Process Modelling, Simulation and Control for Chemical

Engineering. Solved problems. Chapter 3: Examples of

mathematical models of chemical engineering systems.
This document contains my own solutions to the problems proposed at the
end of each chapter of the book Process Modelling, Simulation and Control
for Chemical Engineers Second Edition, by William L. Luyben. At such, I
cant guarantee that the proposed solutions are free from errors. Think about
them as a starting point for developing or as a means of checking your own
solutions. Any comments or corrections will be appreciated. Contact me at
francisco.angel.rod@gmail.com

Problem 1
A fluid of constant density is pumped into a cone-shaped tank of total volume
HR2 /3 (Figure ??). The flow out of the bottom of the tank is proportional
to the square root of the height h of liquid in the tank. Derive the equations
describing the system.

Figure 1: Cone-shaped tank.

Solution
The volumetric balance (constant density) for the fluid inside the tank is
then:

dV
= F0 K h
dt
Calling r to the radius of the fluid cone inside the tank, and if is the angle
formed by the cone-shaped tank and the horizontal, we have:
tg =

H
h
=
R/2
r/2

The volume of fluid inside the tank is:

hr2

V =
=
3
3
1

R
H

2

h3

The last equation, together with the volumetric balance expression, allow to
solve for h and V as a function of time.

Problem 2
A perfect gas with molecular weight M flows at a mass flow rate W0 into a
cylinder through a restriction. The flow rate is proportional to the square root
of the pressure drop over the restriction:
p
W 0 = K 0 P0 P
where P is the pressure in the cylinder and P0 is the constant upstream pressure.
The system is isothermal. Inside the cylinder, a piston is forced to the right as
the pressure P builds up. A spring resist the movement of the piston with a
force that is proportional to the axial displacement x of the piston.
Fs = Ks x
The piston is initially at x = 0 when the pressure in the cylinder is zero.
The cross-sectional area of the cylinder is A. Assume the piston has negligible
mass and friction.
1. Derive the equations describing the system.
2. What will the steady state piston displacement be?

Figure 2: Piston + cylinder.

Solution
Because the mass and friction of the cylinder are negligible, we can assume
that forces at each side of him are always balanced. The pressure at the spring
side of the cylinder, according to Figure ??, is atmospheric, so the initial pressure
must be atmospheric (the barometric value is 0). A force balance for the piston
gives:
Patm + Ks x/A = P
The volume variation of the cylinder gives:



p
P0 Patm Ks x/A
W0
RT
P0 P
RT
dx
=
=
=
A
dt

M
P
M
Patm + Ks x/A
2

dx
=
dt

RT
M

p

P0 Patm Ks x/A
APatm + Ks x

with initial condition xt=0 = 0.

The steady state piston displacement will be reached when the volume no
longer changes:
P0 Patm
x=

Ks x
=0
A

A(P0 Patm )
Ks

Problem 3
A perfectly mixed, isothermal CSTR has an outlet weir. The flow rate over
the weir is proportional to the height of liquid over the weir (how ) to the 1.5
power. The weir height is hw . The cross sectional area of the tank is A. Assume
constant density. A first order reaction takes place in the tank:
k

1
A
B

Derive the equations describing the system.

Figure 3: CSTR.
Solution
The total continuity equation gives (assuming constant density of the process
fluid):
dhow
A
= F0 KF (how )3/2
dt
The A component continuity equation gives:
A

d(how CA )
= F0 CA0 KF (how )3/2 CA k1 Ahow CA
dt

Problem 4
In order to ensure an adequate supply for the upcoming set-to with the Hatfields, Grandpa McCoy has begun to process a new batch of his famous Liquid
Lightning moonshine. He begins by pumping the mash at constant rate F0 into
an empty tank. In this tank the ethanol undergoes a first-order reaction to form
a product that is the source of the high potency of McCoys Liquid Lightning.
Assuming that concentration of ethanol in the feed, C0 , is constant an that the
operation is isothermal, derive the equations that describe how the concentration C of ethanol in the tank and the volume V of liquid in the tank vary with
time. Assume perfect mixing and constant density.
Solution
The total continuity equation gives:
dV
= F0
dt
The ethanol continuity equation gives:
d(V C)
= F0 C0 kV C
dt
With initial conditions: Vt=0 = 0 and Ct=0 = C0 .

Problem 5
A rotating metal drum heat exchanger is half submerged in a cool stream, with
its other half in a hot stream. The drum rotates at a constant angular velocity
(radians per minute). Assume TH and TC are constant along their respective
sections of the circumference. The drum length is L, thickness d, and radius R.
Heat transfer coefficients in the heating and cooling zones are constant (UH and
UC ). Heat capacity CP and density of the metal drum are constant. Neglect
radial temperature gradients and assume steady state operation.
1. Write the equations describing the system.
2. What are the appropiate boundary conditions?
Solution
Assumptions:
1. The entalphy of the heat exchanger material can be represented as h =
Cp T .
2. The energy transport by conduction in the direction is negligible.
3. The thickness is much smaller than the exchanger radius.
For a time interval t, the energy entering and leaving a volume of size
dRL is:
4

Figure 4: Rotating heat exchanger.

