Contents

1.0 Background.......................................................................................................... 2
2.0 Material Balance.................................................................................................... 3
3.0 Energy Balance...................................................................................................... 5
4.0 Reactor Sizing Considering the Energy Balance and Main Reaction.....................................8
5.0 Estimation of Diffusion- and Reaction-Limited Regimes.................................................19

STAGE 1
1.0 Background
We are assigned to design a reactor and a separator for the production of isobutylene
by performing reaction system analysis and sizing. In this project, we are required to produce
as much as 100000 metric tonnes of isobutylene yearly through the process of butane
dehydrogenation. Isobutylene (or 2-methylpropene) is a hydrocarbon of industrial
significance that is used as an intermediate in the production of a variety of products such as
MTBE and ETBE, isooctane from the alkylation process, and also antioxidants. There are
several steps or stages that have to be analysed and evaluated thoroughly. This includes
performing overall material mass and energy balance for the dehydrogenation process,
followed by reactor sizing by taking into consideration the effect of diffusion and also side
reactions, and finally, obtaining the weight of catalyst used and other parameters concerned.
An overview of the dehydrogenation of isobutene to produce isobutylene; initially, we
have decided to select Catofin technology (Domenico Sanfilippo I. M.) which is a technology
that use fixed-bed adiabatic reactors. Characteristics of Catofin technology are:

Low consumption of isobutane, due to the high selectivity ensured by the Pt catalyst.

Heat of reaction supplied by the formation of coke

Catalyst endowed to potential poisons such as water vapour and heavy metals, high
level of thermal stability, resistance to friction and tolerance.
Characteristics
Type of

Catofin
Fixed-bed

Oleflex
Mobile

STAR
Tubular,

FBD
Fluidized-bed

Reactor
Catalyst

adiabatic
Platinum

adiabatic-bed
Platinum

fixed-bed
Platinum

Chromium

Pressure
Temperature

Low
High
High
High
High
High
Table 1: Comparison of Production Technologies

oxides
Low
High

The catalyst chosen is platinum together along with tin as its promoter. The initial
temperature of the feed is assumed to be 550 oC and the pressure of the inlet is at 1 atm. The
same condition is applied to the reactors and the conversion of isobutane is 50% (X=0.5). By
performing the necessary mass and energy balance in the first stage, we are able to identify
the inlet parameters such as the amount of feed rate flow. Proceeding to the next stage, we
2

have then identified adsorption reaction as the rate limiting step via journal and patent
reviews. Before performing the reaction rate law, we have to include the pressure drop that
exists in the system and performing the required stoichiometry. Finally, in the third stage, we
have to prove that the system is only limited by surface reaction.
Hence, whilst carrying out this project, we developed a better insight on the
mechanism that occurs in a process such as the internal and external diffusion. We have also
learned to apply the fundamentals of CRE knowledge in solving various engineering related
problems.

2.0 Material Balance

Assuming an operating hours of 8000 hours for a year as about 760 hours of the rest time is
for the plant turnaround works.
1 metric tonne=1000 kg

Molar weight of Isobutylene=56.106 kg /kmol

1 year =8000 operating hours

Isobutylene(kmol /hr)=

100000 metric tonnes

1000 kg
1 kmol
1 year

year
1 metric tonne 56.106 kg 8000 hr

222.7926 kmol /h r

Isobutylene(kg /hr)=

100000 metric tonnes

1000 kg
1 year

year
1 metric tonne 8000 hr
12500 kg/h r

Feed:
The inert/alkane ratio is increased from 0 to 3 at 550C and 1 atm, the equilibrium conversion
increases from 44 % to 64 %. Thus, assume a reaction conversion of 50% and 1 for the
steam/isobutane ratio. Also, under typical dehydrogenation conditions (550C, 1 atm) the
equilibrium conversion decreases from about 44 % to 25 % when the H2/alkane ratio
increases from 0 to 3. Assume the H2/alkane ratio equals to 0.5.
3

