Kinetic data of reaction from reference book

MEK is produced by dehydrogenating 2-butanol in a catalytic reactor. The reaction is

endothermic and reversible, and follows the stoichiometry shown in equation ().

C4H10O C4H8O + H2 Hro = 73900 kJ/kgmol

Rate equation:
P P
C(PAi Ki Hi ) kmol
K
rA = K P rA in , P in bar
PKi (1+KA PAi + AK Ai ) m2 .h
PKi

The surface area of the catalyst is 6/dp which for sphere particles 0.32 cm diameter gives
S = 6*102/0.32 = 1875 m2/m3 of particles.

For a random packed bed of cylindrical particles the porosity is =0.393, then the surface
area per unit volume of packed bed will be:

m2
= S(1 ) = 1875(1 0.393) = 1138.125 3
m
P P
1138.125C(PAi Ki Hi ) kmol
K
rA = KAK PAi rA in , P in bar
PKi (1+KA PAi + ) m3 .h
PKi

5964
log C = + 8.464
Ti

3425
log K A = + 5.231
Ti

486
log K AK = Ti
0.1968

kmol
C in , when
m2 . h
1
K A in , K AK is dimensionless, Ti in K
bar

2790
Equilibrium constant: log K = + 1.510 log Ti + 1.871 K in bar, Ti in K
Ti
How we enter values into hysys

Rate equation:
P P
C(PAi Ki Hi ) k k
rA = K
K
P K = k forward = k f
PKi (1+KA PAi + AK Ai ) backward b
PKi

P
C Ai Kb PHi
PKi
rA = K P
1+KA PAi + AK Ai
PKi

Forward reaction:

5964
log C = + 8.464
Ti

5964
C = 10 Ti + 108.464
5964
1138.125C = 1138.125 10 Ti + 1138.125 108.464

5964 5964
log(1138.125C) = log(1138.125) + + log(1138.125) + 8.464 = +
Ti Ti
14.57638

ln x
log x = ln 10 ln x = 2.3 log x

13717.2
13717.2
ln C = + 19.4672 C = 284772165.7e Ti
Ti

E
A=284772165.7 = 13717.2 E = 114044.8 j/mol
R

13717.2
13717.2
ln k f = + 33.52567 k f = 363090717863118e Ti
Ti

Backward reaction:
2790
log K = + 1.510 log Ti + 1.871
Ti

6417
6417
ln K = + 7.9879 ln Ti + 4.3033 K = 73.943 T 7.9879 e Ti
Ti

13717.2
7300.2
C 284772165.7e Ti

kb = = 6417 = 3851217.9 T 7.9879 e Ti
K
73.943 T 7.9879 e Ti
 E
A=3851217.9 =-7.9879 = 7300.2 E = 60693.863 j/mol
R

13717.2
7300.2
kf 363090717863118e Ti
7.9879
kb = = = 4910386789212.60 T e Ti
K 6417

73.943 T 7.9879 e Ti

First constant in denominator:

3425
log K A = + 5.231
Ti

7877.5
7877.5
ln K A = + 12.0313 K A = 167929.58e Ti
Ti

E
A=167929.58 = 7877.5 E = 65493.535 j/mol
R

Second constant in denominator:

486
log K AK = 0.1968
Ti

1117.8
1117.8
ln K AK = 0.45264 K AK = 0.63595e Ti
Ti

E
A=0.63595 = 1117.8 E = 9293.39 j/mol
R
Trial from plant design

MEK is produced by dehydrogenating 2-butanol in a catalytic reactor. The reaction is

endothermic and reversible, and follows the stoichiometry shown in equation ().

C4H10O C4H8O + H2 Hro = kJ/mol

The reaction rate is dependent on partial pressures and temperatures according to the
relation in equation () where A stands for 2-butanol, K for MEK and H for hydrogen.

k1 pA p1
K k2 pH
rA =
1+KA pA +KAK pA p1
K

The reaction rate constants k1 and k2 and adsorption constants KA and KAK are dependent
on the temperature as shown in Table and pA, pK and pH are the partial pressures
expressed in bar
13717.2
kmol
C = 284772165.7e Ti
C in
m2 .h

1000 13717.2 13717.2 mol

1 = 284772165.7e Ti = 79103379.36e Ti 1 in
60 60 m3 . s
7300.2 kmol

= 3851217.9 T 7.9879 e Ti in
m3 . . h

1000 7300.2 7300.2 mol

2 = 3851217.9 T7.9879 e Ti = 1069782.75T7.9879 e Ti
60 60 m3 . . s

7877.5
1
K A = 167929.58e Ti
bar

1117.8
K AK = 0.63595e Ti
The construction of the equilibrium curve for the MEK process from plant design

k1 pA p1
K k2 pH
rA =
1+KA pA +KAK pA p1
K

rA =0 k1 pA p1
K k 2 pH =0

pi Fi
yi = =
P Ftot

FA FH
k1 k2 P=0
FK Ftot
(1Xeq )
FA = FA0
(1+Xeq)

