dp
xi
d pi
Solution
For the calculation of the minimum fluidization velocity the following expression is used:
dp (102cm) % xi/dpi
The density of the fluid is required at inlet pressure and a temperature of 100°C.
The inlet pressure is calculated from the outlet pressure and the expected pressure drop:
pout = 772 mm Hg
pressure drop Óp:
2
ÔD
S 78.54 cm 2
4
W 5
Õp 0.06366 kg / cm 2
S 78.54
0.0616 atm
46.83 mm Hg
273.2 818.83
×g 1.29294 * * 1.0198 kg / m 3
373.2 760
Density of the sand
ØS 2600 kg / m 3
ß1 / 2
å 1 â
æ ã 2é è ç à
ã R 2 à
ä æ0 á
t WR E'
where ê ; tR ; ì R k 0R exp(ë ) t R and í0 is the value of the deactivation
tR FS RT
function for the catalyst entering the fluidized bed.
When the particles are perfectly mixed the average of î in the reactor, ï is given by:
ø 1 õ ø 1 õ ò
ù expöö óerfcö ó
2 ó öù ó 2ñ R
÷2 ñ R ù0 ô 2ñ R
÷ 0 ô
r kc 2 ú
Tigrel & Pyle adopt a two-phase model for the fluidized bed, assuming perfect mixing of
gas in the emulsion phase and plug flow in the bubble phase and a transfer of gas
between bubble and emulsion phase.
Considering a mean bubble size derive the following expression for the fraction of feed
component A unconverted at the top of the bed
1 e z ð
2
exp( z ) 4k * ý
yT þ 1
1 2û1 ük * þÿ 1 e z
u mf us kH kH
where 1 k* z
u u u uaV
and u = superficial gas velocity (cm/sec)
ua = absolute bubble rising velocity (cm/sec)
us = downward velocity of catalyst particle (cm/sec)
K = transversal mass transfer coefficient (cm3/sec)
H = total bed height (cm)
V = bubble volume (cm3).
Plot the conversion as a function of the fluid velocity for solids velocities of 1.0, 3.0, and
10 cm/sec for a mean bubble diameter of 30 cm, a value of 0 = 0.9 and a reactor height
of 9 m.
Solution
ye yb
exp( Zz) (2)
(y e y b )o
kH x
where Z and z
uaV H
since yb = 1 at z = 0.
Since the emulsion phase is completely mixed, the equation may be written on the total
volume of the emulsion phase. Amount of A entering emulsion phase with flow:
u mf u S x 1
Amount of A reacted:
H k y e2
at z = 0 yb y e (1 y e )
z=1 y b T y e (1 y e )e Z
Since the amount of gas flowing through a unit cross section in the bubble phase is
u " u mf ! , the amount of A transferred is:
%Z
#u & u mf $#1 & y e $ 1 & e
so that
,Z
'u * u mf ('1 * y e ( 1 * e + 'u mf * u s ('1 * y e ( Hk )y e2 (4)
u mf us kH
Let 2 11 3 k*
u u u
1 C De F Z C B
Let E
2k * A
y e2 I 2Gy e H 2G 0
2
from which y e LJ K J K 2J (8)
1 Z \e _ Z Z [ Y V
2
\ exp(Z Z) 4]k *
yT ^ W 1^ Z 1
1Z [ 2T1 Z [ Uk * ] WX 1 Z \e _ Z Z [
dp(m)
5 15 25 35 45 55 65 75 85 95 105 115
(×106)
p(dp)(m-1)
6 22 46 76 118 170 200 152 99 63 36 12
(×102)
The solid density is 2500 kg/m3; the specific heat: 0.2 kcal/kg°C. The void fraction a of
the packed bed is 0.5. At the minimum fluidization velocity u mf = 7.2 m/h the void
fraction amf is 0.6. Gas properties: bg = 1 kg/m3; cp = 0.25 kcal/kg°C; c = 0.144 kg/h m;
De = 0.14 m2/h.
Solution
Removing the heat of reaction necessitates an internal heat exchanger. This exchanger
will also help to limit the bubble diameter. Take vertical tubes of 0.06 m OD on a 0.14-m
triangular pitch. This limits the effective diameter of the bubbles to 0.1m. Note that this is
a very crude way of determining the (average) bubble diameter, which is the main
variable in the Kunii and Levenspiel model.