X =0.5
H 2 =0.5
S =1
Molar weight of Isobutane=58.12 kg /kmol

Molar weight of Hydrogen=2kg /kmol

From stoichiometry,
F A =F A 0 (1 X )
F A 0=

FA
1X

Isobutane Feed ( kmol/hr )=

Isobutane Feed ( kg /hr )=

222.7926
=445.5852kmol /hr
10.5

445.5852 kmol 58.12kg

=25897.4118 kg /hr
hr
kmol

Hydrogen Feed( kmol/hr )=0.5 445.5852 kmol /hr =222.7926 kmol /hr

Hydrogen Feed( kg/hr )=

222.7926 kmol 2 kg

=445.5852 kg/hr
hr
kmol

Steam Feed (kmol /hr)=1 445.5852 kmol /hr=445.5852 kmol /hr

Steam Feed (kg /hr)=

445.5852 kmol 18 kg

=8020.5336 kg /hr
hr
kmol

Output:
According to the chemical reaction of dehydrogenation of isobutane to isobutylene, 1 mol of
isobutane will react to produce 1 mol of isobutylene and 1 mol of hydrogen gas.
iC 4 H 10 iC 4 H 8+ H 2
Hydrogen Generated (kmol /hr )=0.5 445.5852kmol /hr=222.7926 kmol/hr

Hydrogen Generated (kg /hr)=

222.7926 kmol 2 kg

=445.5852 kg /hr
hr
kmol

Hydrogen Output (kmol/ hr )=Hydrogen Generated+ Hydrogen Feed

222.7926 kmol /hr + 222.7926 kmol/hr

 445.5852 kmol /hr

Hydrogen Output (kg/hr )=

445.5852 kmol 2 kg

=891.1704 kg/ hr
hr
kmol

Steam Output (kmol /hr)=Steam Feed (kmol /hr)=445.5852 kmol /hr

Steam Output (kg /hr)=

445.5852kmol 18 kg

=8020.5336 kg/hr
hr
kmol

Isobutane Output (kmol/ hr )=0.5 445.5852 kmol/hr =222.7926 kmol /hr

Isobutane Output ( kg/hr )=

iC4H10

H2

Steam

222.7926 kmol 58.12 kg

=12948.7059 kg/hr
hr
kmol

445.5852 kmol/hr
25897.4118 kg/hr

X=0.5

222.7926 kmol/hr
445.5852 kg/hr
445.5852 kmol/hr
8020.5336 kg/hr

222.7926 kmol/hr
12948.7059 kg/hr

iC4H10

222.7926 kmol/hr
12500 kg/hr

iC4H8

445.5852 kmol/hr
891.1704 kg/hr

H2

445.5852 kmol/hr
8020.5336 kg/hr

Steam

FT = 1336.7556 kmol/hr
FT0 = 1113.9630 kmol/hr
m
T = 34360.4099 kg/hr
m
T 0 = 34363.5306 kg/hr
Figure 1: Material Balance for the Production of 100000 Metric Tonnes Isobutylene
3.0 Energy Balance
Isobutane Isobutylene+ H 2
The energy required to remove two atoms of hydrogen from alkane molecule is in the range
of 113 134 kJ/mol. The highly endothermic nature of the reaction leads to a strong
temperature decrease. In the case of the dehydrogenation of propane, there is an adiabatic
temperature decrease of 200C. Hence, since dehydrogenation of isobutane requires an
energy which is also in the range of 113 134 kJ/mol, the temperature is assumed to be
decreased to 350C as outlet temperature of the reactor.

Isobutane
H2
Isobutane
Steam
TH02=550H R
Steam

H 25

Isobutylene 5
Isobutane
H2
Steam

H
Isobutylene
Isobutane
H2
H Steam
P
T =350
Figure 2: Calculation Path for Dehydrogenation of Isobutane to Isobutylene
Species
Isobutane
Isobutylene
Hydrogen
Steam

A(103)
B (105)
C (108)
D (1012)
89.46
30.13
18.91
49.87
82.88
25.64
17.27
50.50
28.84
0.00765
0.3288
0.8698
33.46
0.6880
0.7604
3.593
Table 2: Heat Capacity Constants of Gases in Ideal-Gas State

Reactants:
25

H R =

( A + BT +C T 2+ D T 3 ) dT T [ ]