X eq
FH = FK = FA0
1 + X eq

(1 + X eq )
Ftot = FA + FH + FK = FA0
(1 + X eq )

1 X eq X eq
k1 k2 P=0
X eq 1 + X eq

k2
(1 X eq )(1 + X eq ) = PX 2
k1 eq

1
=

1+ 2
1
Catalyst from reference book

Perona & Thodos in their experimental work to get kinetic data, employed a single tube reactor
1.25 cm in diameter packed with brass beads 0.32 cm in diameter. Although brass spheres are
acceptable for an investigation on pilot scale equipment, the cost of fabricating catalyst particles
of this shape is prohibitive for the quantity required for commercial scale reactors.

However, it was essential to select a particle shape that closely resembled spheres to ensure
that the rate equations developed by Perona & Thodos remain applicable. Therefore right
circular cylinders were chosen (0.32 cm diameter, 0.32 cm length) because they have the same
specific surface voidage fraction and exhibit similar pressure drop characteristics to those of
spheres. Fabrication costs are relatively low since the particles would be manufactured by the
cutting of extruded brass rod in one operation.

***In this experimental reactor some channeling may occur since the ratio (tube
diameter/catalyst particle diameter) is only 4:1. However these authors conclude their
publication with an example calculation in which they specify a tube diameter of 7.5 cm with
catalyst particles 0.32 cm in size. Hew it is necessary to estimate a suitable reactor tube
diameter for the commercial scale reactor.

***The reaction is endothermic so that the tube axis temperature will be the minimum and
reaction rate was very slow below 300C. Furthermore cracking becomes significant above
500C and therefore it is necessary to control the reaction between these temperatures.

The catalyst bed consists of cylindrical brass particles with properties given in Table ().

The catalyst activity decays quickly at too high temperature (above 500C) which limits the
maximum temperature of the heating utility.

diameter dp 0.0032 m
length 0.0032 m
density p 8500 kg/m3
Thermal conductivity Kp 125.4 w/(m.k)
Heat capicaty Cp 0.38 kJ/(kg.k)
Porosity of the bed 0.393
Equilibrium conversion from reference book

AK+H

1-Xeq Xeq + Xeq

pA0 (1 Xeq)
pA =
(1 + Xeq)

pA0 (c + Xeq)
pH = pK =
(1 + Xeq)

= yAO = 1 (1 + 1 1) = 1 c = 0

pK pH pA0 Xeq2 pA0 Xeq2

= = =
pA (1 Xeq)(1 + Xeq) 1 Xeq2

2790
Equilibrium constant: log K = + 1.510 log Ti + 1.871 K in bar, Ti in K
Ti

By combining last two equations, we can evaluate equilibrium conversion at different

temperatures.
 1.2 equilirium curve
1

0.8
Xeq

0.6

0.4

0.2

0
0 100 200 300 400 500 600
temperature (C)

Figure (): Equilibrium curve at 3.5 bar pressure

Rate law as function of conversion and volume of CSTR and PFR reactors

k1 pA p1
K k2 pH
rA =
1+KA pA +KAK pA p1
K

pA0 (1 x)
pA =
(1 + x)

pA0 (c + x)
pH = pK =
(1 + x)

= yAO = 1 (1 + 1 1) = 1 c = 0

(1 x) p x
k1 k 2 A0
(1 + x)
rA = pA0 (1 x) (1 x)
1 + KA + K AK
(1 + x)

-The volumes of a CSTR and PFR reactors are calculated according to next equations
respectively:
 FA0 FA xFA0
V= =
rA rA
x
FA0 dx
V=
rA
0

Where, V is the reactor volume, m3, FA0 is the initial flow rate of the limiting reactant,
kmol/s, FA is the final flow rate of the limiting reactant, kmol/s, and rA is the reaction rate
with respect to the limiting reactant, kmol/m3.s and x is the conversion.

-We learn in chemical reaction engineering that for isothermal reactions greater than zero
order;

CSTR volume usually > PFR volume

For same conversion and reaction conversion (T, P, flow rate, etc.)

The reason the isothermal CSTR volume is usually greater than PFR volume is that:

CSTR is always operating at the lower reaction rate, on other hand, PFR starts at high rate at
the entrance and gradually decreased to the exit rate, thereby require less volume because
volume inversely proportional to the rate.

This is

Just talking
-Choosing a suitable reactor type depends on many factors such as the mode of operation, the
capacity of the plant, the number of raw materials and products, and the reactor cost.