Select the superficial velocity of the feed to be: 1800 m/h. The feed rate of propylene is:
(40.4 × 106)/(8000 × 53 × 0.78) = 120 kmol/h and the total gas flow at standard
conditions = 120/0.24 × 22.4 – 11,200 m3/h. The bed diameter is found to be 3.45 m and
the number of vertical tubes 552.
The mass transfer coefficients are calculated from (13.5.3-4) and (13.5.3-5):
1/ 4
7 .2 0.141 / 2 l 12.70 l 10 7
ik bc jb 4 .5 x m 5.85 5 .4
4464 h k1
0 .1 i0.1j
1/ 2
v 0.6 w 0.14 w 4322.8 s
nk ce ob 6.78t q 4100 h p1
u 0.13 r
it follows that
1x fb 0.586
ze 1000 y 1420 kg / m 3
fb 0.414
Viz 1.17
Vb | {1
so that, with
ub 4322.8
360
}u mf / mf ~ }7.2 / 0.6 ~
and c = e
Viz 1.17
c 1000 3.26 kg / m 3
Vb 359
Since only 1.5 percent of the bed solids are in the bubbles, the volume fraction of solids
in the bubble is obtained from
1 mf
1 f b
m 3s
b 0.015 0.01
fb m3b
b b s 0.01 2500 25 kg / m 3 b
With
m3
k 1.44
kg cat.h
After integration:
CA 1080 L f
1 xA 0.22 exp exp 0.25L f
C Ai 4322.8
from which Lf = 6.04 m. The total bed volume may be calculated to be 56.6 m3, the
emulsion volume 33 m3, and the amount of catalyst, W, roughly 33,000 kg.
Assuming plug flow, one would obtain from 1–x = e-k(W/F’), where F’ would be the total
feed rate in m3/h at 400°C, an amount of catalyst of 29,031 kg. Assuming complete
mixing of the gas phase one would obtain from F’x = k(1–x)W an amount of 67,980 kg.
Solution
The model equations are of the type introduced in Section 13.6. Continuity equations for the gas-
phase components are
dC i k ij' C j
u s,g £ s [1 ¢ ¡( z )] (a)
dz j 1 ¤ K Arh C Arh
The superficial flow velocity of the gas, us,g, and the void fraction ε (z) are updated in each Δ z
used in the numerical integration. First, the weight fraction of component i is calculated from
Ci M i
wi ( z )
Ci M i
i
1 Mi
¥ g ( z)
MV i wi
The continuity equation for the coke on the catalyst can be written
dC C ± '
k 10 jC j
®
¯ ¬« M [1 ª ©(z)]§¨¦
ms ³
¯ j 1 ² K Ar C Ar ¬ s C
(b)
dz
° h h
10 i ´1 k ij' C j
dT
(mGO c pg ¼ m s c ps ) » s (¹ ºH ij )[1 ¹ ¸( z )]¶·µ (c)
dz i 1 j 1 1 ¼ K Arh C Arh
The heat capacity of the catalyst, cps is taken to be constant throughout the reactor, but that of the
gas is calculated from
w i C 0p (i)
c pg ½
i Mi
in which C0p(i) (in kJ/kmol K) is the molar heat capacity of lump i at the reactor temperature.
The reaction enthalpy Δ Hij for the formation of i out of j is obtained from the molar
enthalpies Hi and Hj:
¿H ij Hi ¾ H j
where
T
Hi ÂH f0, i Á ÀT c 0p (i)dT
0
Figure 13.4-2
Yield profiles of the lumps of the LFO fraction in the riser reactor.
Figure 13.4-3
Void fraction profile in the riser reactor.
Figure 13.4-4
Weight percent coke versus height in the riser reactor.
Figure 13.4-5
Temperature profile in the riser reactor.
13.5 Simulation of a circulating fluidized bed riser reactor for the gasification of biomass
(synthesis gas production).
The weight fractions of char, gases, and tar produced, as well as the composition of the
gases produced depend on the type of biomass used. For 0.5-1.0 cm wood chips, Di Blasi
et al. [Di Blasi, C., Signorelli, G., Di Russo, C., and Rea, G., Ind. Eng. Chem. Res., 38,
2216 (1999)] experimentally found wCp1 0.33 , wGp1 0.48 , and wTp1 0.19 , and a gas
composition corresponding to 3.1 wt% CH4, 15.6 wt% CO, 27.1 wt% CO2, 52.1 wt%
H2O, and 2.1 wt% H2. Tar (liquid at ambient conditions and as such also referred to as
liquids) groups the carbonaceous components of high molecular mass. Their
stoichiometric composition can be represented by CH1.522O0.0228 [Bryden, K.M., and
Ragland, K.W., Energy Fuels, 10, 269 (1996)] and their mean molecular mass is taken 95
kg/kmol [Corella, J., Aznar, M.P., Delgado, J., and Aldea, E., Ind. Eng. Chem. Res., 30,
2252 (1991)]. At the temperatures in the reactor, the tar can be considered to be gaseous.