550

Isobutane :
25

[ ( 89.46 103 ) + ( 30.13 105 ) T +(18.91 108 ) T 2 +( 49.87 1012 ) T 3 ] dT

550

83.0986 kJ /mol

Hydrogen :
25

[ ( 28.84 103 ) +( 0.00765 105 ) T +( 0.3288 108 ) T 2 + ( 0.8698 1012) T 3 ] dT

550

15.3150 kJ /mol

Steam :
25

[ ( 33.46 103 ) + ( 0.6880 105 ) T +( 0.7604 108 ) T 2 +( 3.593 1012) T 3 ] dT

550

18.9444 kJ /mol

H R =83.4979 kJ /mol +(15.3150 kJ /mol)+(18.9444 kJ /mol)

6

117.7573 kJ /mol

The enthalpy of formation of iC4H10, iC4H8, and H2 are

Hf

iC4H10 = 134.5 kJ/mol

Hf

iC4H8 = 16.9 kJ/mol

Hf

H2 = 0 kJ/mol

H 25 = H f ( C 4 H 8 )+ H f ( H 2) H f (C 4 H 10)
16.9 kJ /mol+ 0 kJ /mol(134.5 kJ / mol)
117.6 kJ /mol

Products:
350

H P =

( A +BT +C T 2+ D T 3 ) dT T [ ]

25

Isobutane :
350

[ ( 89.46 103 ) + ( 30.13 105 ) T +(18.91 108 ) T 2 +( 49.87 1012 ) T 3 ] dT

25

44.9205 kJ /mol

Isobutylene :
350

[ ( 82.88 103 ) +( 25.64 105 ) T +( 17.27 108 ) T 2+( 50.50 1012) T 3 ] dT

25

40.2826 kJ /mol

Hydrogen :
350

[ ( 28.84 103 ) +( 0.00765 105 ) T +( 0.3288 108 ) T 2 + ( 0.8698 1012) T 3 ] dT

25

9.4214 kJ /mol

Steam :
350

[ ( 33.46 103 ) + ( 0.6880 105 ) T +( 0.7604 108 ) T 2 +( 3.593 1012) T 3 ] dT

25

 11.3889 kJ / mol
H P =44.9205 kJ /mol+ 40.2826 kJ /mol+9.4214 kJ /mol +11.3889 kJ /mol
106.0134 kJ /mol

H Rx = H R + H 25 + H P
117.7573 kJ /mol+117.6 kJ /kmol +106.0134 kJ /mol
105.8561kJ /mol

STAGE 2
4.0 Reactor Sizing Considering the Energy Balance and Main Reaction
Mechanism
iC 4 H 10+ S iC 4 H 8 S
iC 4 H 10 S +S iC 4 H 8 S+ H 2 S
iC 4 H 8 S iC 4 H 8 + S
H 2 S H 2 +S

Adsorption :r A =k A P A CV

C A S
. .. . (1)
KA

Surface reaction :r S =k S C A S CV

Desorption:r DE=k DE C E S

C E SC H S
KS

PE CV
K DE

]
8

r D H =k D H C H S
2

PH CV
KDH
2

Assume Absorption as rate determining step:

When r S 0, C A S =

C E SCH S
. . .. .....( 2)
K SCV
2

PEC V
=K E PE C V . .. . ..(3)
K DE

When r DE 0, C E S=

where

When r D H 0,C H S=
2

1
=K E
K DE

P H CV
=K H PH CV .. . . ..( 4)
KD H
2

where

1
KDH

=K H

Substitute (3) and (4) into (2):

C A S =

K E K H PE PH CV
( 5)
KS
2

Site balance:
CT =C V +C A S+ C E S +C H

CV +

K E K H P E P H CV
+ K E PE C V + K H P H C V
KS

CV 1+

CV =

K E K H PE P H

1+ K E H

KS

+ K E PE+ K H PH
2

CT
. . .(6)
PE PH + K E PE+ K H PH
2

where

K E KH
=K EH
KS
2

Substitute (5) into (1):

