4.1.

4 Reaction Kinetics

The reaction is an endothermic and kinetically controlled. It is a heterogeneous

catalytic reaction which occurs in vapor phase over the catalyst. The reaction kinetics of
dehydrogenation of IPA to produce acetone is first order with respect to concentration of IPA
[20] and can be estimated from the following equation [21].

−r i=k o e−E / RT C i

where,

-ri = rate of disappearance of IPA

T = reaction temperature, 350°C = 623.15 K

E = Activation energy = 72.38 MJ/kmol [20]

ko = Arrhenius constant = 3.51 × 105 m3 gas / m3 bulk catalysts [20]

4.1.5 Performance Equation for Reactor

Performance equation for PFR is given as: [21].

X
W dX
=∫ i
F io 0 −ri

where,

W = weight of catalyst, kg

Fio = input concentration of IPA, kmol/h

Xi = conversion of IPA

-ri = rate of disappearance of IPA

The rate equation was written in terms of conversion as given below [18].

1−X i
−r i=k Cio ( )
1+ ϵ i X i

where,
 −E 6
k = reaction constant, sec-1 = k e RT = 3.51 × 105 × e−72.38 ×10 /(1000× 8.314 ×623.15)
o

= 0.30075 s-1

Values of E, T and k were already mentioned in section 4.1.4.

As our reaction is as given in Equation 8;

ϵi = (2-1)/1 = 1

From the material balance, we calculated Fio = 98.4 kmol/h

Cio = Fio/ V; where V is calculated in litres using density of IPA

= 0.01810 kmol/l

Putting all the values in rate equation we arrived at the relationship as given below.

−r i=0.30075× 0.01810 ׿

Now, we create Table 4.1 for each value of Xi ranging from 0 to 0.9 and calculate the value
of –ri respectively.

Table 4.1: Table showing calculated values of –Xi and -1/ri

Sr. No. Xi -ri -1/ri

1. 0 0.003939 253.87
2. 0.1 0.003322 310.56
3. 0.2 0.002626 380.80
4. 0.3 0.002121 471.47
5. 0.4 0.001688 592.41
6. 0.5 0.001313 761.61
7. 0.6 0.000984 1016.260
8. 0.7 0.000695 1438.849
9. 0.8 0.000438 2283.105
10. 0.9 0.000207 4830.918

The following graph as shown in Fig. 4.2 was obtained.

 1
Fig. 4.2: Graph between X i and
−r i

The area under this curve was found by Simpson’s rule.

Area =b-a/3n(253.87+4(310.56 + 471.47+761.67+1438.849) + 2(380.80 +

512.417+1016.2601 + 2283.105) +4830.910)

Area = 851.99= 852

Xi

Hence, ∫ dX i /−r i = 852

0

So, using performance equation, weight of catalyst, W = 98.4 × 852 = 83836.8 kg

4.1.6 Volume of Catalyst

Now, we know the weight of catalyst with the help of performance equation for the
case of fixed bed plug flow catalytic reactor. Using the density of copper particles, we can
calculate the volume of catalyst bed as well.

Density of copper particles = 8940 kg/m3 [24]

Volume of catalyst bed, Vc = 83836.8/8940 = 9.38 m3

4.1.7 Space Time

Time needed to heat the one reactor volume is called space time. It is given by the
following formula [21].
Space time = W Cio/ Fio

= 83836.8 × 0.01810 / 98.4 = 15.4 kg.hr/m3

4.1.8 Volume of reactor

The catalyst used in our case is spherical copper particles. For fixed bed reactors, the
spherical particles must have diameter in range of 3 to 7 mm and porosity in range of 0.4 to
0.41 [22]. So, we consider using the spherical copper particles of diameter 3mm with
porosity, Ψ = 0.4. Volume of reactor is given by the following formula [23].

Vc
V r=
1−Ψ

= 9.3/ (1-0.4) = 15.5 m3

4.1.9 Number of Tubes

For this, the preferred lengths of the tubes are: 6, 8, 12, 16, 20, 24 ft [24].

Length of tube selected = 24 ft = 7.32m

There is an assumption to prevent the deviation from plug flow as given below [25].

Dt/ Dp≥ 15

where,

Dt = diameter of tube and Dp = diameter of particle

We assumed diameter of tube = 75 mm

Dt/Dp = 75/3 = 25 > 15

Volume of 1 tube = 3.14 × 0.075 × 0.075 × 7.32 / 4 = 0.0323 m3

No of Tubes = Total volume / volume of 1 tube = 15.5/ 0.0323 = 479.876 = 480 tubes

4.1.10 Height of Reactor (Shell)

 Length of the tubes was assumed to be 7.32 m. By using the following assumptions,
we can calculate the shell height.

Allowance of the reactor height is 20 – 50 % of shell height [20].

We assume allowance of 30 % of the tube height.

Shell height = 7.32 + 2 × 0.30 (7.32) = 11.712 m

4.1.11 Diameter of Reactor

Diameter of shell is calculated using Harvey equation [26].