The char produced has the same size as the biomass particles, but a lower density. The
heat required for the biomass pyrolysis can be provided by the combustion of the
pyrolysis gases and the tar, as described hereafter.
Tar can undergo so-called secondary pyrolysis, described by:
k p2
Tar Å Gas p 2 (p2)
kc 2
CH 4 Ê 1.5 O 2 Ë CO Ê 2 H 2O (c2)
kc3
2 CO Í O 2 Ì 2 CO 2 (c3)
kc 4
2 H 2 Ï O 2 Î 2 H 2O (c4)
The combustion reactions are highly exothermic and can provide the heat required for the
primary pyrolysis.
The water gas shift reaction is also to be accounted for:
k wg
CO Ð H 2O Ñ CO 2 Ð H 2 (wg)
Finally, the combustion of char and the gasification of char by CO2, H2, and H2O are
described by:
kc5
C Ï O 2 Î CO 2 (c5)
k g1
C Ó CO 2 Ò 2 CO (g1)
kg2
C Õ 2 H 2 Ô CH 4 (g2)
kg3
C Ö H 2O × CO Ö H 2 (g3)
The char combustion is exothermic, whereas the char gasification reactions are
endothermic.
The reaction kinetics found in the literature is summarized in Table 1. Because of
the different types of solids involved (biomass, char), all reaction rates are expressed per
m 3r . Values for the pre-exponential factors and the activation energies are given in Table
2. The combustion of hydrogen is considered infinitely fast.
A fraction of the char leaving the reactor can be recycled.
TABLE 1
REACTION RATE EQUATIONS
Reaction Rate equation Units Ref.
(p1) rp1 k p1 (a v ) B Ù sB Ø B [kg B /m 3rs] [1]
(c2) rc 2 k c 2 Ü Tg C CH
0 .5 [3]
4 C O2
(c3) rc3 k c3 Ý C CO C O
0.25 [3]
2 C H 2O
(c4) rc 4 k c4 Þ C H2 C O2 [3]
(c5) ~r k c5 (a v ) C á sC C O 2 [6]
c5
(g1) ~r k g1 (a v ) C â sC C CO 2 [7]
g1
(g2) ~r k g 2 (a v ) C ã sC C H 2 [7]
g2
(g3) ~r k g 3 (a v ) C Ú sC C H 2O [7]
g3
E c1 80.235 10 6 [J/kmol]
(c2) A c2 9.2 10 6 [kmol/m 3r s] [3]
E c2 80.235 10 6 [J/kmol]
(c3) A c3 1.3 1011 [kmol/m 3r s] [3]
E c3 125.590 10 6 [J/kmol]
(c4) A c4 1 1011 [kmol/m 3r s] [3]
6 [J/kmol]
E c 4 83.144 10
(wg) A wg 2.78 [mol/m 3r s] [4],
[5]
E wg 12.58 10 6 [J/kmol]
[-]
AE 0.0265
[J/kmol]
EE 32.9 10 6
(c5) A c5 5.67 10 9 [kmol/m 3r s] [6]
E c5 160 10 6 [J/kmol]
(g1) A g1 1 10 7 [kmol/m 3r s] [7]
[J/kmol]
E g1 218 10 6
(g2) A g2 1 10 5 [kmol/m 3r s] [7]
E g2 218 10 6 [J/kmol]
E g3 218 10 6 [J/kmol]
Reactor model
For the simulation of the circulating fluidized bed riser the one-dimensional plug flow
model with slip between the gas and solid phases as described in Section 13.6 can be
used.
When calculating the primary pyrolysis and the char combustion and gasification reaction
rates, the variation of the particle size (char) by the combustion and gasification reactions
is to be accounted for.