KE K H PE PH CV

r A =k A P A C V

k A P A CV

k A CV PA

where

K E K H PE PH CV
KS
2

KA

KAKS

PE PH
. .. ( 7)
K
2

K A KS
=K
K E KH
2

Substitute (6) into (7)

k A CT PA
r A=

1+ K E H

P E PH
K
where k ' =k A CT
PE P H + K E PE + K H P H

1+ K E H

K
PE P H + K E P E + K H PH

k' P A

PE P H

Rate law
PE P H
K
PE PH + KE PE+ K H PH

k' PA
r ' A =r A =

1+ K E H

10

iC 4 H 10 iC 4 H 8+ H 2

)]

141 103 1 1

mol /kgcat s
8.3144 T 0 T

where k ' (T )=0.0507 exp

5.07 107 exp

K (T )=2.110 7 exp

2.1 1012 exp

141 103 1 1

8.3144 T 0 T

)] mol/kgcat s Pa

)]

122 10 1 1

8.3144 T 0 T

122 103 1 1

8.3144 T 0 T

)] Pa

2
10
2
=9.7210 Pa
K E H =9.72
2

1
5
1
=7.33 10 Pa
K E=7.33

1=3.87 105 Pa1

K H =3.87
2

(Sanna M. K. Airaksinen, 2002)

Stoichiometry

H2

Species

Inlet

Change

Isobutane

FA 0

F A 0 X F A =F A 0 (1 X )

Isobutylene

FA 0E

FA 0 X

F E=F A 0 ( E + X )

C E=C A 0

Hydrogen

FA 0H

FA 0 X

F H =F A 0 ( H 2 + X )

C H =C A 0

Steam

FA 0S

Rearranging

Outlet

F S=F A 0 S

Concentration
1X T 0
C A =C A 0
y
1+X T

)( )

C S=C A 0

+X T
( 1+X
)( T ) y
E

H + X
1+X

)( )

S
1+X

T0
y
T

T0
y
T

)( )

Pressure

11

P A P A 0 1X
=
RT R T 0 1+X

)( T ) y

P A =P A 0

( 1+1XX ) y

PE PA 0 E+ X
=
RT R T 0 1+X

)( TT ) y

PE =P A 0

+X
( 1+X
)y

T0

PH PA 0 H + X
=
RT R T 0 1+X

T0
y
T

PH =P A 0

PS P A 0 S
=
RT R T 0 1+X

T0
y
T

PS =P A 0

(
(

)( )
)( )

H + X
y
1+ X
2

( 1+X
)y
S

Table 3: Stoichiometry Table

where H =0.5
2

S =1
E=0
y A 0=

F A0
FA0
=
F T 0 F A 0 + F A 0 H + F A 0 S
2

FA 0
F A 0 + F A 0 (0.5)+ F A 0 (1)

0.4
= y A 0 =0.4 ( 1+11 ) =0.4

F E=

222.7926 kmol 1000 mol

1hr

=61.8868 mol /s
hr
1 kmol
3600 s

F A 0=

FE
F
61.8868
= E=
mol /s
E + X X
X

Assume P0 =10 atm

P A 0= y A 0 P 0=0.4 ( 10 atm ) =4 atm=405300 Pa

12

Design Equation
FA 0

dX
=r ' A
dW

Combine
FA 0

dX
'
=r A
dW

'

k P A

FA 0

PE PH

K
dX
=
dW 1+ K E H P E PH + K E P E + K H P H
2

dy
T
( 1+ X )
=
dW 2 y
T0

( )

where =

2 0
c (1) Ac P0

0=

G (1 ) 150 ( 1 )
+1.75 G
3
DP
0 g c D P

D
A c=
4

13

G=

FT 0 MW 0,mix
Ac

y A 0=0.4

y H , 0=
2

F H ,0
FA 0H
=
=0.2
F T 0 F A 0 + F A 0 H + F A 0 S
2

FS0
F A 0 S
=
=0.4
F T 0 F A 0+ F A 0 H + F A 0 S

yS 0 =

MW mix = y A 0 MW A + y H , 0 MW H + y S 0 MW S
2

0.4( 0.05812)+0.2( 0.002)+0.4 (0.018)