2
( D s−K 1 ) π
NT=
[ 4 ]
+ K 2 −Pt ( Ds −K 1 )( nK 3 + K 4 )
2
1.23 ( Pt )

where,

NT = No. of tubes = 480

PT = pitch of tube = 1.25 × tube diameter [26]

= 1.25 × (75/1000) = 0.09375

We assumed to use tubes in triangular form. We used the values of K1, K2, K3 and K4 from the
literature [26].

K1 = 1.08, K2 = -0.9, K3 = 0.69 and K4= -0.3

n = no. of passes = 1

Putting all the values,

Ds= 3.3443 m

For plug flow reactor; length to diameter ratio shall lie between 3 and 5 [25].

For our desired reactor,

Length = 11.712 m

Diameter = 3.3443m
Length to diameter ratio for desired reactor = 11.712/ 3.3443 = 3.5

Hence, lies within allowable limit.

4.1.12 Reactor Thickness

Our reactor is an internal pressure vessel since its working at the pressure of 1.8 bars.
So, the formula for thickness of internal pressure vessel is given as below [27].

P×D
t=
( )
( f ×J )−0.6× P
+C

where,

t = thickness

P = pressure at which reactor is operating = 1.8 bars = 26.107 psi

D = diameter of the reactor, in inches = 3.3343 m = 131.272 in.

f = allowable maximum stress = 11300 psi [28]

J = joint efficiency = 0.8 in case of carbon steel material [29]

C = corrosion allowance = 3 mm [29]

Putting all the values, t = 458 inches = 11.633 mm

Hence, the next standard value of thickness of reactor shell is 12 mm.

4.1.13 Head Selection and Design

The ends of the cylindrical vessel are closed by heads. These are of various types. We
assume to the heads to be torispherical type head.

Thickness of head is calculated using given formulas [25].

Pi R C C S
e=
2 Jf + Pi ( C s−0.2 )

R
C S=
1
4 ( √ )
3+ C
RK
where,

Rc = crown radius = diameter of shell = 3.34m

Rk = knuckle radius = 0.06 Rc [25]

= 0.2 m

J = 0.8

f = stress factor = 80 (for carbon steel)

Putting all values, the following results were obtained.

CS= 31.5416

e = 0.76 mm

4.1.14 Pressure Drop Calculations

There are three equations for the calculation of pressure drop as mentioned below [30].

 Ergun’s equation
 Kozeny - Carman equation
 Blake - Plummer equation

It is pointed out that Ergun’s equation is applied to calculate the pressure drop across
fixed bed consisting of small size particles ( Dp = 25 mm) [26]. Also, we have assumed the
diameter of spherical copper particles to be 3 mm. But, the choice of equation would also
depend on the packed bed Reynolds number and flow regime.

Ergun’s equation is represented as mentioned below [28].

2
∆ P 150 μ G ( 1−∈ ) G 2 (1−∈ )
= +1.75
L K . g . ρ D 2 ∈3 K . g . ρ D ∈3

where,

L = length of reactor = 11.712 m = 38.5 ft

µ = viscosity of gaseous feed (IPA) = 0.000564 lb/ft.hr [28]

G = mass velocity (Calculations of mass velocity is mentioned further in the section)

ρ = feed density (IPA) = 0.1215 lb/ft3[28]

D = DP = diameter of particle = 3 mm = 0.0009146 ft

ϵ = Ψ = porosity = 0.4

g = gravitational constant = 4.17 × 108lb.ft/lb.h2 [31]

K = conversion factor = 0.8

The first part of equation represents laminar flow and the second part represents
turbulent flow. If the fixed bed Reynolds number comes to be less than 10, it will be laminar
regime and Ergun’s equation reduces to Kozeny – Carman equation that is given below [30].

2
∆ P 150 μ G ( 1−∈ )
= +1.75
L K . g . ρ D 2 ∈3

Reynolds number (Re*) would be calculated as follows.

ρGD
ℜ¿ = =( 0.0009146 ×14.482 ×0.1215 ) ÷ ( 0.000564 ×0.6 )=4.75
( 1−∈ ) × μ

Hence, it is the case of laminar flow regime and Re* is less than 10. Hence, we use
Kozeny – Carman equation.

To calculate mass velocity (G), we first needed to find area through which feed
passes. That area would be area of tubes subtracted from area of reactor.

That was calculated as:

3.343 2 0.075 2
( (
π×
2 ) ) ( ( )
×11.312 −480 π ×
2 )
× 7.32 =83.766 m2

( 98.4 × 60.01 )
So, G= =70.599 kg/m2.h = 14.482 lb/ft2.h
83.766

So, putting all the values in Kozeny – Carman equation, the pressure drop was calculated.

ΔP = 1.774 psi = 0.122 bars (which is 6.77% of operating pressure).

The Results of the design of reactor are tabulated in Table 4.2

 Table 4.2: Results of reactor design

Sr. No. Type of reactor Shell & tube fixed bed reactor
1. Operating temperature 350°C
2. Operating pressure 1.8 bars
3. Volume of reactor 15.5 m3
4. Volume of catalyst 9.38 m3
5. Weight of catalyst 83836.8 kg
6. No. of tubes 480
7. Shell height 11.712 m
8. Diameter of shell 3.34 m
9. Thickness of shell 12 mm
10. Pressure drop 0.122 bars
11. Head type Torispherical head
12. Support type Bracket support