The biomass pyrolysis, reaction (p1), is relatively slow and gas-solid mass transfer
limitations can be neglected. Gas-solid mass transfer limitations encountered in the
combustion and gasification of char — reactions (c5) and (g1)-(g3) — can be accounted
for as described in Chapter 3. For rc5, for example:
1
rc5 (a v ) C ì sC C O2 (a)
(1 / k m ) ë (1 / k c5 )
The gas-solid mass transfer coefficient, km, can be calculated according to [Gupta, A.S.,
and Thodos, G., AIChE J., 9, 751 (1963)]:
where Re is the particle diameter based Reynolds number. The particles used in the
simulations are considered small enough to allow neglecting intra-particle diffusion
limitations.
The gas-solid heat transfer can be modeled in terms of the gas-solid heat transfer
coefficient and the temperature difference between the gas and the solid phase:
The gas-solid heat transfer coefficient is modeled as [Gupta, A.S., and Thodos, G.,
AIChE J., 9, 751 (1963)]:
Data
The circulating fluidized bed riser is 12 m tall and operated adiabatically.
Consider the gasification of 650 µm biomass particles, assumed ash free. The moisture
content of the biomass fed is 10 wt% on a dry basis. The moisture evaporation is assumed
to be infinitely fast. The biomass is fed at room temperature (300 K), whereas the air fed
is preheated to 600 K. The air is considered to be composed of oxygen (21 %) and
nitrogen (79 %). Atmospheric pressure operation is considered. The air inlet velocity is
2.5 m/s. A fraction of the char leaving the reactor is adiabatically recycled.
The reactor temperature can be controlled by adjusting the feed air to dry biomass weight
ratio and the char recycle. In general, high-temperature biomass gasification allows
reducing the production of char and liquids, but faces the ash melting problem (ash
melting temperature ≈ 900 - 1100 K). Consider simulations with different inlet air to dry
biomass weight ratios, corresponding to outlet temperatures close to and well above the
ash melting temperature. (For example, for a reactor outlet temperature of 1350.5 K, the
inlet air to dry biomass weight ratio is 1.0, the char-to-biomass mass flow ratio at the
bottom of the reactor is ≈ 0.6 with 90% of the char leaving the reactor being recycled
adiabatically. For a reactor outlet temperature of 1004.5 K, the inlet air to dry biomass
weight ratio is 0.5.)
Additional data:
- diffusivity = 2.0∙ 10 -5 m2/s
- viscosity = 5.3∙ 10-5 Pa s
- conductivity = 0.17 W / m K
Solution method
Solve the set of species continuity and energy equations using a fourth-order Runge-
Kutta routine.
Solution
Modeling the riser with a one-dimensional plug flow model with slip between the phases, the gas
phase species continuity equations can be written (with all terms in [kmol / m 3r s] ):
For N2:
ñ ò g u g C N2
0
ñz
ü ý g u g Ci û w p1, G ø û w p 2, G M TAR ø
rp1 w Gp1 ù i öõ r ù i öõóô r
üz ù Mi ö p2 ù Mi ö j i ,j j
ú ÷ ú ÷
with ug the interstitial gas phase velocity and j = (c1)-(c5), (g1)-(g3), (wg).
For the solid phase species, the continuity equations can be written (all terms in [kg / m 3r s] ):
For the biomass (B):
ÿ ðB us
sB
þ rp1
ÿz
sC C u s
rp1 w Cp1 M C r j
z j
ñ Tg
ò g
g c p ,g u g H j r j Q gs
ñz
Ts
u s s, k k c p, k H j
r j Q gs
k z j
with j = (p1), (c5), and (g1)-(g3), and k: Biomass and Char.
When calculating the primary pyrolysis and the char combustion and gasification reaction rates,
the variation of the particle size (char) by the combustion and gasification reactions is to be
accounted for. Considering spherical particles, the specific external particle surface area, av, is
given by:
6
av (e)
dp
The required data on the standard heats of formation and specific heat capacities are given in
Table 13.5-1.