0.030848 kg /mol

F T 0=

FA 0 F A0
=
y A 0 0.4

A0=

0.024169 mol
1 dm3
0.05812kg
3

=1.40470228 kg/m
3
3
mol
dm
0.001 m
3

0.030054 mol
1dm
0.002 kg
H , 0=

=0.060108 kg/m3
3
3
mol
dm
0.001 m
2

S 0=

0.01465875mol
1 dm3
0.018 kg
3

=0.2638575 kg /m
3
3
mol
dm
0.001 m

0= y A 0 A 0 + y H

,0

H ,0 + y S 0 S 0
2

0.4 ( 1.40470228 ) +0.2 ( 0.060108 ) +0.4 ( 0.2638575 )

3

0.6794 kg /m

A 0 =1.2195 105 Pa s
5

H , 0=1.2207 10 Pa s
2

S 0 =3.0593 10 Pa s
14

(Bruce E. Poling, 2008)

= mix=

y i 0 i0 ( MW i )0.5
y i 0 (MW i )0.5
0.5

5
5
0.4 ( 1.2195 10 ) ( 0.05812 ) +0.2 ( 1.2207 10 ) ( 0.002 )
5
0.5
+0.4 ( 3.0593 10 ) (0.018)

0.5
0.5
0.5
0.4 ( 0.05812 ) + 0.2 ( 0.002 ) +0.4 (0.018)

0.5

1.8404 10 Pa s
gc =1.0( metric system)
Assume D=0.05 m

Specifications of the commercial catalyst:

D P =0.004572 m
c =984.4 kg/m

=0.45

(A. Rosjorde, 2007)

Ua
'
( T T ) +r A H Rx ( T )
b a

dT
=
dW
F A 0 ( i C Pi + C P X )
where U=56.784 W /m2 K =56.784 J / s m2 K
b= c ( 1 )=984.4 ( 10.45 )=541.42 kg /m

Assume T a=653 K
H Rx ( T ) =105.8561kJ / mol=105856.1 J / mol

15

C P ,i = A +B (T 273)+C (T 273) + D(T 273) where T [ ] K

C P , A = ( 89.46 103 )+ ( 30.13 105 ) (T 273)+ (18.91 108 ) (T 273)2 + ( 49.87 1012 ) (T 273)3

C P , E= ( 82.88 103 ) + ( 25.64 105 ) (T 273)+ ( 17.27 108 ) (T 273)2 + ( 50.50 1012 ) (T 273)3

C P , H =( 28.84 103 ) + ( 0.00765 105 ) (T 273)+ ( 0.3288 108 ) (T 273)2 + ( 0.8698 1012) ( T
2

C P , S=( 33.46 103 ) + ( 0.6880 105 ) (T 273)+ ( 0.7604 108 ) (T 273)2 + ( 3.593 1012) (T 273
C P = C P , products C P ,reactants
[ ( C P ,E + C P , H ) C P , A ] 103 J /mol K
2

H =0.5
2

S =1
E=0
C
3

P
,
A+
0.5
C
i C P ,i=(
P , H +C P ,S )10 J / mol K
2

a=2 (

L=

D
)L
2

W
c ( 1 ) A c

16

POLYMATH Report

No Title
05-Dec-2013

Ordinary Differential Equations

Calculated values of DEQ variables

Variable

Initial value

Minimal value

Maximal value

Final value

11.32705

11.32705

abc

0.4

0.4

0.4

0.4

Ac

0.0019638

0.0019638

0.0019638

0.0019638

alpha

0.0143117

0.0143117

0.0143117

0.0143117

beta

7708.983

7708.983

7708.983

7708.983

Cp_A

0.2062694

0.1791016

0.2062694

0.1791066

Cp_E

0.1800602

0.1579131

0.1800602

0.1579172

Cp_H2

0.029732

0.0292927

0.029732

0.0292927

Cp_S

0.0389464

0.0369578

0.0389464

0.0369581

10 dCp

3.522798

3.522798

8.104152

8.103309

11 delta_E

12 delta_H2

0.5

0.5

0.5

0.5

13 delta_S

1.