The high capacity of MEK production process ( million kg/yr) and the use of one raw
material make it suitable to use continuous reactors where they usually selected for large-
scale production processes that use a single or only a few raw materials.
CSTR and PFR reactors can be used as a continuous reactor.
-Many factors affected the selection of the appropriate reactor type (CSTR or PFR), mainly;
safety issues, volume and cost.
Volume
The volumes of a CSTR and PFR reactors are calculated according to equations () and ()
respectively:

FA0 FA
V=
rA
x
FA0 dx
V=
rA
0
Where, is the reactor volume, m3, FA0 is the initial flow rate of the limiting reactant,
kmol/s, is the final flow rate of the limiting reactant, kmol/s, and is the reaction rate
with respect to the limiting reactant, kmol/m3.s and x is the conversion

PFR reactor Provide more liquid hold up than CSTR. Therefore, it needs less volume for a
chemical reaction as a result.

Cost

The cost of the reactor depends on the volume and the amount of catalyst used, as shown
in the previous section CSTR has a larger volume and it needs a greater amount of catalyst,
comparing it with PFR that uses a less amount due to its small volume. Thus; the cost of
CSTR will be much higher.

Safety

From safety point of view continuous stirred tank reactors will have a sealing problem due
to the presence of agitators which considered as a continuity maintenance problem. On the
other hand PFR reactor doesnt have this problem

Pfr /fixed bed /shell and tube reactor

Reactor design
1-Temperature

The PFR can be modeled as isothermal, in this case, the reactor temperature is specified

2-Pressure Drop

In heterogeneous reactions, a proper accounting for the effects of pressure drop on the
reaction system should be taken in consider, especially in the reactions that involves a gas
phase reactant, where the concentration of the reacting species is proportional to the total
pressure,

***Across each reactor,the pressure drop according to Eurgens equation:

dP (1 cat )2 u0 (1 cat )u20

= 150 1.75
dL cat 3 d2P cat 3 dP
Where, P denotes pressure, Pa, denotes the fluid viscosity, Pa.s, is the packing porosity,
u0 denotes the superficial velocity, m/s, dp is the packing particle diameter, m, is the fluid
density, kg/m3, and g is the gravitational acceleration constant, m/s2.
It is observed from equation () that the pressure drop across the packed bed depends on
the packing size and fluid properties, under turbulent conditions the second part of the
equation dominates.

3-Catalyst

Volume and catalyst load

The design of a PFR reactor includes the determination of the reactor volume and the catalyst
load.
The volume of a PFR reactor is given by:
x
FA0 dx
V=
rA
0

Where, is the reactor volume, m3, FA0 is the initial flow rate of the limiting reactant, kmol/s,
and is the reaction rate with respect to the limiting reactant, kmol/m3.s.
And the amount of catalyst used is calculated according to equation ()

W = PV(1 cat )
Where, W is the catalyst weight, kg, is the catalyst density, kg/m3.
Once the amount of catalyst and the reactor volume are calculated the catalyst load is
determined using the following equation():

=

Where, U is the catalyst loading, kg/m3.

Depending on how the reactor(s) operates, the need for heating or cooling can differ. In the
case of adiabatic reactors no external heating or cooling is needed in principle and the best
reactor operating conditions can be established regardless of process heat integration aspects
(intercooling or reheating between multiple reactor stages can however impact the process heat
recovery potential). Not all reactions can be technically carried out in adiabatic reactors and
external heating or cooling is often necessary to ensure process safety, increase the conversion
of the feed or to increase the selectivity of the desired product (Fogler, 2006; Smith, 2007).

Although there are many reaction technologies, reactors are commonly categorized into three
major sets corresponding to ideal models and specific behaviours. These are batch reactors,
continuous-stirred tank reactors (CSTR) and tubular reactors. Batch reactors are time-dependent
and are suited for small scale production. CSTRs and tubular reactors are operated continuously
and are usually selected for large scale production (Sinnott & Towler, 2009).

Tubular reactors
-Tubular reactors are used in the industry since they are relatively easy to maintain due to no
moving parts and usually have the highest conversion per reactor volume of other types of
reactor (Fogler, 2006, p. 23). Tubular reactors can be used either for homogenous or
heterogeneous reaction chemistry. Homogenous reactors have only one phase in the reaction
environment and heterogeneous have more than one. One common type of heterogeneous
reactor is the packed bed reactor which is essentially a tubular reactor that is packed with solid
catalyst particles (Fogler, 2006, p. 23).

-Typical temperature profiles in adiabatic tubular reactors can be seen in Figure

To keep the reaction rate high and therefore increase the reaction conversion of with a given
reactor cooling of exothermic reactors and heating of endothermic reactors is employed

As a consequence the heat transfer between the reactive stream and utility is strictly connected
with the reaction kinetics which therefore cannot be ignored when designing the utility system.

Synthesis and design approach

First the type of reactor has to be defined. It can be continuous or batch. It can be a stirred tank
or a tubular reactor. It can be un-packed, a packed bed or a fluidized bed. It can be adiabatic,
isothermal, heated or cooled.

Dimensions