TABLE 13.5-1
SPECIFIC HEAT CAPACITY AND STANDARD HEAT OF FORMATION
0
Hf Cp = A + B×T + C×T² + D×T³
Species
(J/kmol) A B C D Unit
-5
N2 31150 -13.6 0.0268 -1.2∙ 10 J/kmol K
7 -5
CH4 -7.48∙ 10 19238 52.1 1.20E-02 -1.13∙ 10 J/kmol K
8 -5
CO -1.11∙ 10 30870 -12.9 0.02789 -1.3∙ 10 J/kmol K
8 -5
CO2 -3.94∙ 10 19800 73.4 -0.05602 1.72∙ 10 J/kmol K
8 -6
H2O (g) -2.42∙ 10 32240 1.9 0.01055 -3.6∙ 10 J/kmol K
-6
H2 27140 9.3 -0.01381 7.65∙ 10 J/kmol K
7 -5
TAR -7.78∙ 10 93450 -40.7 0.0804 -3.5∙ 10 J/kmol K
-5
O2 28110 -0.00368 0.01746 -1.1∙ 10 J/kmol K
8
H2O (l) -2.86∙ 10 75263 J/kmol K
Wood 1659 J/kg K
Char 989 J/kg K
The simulations being carried out in 1D, fluxes, that is, in [kg/m 2rs] , can be used for expressing
the amounts of biomass converted and products formed in a reactor of given length.
Table 13.5-2 summarizes the results of the simulation of the gasification of biomass in a CFB
riser for two different reactor outlet temperatures. Increasing the specific biomass inlet flux, that
is, decreasing the feed air to dry biomass weight ratio, proportionally increases the specific
biomass conversion rate. The latter is defined as the mass of dry biomass converted per unit
volume reactor and per unit time. The reactor temperature, however, logically decreases and, per
kg dry biomass converted, less dry gas and more char is produced, as well as a small amount of
liquids. As a result, despite the proportionally increasing specific biomass conversion rate, the
specific dry gas production is not much increased. The main difference in the dry gas composition
is a decrease in the CO and an increase in the CO2 content. The LHV of the dry gas and liquids
produced only slightly decreases, however, due to the somewhat higher CH4 and H2 content. This
shows the reason for CFB riser type biomass gasifiers to be operated at temperatures well above
the ash melting temperature. Figure 13.5-1 schematically summarizes the simulation results at a
reactor outlet temperature of 1350.5 K and Figure 13.5-2 shows the calculated axial concentration
and temperature profiles in the CFB riser for a reactor outlet temperature of 1271.6 K. The dry
gas composition predicted by the simulation model corresponds reasonably well (± 15%) with
data reported in the literature [Zwart, R., “Technical, Economic and Environmental Potential of
Cofiring of Biomass and Waste in Natural Gas Fired Turbines and Combined Cycles,” ECN-RX-
03-003, Mar. (2003)].
Figure 13.5-1
Schematic overview of the simulation of the gasification of biomass in a circulating fluidized bed riser.
Reactor outlet temperature of 1350.5 K.
TABLE 13.5-2
SIMULATION RESULTS
Outlet temperature [K] 1350.5 1004.5
H 2O 0.29 0.32
N2 41.6 37.6
CO 22.3 8.5
Produced dry gas composition
CO2 13.0 26.1
(vol. %, dry basis)
H2 18.7 19.3
O2 0 0
Produced dry gas LHV (incl.
[MJ/Nm³] 6.4 6.1
liquids)
4.5E-03
4.0E-03
3.5E-03
Concentration [kg/m³reactor]
N2
H2O 3.0E-03
CO2
2.5E-03
H2
CO
2.0E-03
CH4
TAR x200 1.5E-03
O2
1.0E-03
5.0E-04
0.0E+00
0 2 4 6 8 10 12
Height [m]
2500
2000
Temperature [K]
1500
Tg
Ts
1000
500
0
0 2 4 6 8 10 12 14
Height [m]
Figure 13.5-2
Calculated axial concentration and temperature profiles. Reactor outlet temperature of 1271.6 K.
CHAPTER 14
14.1 Calculate the pressure drop for a trickle bed reactor in which air and water
flow down at room temperature through a packed bed of glass beads (0.2 cm
diameter). The superficial gas and liquid velocities are resp. 5 and 0.2 cm/s. The
void fraction of the bed is 0.4. Use the correlations presented in 14.3.2 and
compare the results.