1.

1.

1.

14 density_b

541.42

541.42

541.42

541.42

15 density_c

984.4

984.4

984.4

984.4

16 density_o

0.6794

0.6794

0.6794

0.6794

17 dH_Rx

1.059E+05

1.059E+05

1.059E+05

1.059E+05

18 Diameter

0.05

0.05

0.05

0.05

19 Dp

0.004572

0.004572

0.004572

0.004572

20 FA0

0.036

0.036

0.036

0.036

21 FE

0.0109814

0.0109814

22 FT0

0.09

0.09

0.09

0.09

23 G

1.413785

1.413785

1.413785

1.413785

24 gc

1.

1.

1.

1.

25 K

2.1E+12

1.918E+10

2.1E+12

1.92E+10

26 k

5.07E-07

2.228E-09

5.07E-07

2.231E-09

27 KE

7.33E-05

7.33E-05

7.33E-05

7.33E-05

28 KEH2

9.72E-10

9.72E-10

9.72E-10

9.72E-10

29 KH2

3.87E-05

3.87E-05

3.87E-05

3.87E-05

30 L

72.10088

72.10088

31 MW_A

0.05812

0.05812

0.05812

0.05812

32 MW_H2

0.002

0.002

0.002

0.002

33 MW_S

0.018

0.018

0.018

0.018

34 MWmix

0.030848

0.030848

0.030848

0.030848

35 P0

1.013E+06

1.013E+06

1.013E+06

1.013E+06

36 PA

4.053E+05

0.4205989

4.053E+05

0.4205989

37 PA0

4.053E+05

4.053E+05

4.053E+05

4.053E+05

38 PE

8.403E+04

0.1846128

17

39 PH2

2.027E+05

0.4872186

2.553E+05

0.4872186

40 rate

0.0232384

9.382E-10

0.0232384

9.382E-10

41 Sum_delta_Cp

260.0818

230.7057

260.0818

230.7111

42 T

823.

651.4233

823.

651.4514

43 T0

823.

823.

823.

823.

44 Ta

653.

653.

653.

653.

45 U

56.784

56.784

56.784

56.784

46 viscosity_A

1.22E-05

1.22E-05

1.22E-05

1.22E-05

47 viscosity_H2

1.221E-05

1.221E-05

1.221E-05

1.221E-05

48 viscosity_mix

1.84E-05

1.84E-05

1.84E-05

1.84E-05

49 viscosity_S

3.059E-05

3.059E-05

3.059E-05

3.059E-05

50 void

0.45

0.45

0.45

0.45

51 W

80.

80.

52 X

0.3050384

0.3050384

53 y

1.

1.675E-06

1.

1.675E-06

54 yA0

0.4

0.4

0.4

0.4

55 yH20

0.2

0.2

0.2

0.2

56 yS0

0.4

0.4

0.4

0.4

Differential equations
1
d(X)/d(W) = rate/FA0
2
d(y)/d(W) = -(alpha/(2*y))*(1+abc*X)*(T/T0)
3
d(T)/d(W) = ((U*a/density_b)*(Ta-T)-rate*dH_Rx)/((FA0)*(Sum_delta_Cp+dCp*X))
Explicit equations
1 T0 = 823
2 K = (2.1e12)*exp((122e3/8.3144)*(1/T0-1/T))
Pa

k = (5.07e-7)*exp((141e3/8.3144)*(1/T0-1/T))
mol/(kg.s.Pa)

KEH2 = 9.72e-10
Pa^-2

KE = 7.33e-5
Pa^-1

KH2 = 3.87e-5
Pa^-1

7
8
9

delta_S = 1
delta_E = 0
FA0 = 0.036
Assuming flow rate for one pipe in the reactor

10 P0 = 101325*10
Pa

11
12
13
14
15

delta_H2 = 0.5
FT0 = FA0+FA0*delta_H2+FA0*delta_S
yA0 = FA0/FT0
abc = yA0*(1+1-1)
PA0 = yA0*P0
Pa

18

16 PA = PA0*(1-X)*y/(1+abc*X)
17 FE = FA0*X
FE=61.8868 mol/s

18
19
20
21

PE = PA0*(delta_E+X)*y/(1+abc*X)
yH20 = FA0*delta_H2/FT0
yS0 = FA0*delta_S/FT0
MW_A = 0.05812
kg/mol

22 Diameter = 0.05
m # For one pipe in the reactor

23 density_c = 984.4
kg/m^3

24 void = 0.45
25 Dp = 0.004572
m

26 PH2 = PA0*(delta_H2+X)*y/(1+abc*X)
27 density_o = 0.6794
kg/m^3

28 rate = k*(PA-(PE*PH2/K))/(1+KEH2*PE*PH2+KE*PE+KH2*PH2)
29 MW_H2 = 0.002
kg/mol

30 viscosity_A = 1.2195e-5
Pa.s

31 viscosity_H2 = 1.2207e-5
Pa.s

32 viscosity_S = 3.0593e-5
Pa.s

33 gc = 1
34 Ac = 3.142*(Diameter^2)/4
35 MW_S = 0.018
kg/mol

36 MWmix = yA0*MW_A+yH20*MW_H2+yS0*MW_S
viscosity_mix =
(yA0*(viscosity_A)*(MW_A^0.5)+yH20*(viscosity_H2)*(MW_H2^0.5)+yS0*(viscosity_S)*(MW_S^0
37
.5))
/(yA0*(MW_A^0.5)+yH20*(MW_H2^0.5)+yS0*(MW_S^0.5))
38 G = FT0*MWmix/Ac
39 beta = (G*(1-void)/(density_o*gc*Dp*void^3))*((150*(1-void)*viscosity_mix)/Dp+1.75*G)
40 alpha = 2*beta/(density_c*(1-void)*Ac*P0)
41 U = 56.784
J/(s.m^2.K)

42 density_b = density_c*(1-void)
43 Ta = 653
K

44 dH_Rx = 105856.1
J/mol

45
46
47
48
49

Cp_A = (89.46e-3)+(30.13e-5)*(T-273)+(-18.91e-8)*((T-273)^2)+(49.87e-12)*((T-273)^3)
Cp_E = (82.88e-3)+(25.64e-5)*(T-273)+(-17.27e-8)*((T-273)^2)+(50.50e-12)*((T-273)^3)
Cp_H2 = (28.84e-3)+(0.00765e-5)*(T-273)+(0.3288e-8)*((T-273)^2)+(-0.8698e-12)*((T-273)^3)
Cp_S = (33.46e-3)+(0.6880e-5)*(T-273)+(0.7604e-8)*((T-273)^2)+(-3.593e-12)*((T-273)^3)
dCp = (Cp_E+Cp_H2-Cp_A)*1000
J/mol.K

19

50 Sum_delta_Cp = (Cp_A+delta_H2*Cp_H2+delta_S*Cp_S)*1000
J/mol.K

51 L = W/(density_c*(1-void)*Ac)
52 a = 2*3.142*(Diameter/2)*L

From the Polymath results, flow rate of isobutylene, FE for one pipe in the reactor is
0.0109814 mol/s while the isobutylene production from the reactor is 61.8868 mol/s.
No. of pipesrequired=

61.8868
=5636 pipes
0.0109814
20

(0.05)
For single pipe, Area=
=1.9635 103 m2
4
For reactor , Area=5636 ( 1.9635 103 )=11.0663 m 2

For reactor , Diameter=

4 (11.0663)
=3.7537 m

Hence, 5636 pipes are required in the fixed bed reactor with a diameter of 3.7537 m.
Also, form the polymath graph, the optimum conversion for the reaction is selected at
X=0.28.