Solution
a) Larkins: (14.3.2-1)
-2 0.416
log . 2
-L & -G , -L )
log * ' & 0.666
*
+ -G '
(
/L and /G are the single phase pressure drops calculated by means of the Ergun equation.
d PG
Re 3
2 (1 1 0)
1.03 2 Q 10 T6 P .6 M
3
(1.769 ^ 10 a5 ) 2 \ .6 Y
3
b 211.21 kg m 2 b 211.21 Pa m
dL
log c 0.1724
dG
g2 0.416
log e e 0.5979
gL f gG 0.1724 2 f 0.666
g2 .5979
e 10 e 3.9621
gL f gG
n Pa k
o2 h 2688.35l h .2653 atm m
i
mmj
b) Sweeney (14.3.2-2)
13 13
v wL s v wG s
t q xt q p1
u w2 r u w2 r
13 13 13
yL { yG z y2
n Pa k
o2 h 2580.02 l h .2546 atm m
i
mmj
c) Midoux (14.3.2-3)
0 .5 ~ 0 .5 ~0.27
2
L
L
1 1.14
L
G
G
2.5923
2
6.67
L
Pa
2 3116.89 .3076 atm m
m
14.2 Calculate the liquid hold up for the case considered in the previous problem.
Solution
Liquid hold up
Midoux (14.3.2-5)
0.40
0.66 L
G
L 0.40
1 0.66 L
G
14.3 Check by means of the diagram 14.3.2-2 in which regime the reactor described
in Problem 1 operates.
Solution
Re L ¤ 6.46
£
¢ Trickle flow
Re G ¤ 11.35¡
14.4 Design of a Packed Column for Carbon Dioxide Absorption (after Danckwerts
and Sharma [15]).
Carbon Dioxide is to be absorbed at 20 atm abs (20.3 bars) and 30°C from a gas
stream of 900 kmol/h with the following molar proportions: N2/H2/CO2: 1/3/1.33 by
means of a 2.5-molar monoethanolamine (MEA) solution
CO2 + 2R2NH → R2NCOO- + R2NH2+
The CO2 content is to be reduced to 2.10-3 percent. The content of dissolved CO2 in
the MEA will be 0.15 and 0.40 mol CO2/mol MEA at the top and bottom of the
column, respectively. A column packed with 1 1/2 in. Rashig rings will be used.
The model is that of Section 14.2.2, which assumes the gas and liquid to be in plug
flow.
Furthermore, since the reaction is very rapid, the bulk concentration of A is taken to
be zero.
The amount of CO2 to be absorbed is
1.33
900 ¦ ¥ 225 kmol h
5.33
so that the liquid flow rate has to be
225
L§ § 360 m 3 h
(0.40 ¨ 0.15)2.5
The choice of the column diameter is based on the gas flow rate that would give
flooding at the bottom. From Fig. 14.3.1-1 it follows that for (L F' ) ª L ª g © 2.66
(with «g calculated from the ideal gas law) the gas flow rate leading to flooding is
obtained from
G f2 (a V ¯ 3 )(® L ® W ) 0.2
¬ 0.007
g g L
Provided the concentration of free CO2 is less than that of free amine, the
concentration of free MEA is CBO(1-2¹) and that of R2NCOO- and of R2NH2+ is
CBO¹, where ¹ is the number of moles of CO2 absorbed per mole of total amine and
CBO is the initial concentration of MEA. The equilibrium concentration of CO2 is
then given by
2
º
C CO 2 ¼ KC
(1 » 2º ) 2
Danckwerts and Sharma selected a value of 9.0 × 10-6 kmol/m3 for KC. At the top of
the column, where ¹ = 0.15, the equilibrium concentration of CO2 is 4.1×10-7
kmol/m3. The corresponding back pressure is found, using Henry's law, to be 1.6 ×
10-5 atm while the partial pressure of CO2 at the top of the column is 2.10-5×20 =
40.10-5 atm; therefore, the back pressure is negligible. The same conclusion would
be arrived at for the conditions at the bottom of the column.
The kGa'v value was taken from a correlation mentioned in Norman [17] for air in
ammonia at 20°C and 1 atm total pressure.
0.38
0.72 Â ÄLL ¿
k G a'v Æ c Å G À ½
Á Ã ¾
When kGa'v is expressed in kmol/m3h atm and G and ÇLL/È in kg/m2h, the constant
c has the value 0.03975. With S.I. units (bar and s, instead of atm and h) c =
0.09015. This correlation can be used provided it is corrected for the total pressure
and adapted to the system CO2-MEA by accounting for the Schmidt numbers.