STAGE 3
5.0 Estimation of Diffusion- and Reaction-Limited Regimes
Weisz-Prater Criterion for Internal Diffusion:
C = 21
where k=k ' P0 MW mix
7

5.07 10 mol
0.030848 kg

1013250 Pa
=0.01585 s1
kg s Pa
mol

R=

D P 0.004572
=
=2.286 103 m
2
2

D AB@ 573 K
R

=0.133 s1

CITATION Seb 990 (Sebastian C . Reyes J . H . , 1997)

3 2

D AB@ 573 K =( 2.286 10 ) ( 0.133 )=6.9503 10 m /s

D AB@ 823 K =D AB@ 573 K

823
573

1.75

( )

823
=( 6.9503 107 )

1.75

( 573 )

21

1.3097 10 m /s
The typical value of c =0.8~ =3.0
=0.45
D AB c (1.3097 106 )(0.45)(0.8)
7 2
De=
=
=1.5716 10 m / s
~
3.0

1=R k /D e= ( 2.286 103 )

0.01585
=0.7260
1.5716 107

3
3
coth 11 ) =
( 0.7260 coth ( 0.7260)1 )=0.9665
2( 1
1
0.72602
2

C = 1=0.9665(0.7260) =0.5094
Since C 1, there is no internal diffusionlimitation .

Mears Criterion for External Diffusion:

Sh ' =

kc D p
D AB 1

( )

where DP =0.004572 m
D AB=1.3097 106 m2 / s
=0.45
0=0.6794 kg /m3
= mix=1.8404 105 Pa s

22

D2 (0.05)
A c=
=
=1.9635 103 m2 (for one of the pipes PBR)
4
4

C A 0= y A 0

P0
10
=0.4
=59.2716 mol/m 3
3
RT0
( 0.082 10 ) ( 823 )

obtained
X =0.28( polymathstagetwo)

0=

F A0
0.036
=
=6.0737 104 m3 / s
C A 0 59.2716

U=

0 6.0737 104
=
=0.3093 m/ s
Ac 1.9635 103

0 D p U (0.6794)(0.004572)(0.3093)
=
=52.2035

1.8404 105

' =

52.2035
=
=94.9155
(1) 10.45

Sc=

1.8404 105
=
=
=20.6831
D AB 0 D AB 0.6794 (1.3097 106 )

'

' 1 /2

1/ 3

Sh =1.0 ( ) Sc =1.0 ( 94.9155 )

kc=

1 /2

(20.6831 )1 /3=26.7428

Sh' D AB ( 1 ) 26.7428 ( 1.3097 106 ) ( 10.45 )

=
Dp
0.004572 ( 0.45 )
3

9.3632 10 m/s

r ' A b Rn
k c C Ab

where b=

c
984.4
=
=1789.8181 kg /m3
1 10.45
23

R=2.286 10 m
n=1(first order)
C Ab =C A 0 ( 1 X )=C A 0 ( 1X )=59.2716 ( 10.28 ) =42.6756 mol /m3
k c =9.3632 103 m/ s
obtained
3
r A =3.2690 10 m /kg s ( polymath stage two)
'

r ' A b Rn (3.2690 105 )(1789.8181)(2.286 103)(1)

=
k c C Ab
(9.3632103)( 42.6756)
3.3473 104

Since

r ' A b Rn
< 0.15,external mass transfer effects can be neglected .
k c C Ab

Hence, the reaction is only affected by surface reaction.

6.0 Reference

1. A. Rosjorde, S. K. (2007). Minimizing the entropy production in a chemical

process for dehydrogenation of propane. Energy 32, 335343.
2. Bruce E. Poling, G. H. (2008). Perry's Chemical Engineers' Handbook 8th
Edition. United States of America: McGraw Hill.
3. Domenico Sanfilippo, I. M. (n.d.). Dehydrogenation Process. 687-669.
4. Sanna M. K. Airaksinen, M. E. (2002). Kinetic Modeling of Dehydrogenation of
Isobutane on Chromia. Ind. Eng. Chem. Res. 2002, 41, 5619-5626.
5. Sebastian C. Reyes, J. H. (1997). Frequency Modulation Methods for Diffusion
and Adsorption Measurements in Porous Solids. J. Phys. Chem B, 614-622.
6. Richard M. Felder, W. (2005). Elementary Principles of Chemical Processes 3rd
Edition. United States of America: John Wiley & Sons, Inc.

24

7. H. Scott Fogler (2006). Elements of Chemical Reaction Engineering 4 th Edition.

United United States of America: Pearson Education, Inc.

25