These contain the viscosities of mixtures N2, H2, CO2, and the diffusivity of CO2 in
such mixtures, and the corresponding values for the air-ammonia mixtures. Using
the correlations developed in Reid and Sherwood [18] the Schmidt number for the
gas mixture is calculated to be 0.80 and that for the air-ammonia mixture 0.65. Now
kGa'v is calculated as follows, for an average G of 1758 kg/m2h and an average
2
ÇLL/È of 60543 kg/m h:
23
0.72 0.38 Î0.65 Ë Î 1 Ë
k G a ' v Ï 0.03975(1758) (60543) Ì É Ì É
Í 0.80 Ê Í 20 Ê
kmol
Ð 24.65 Ð 0.00685 kmol m 3 s bar
m 3 h atm
The rate of the global phenomenon can be written as
NA Ñ k G p t ( y AG Ò y AGi ) Ñ FA k L C Ai
with N A Ø FA k L C Ai .
Such a high value of ê justifies setting the concentration of CO2 in the bulk liquid
equal to zero.
The parameter curves in the Van Krevelen and Hoftijzer diagram were originally,
according to the film theory, (a/b)(DB/DA) (CB/CAi). To account for the results of
the penetration theory, indicating that the mass transfer coefficients are proportional
to the square roots of the diffusivities, Danckwerts and co-workers have used
(a / b)(C B / C Ai ) D B / D A as the parameter group in the Van Krevelen and
Hoftijzer diagram. The value of the latter group amounts to
CB DB 0.81 2.77 ñ 10 ó6
ò ï ï 3 .0
2C Ai DA 2 ñ 0.1 5.04 ñ 10 -6
From Chapter 6 (Figure) the enhancement factor is found to be 3.5. Using the
original parameter group, the value of which would be 2.2, FA would amount to 3.0.
p Ab 4 .0 kmol
N A a'v ô ô ô 29.2
1 H 1 40 m 3r h
ö ö
k G a'v FA k L a ' v 29.27 3.5 õ 0.729 õ 140
With this value pAi is found to be 3.0 atm instead of 4.0 as assumed. A second cycle
of calculations is necessary, leading to NAa'v = 33.22 kmol/mr3h and a third to NAa'v
= 33.98 kmol/mr3h. Further iterations are unnecessary, so that the calculations can
proceed to the next increment in pA. The height of the column is found to be 4.60
m. Note that, as the top of the column is approached, the CO2 content becomes so
low that CB varies little and pseudo-first-order behavior is achieved. In that part of
the column the calculations could be based on Chapter 6, with CA = 0, of course.
14.5 Design Aspects of a Packed Column for the Absorption of Ammonia in Sulfuric
Acid (after Ramm [14]).
Let kG = 0.3 kmol/m2h atm = 9.6×10-5 kmol/m2s bar, kL = 0.005 m/h and the Henry
coefficient 0.0133 kmol/m3 = 0.0131 kmol/m3bar. Whether (6.3.c-3) or (6.3.c-8) are
applicable depends on C'B = bDANA/aDBkL or, since NA = kGpA, when the reaction
plane coincides with the interface C'B = (bDAkG/aDBkL)pA. Suppose, as a first
approximation, DA = DB, then
0.35
C' B ÷ pA ÷ 35p A
2 ø 0.005
At the bottom of the column, where pA = 0.05 atm
which is lower than CB = 0.6 kmol/m3. The CB at the bottom can be calculated from
an overall balance:
Fû(p A ) in ý (p A ) out ü 0.05 ý 0.01
þ Lû(C B ) in ý (C B ) out ü þ 45 ÿ þ 9û0.6 ý (C B ) out ü
2p t 2
Consequently, the column has to be calculated in two parts: the top part in which
CB>C'B so that (6.3.c-8) has to be applied and the bottom part in which CB<C'B and
in which (6.3.c-3) is valid. The location of the dividing line may also be obtained by
means of a material balance, on the bottom part, for example:
(p A ) in ð p A a
F L(C' B ðC B ) 45(0.05 - p A ) 2 9 (35p A ð 0.5)
pt b
from which pA = 0.0166 atm = 0.0168 bar and the corresponding C'B = 35pA = 0.58
kmol/m3.
1 1 H 1 0.0133 1
K G k G k L 0.35 0.005 0.18
so that
4.94 ø 10
5 kmol m 2 s bar
kmol
KG ÷ 0.180 ÷
m 2 h atm
The continuity equation for A in a differential element is written as
dp A
F N A dO
pt
where = (a/b)(DA/HDB). The equation is easily integrated and yields O = 180 m2.
from which O = 65 m2. The total required interfacial area is 245 m2. The total
volume of the column follows from V = 0/a'v where a'v would be calculated from
the correlation by Onda at al. (14.3.1-2).