Entering: tRdLCp T
Leaving: tRdLCp T +

dT
d

+ 2tLRUj (T Tj )

With Uj and Tj corresponding to the heat transfer coefficient and temperature at the cooling or heating zone.
An energy balance in the cooling zone, gives, after dividing by tRL:
dT
wdCp = 2UC (T TC )
d
dT
UC (T TC )
=
d
wdCp
The analogous energy balance for the heating zone gives:
dT
UH (T TH )
=
d
wdCp
The energy balance for the cooling zone applies in the range : [/2, ],
whereas the energy balance for the heating zone applies in the range : [0, /2].
Solution of the differential equations gives two integration constants, which are
determined applying the following boundary conditions:
Th (0) = Tc (2)
Th (/2) = Tc (/2)

Problem 6
Consider the system that has two stirred chemical reactors separated by a plugflow dead time of D seconds. Assume constant holdups (V1 and V2 ), constant
throughput (F ), constant density, isothermal operation at temperatures T1 and
T2 , and first order kinetics with simultaneous reactions:
k

1
A
B

2
C
A

No reactions occur in the plug-flow section. Write the equations describing the
system.

Figure 5: CSTRs separated by a dead time.

Solution
The species balances for the first reactor are:
dCA,1,t
= F CA0 F CA,1,t k1,T1 V CA,1,t k2,T1 V CA,1,t
dt
dCB,1,t
V
= F CB,1,t + k1,T1 V CA,1,t
dt
dCC,1,t
V
= F CC,1,t + k2,T1 V CA,1,t
dt
The species balances for the second reactor are equivalent, but using a time
variable t equal to t + D:
V

dCA,2,t
= F CA,1,t F CA,2,t k1,T2 V CA,2,t k2,T2 V CA,2,t
dt
dCB,2,t
= F CB,1,t F CB,2,t + k1,T2 V CA,2,t
dt
dCC,2,t
V
= F CC,1,t F CC,2,t + k2,T2 V CA,2,t
dt

Problem 7
Consider the isothermal hydraulic system sketched below. A slightly compressible polymer liquid is pumped by a constant-speed, positive displacement pump
so that the mass flow rate W1 is constant. Liquid density is given by:
= 0 + (P P0 )
where 0 , , and P0 are constants, is the density, and P is the pressure.
Liquid is pumped through three resistances where the pressure drop is proportional to the square of the mass flow: P = RW 2 . A surge tank of volume
V is located between R1 and R2 and is liquid full. The pressure downstream of
R3 is atmospheric.

1. Derive the differential equation that gives the pressure P in the tank as a
function of time and W1 .
2. Fin the steady state value of tank pressure P .

Figure 6: Hydraulic system.

Solution
A mass balance for the tank gives:
d
= W1 W2
dt
The balance can be re-stated in terms of the pressure, using the expression
for the liquid density and the expression for the pressure drop:
r
dP
P
V
= W1
dt
R2 + R3
V

The steady state value for the pressure is P = W12 (R2 + R3 ).

Problem 8
Develop the equations describing an inverted batch distillation column. This
system has a large reflux drum into which the feed is charged. This material
is fed to the top of the distillation column (which acts like a stripper). Vapor
is generated in a reboiler at the base. Heavy material is withdrawn from the
bottom of the column. Derive a mathematical model of this batch distillation
system for the case where the tray holdups cannot be neglected.
Solution
The inverted batch distillation column is shown in Figure ??. The following
assumptions are made in order to develop the model:
Vapor hold up is negligible.
Trays are ideal.
The column operates with a binary mixture.
Tray contents, reflux drum and reboiler contents are perfectly mixed.
The mole conservation equations (both total and by component) for the Nth
tray are:

Figure 7: Inverted batch distillation column.

d(MN T xN T )
= RxD LN T xN T + VN T 1 yN T 1 VN T yN T
dt
dMN T
= R LN T + VN T 1 VN T
dt
The energy conservation conservation equation for the Nth tray is:
dMN T hN T
= RhD LN T hN T + VN T 1 HN T 1 VN T HN T
dt
The mole conservation equations (both total and by component) for the
reflux drum are:
d(MD xD )
= VN T yN T RxD
dt
dMD
= VN T R
dt
The energy conservation equation for the reflux drum is:
d(MD hD )
= VN T HN T RhD + QD
dt
The mole conservation equations (both total and by component) for the
reboiler are:
8

d(MR xR )
= L1 x1 VR yR P xR
dt
dMR
= L1 V R P
dt
The energy conservation equation for the reboiler is:
d(MR hR )
= L1 h1 VR HR P hR + QR
dt
The mole conservation equations (both total and by component) for the jth
tray are:
d(Mj xj )
= Lj+1 xj+1 Lj xj + Vj1 yj1 Vj yj
dt
dMj
= Lj+1 Lj + Vj1 Vj
dt
Finally, the energy conservation equation for the jth tray is:
d(Mj hj )
= Lj+1 hj+1 Lj hj + Vj1 Hj1 Vj Hj
dt
Where Mj is the holdup of liquid in the jth tray, reboiler (R) or reflux drum
(D) respectively, h is the entalphy of the liquid phase (in a molar basis), H
is the entalphy of the gas phase (in a molar basis), P is the product flow and
V0 = VR . Also, in each tray, an equilibrium relation holds:
yj = f (xj , P, T )

Problem 9
An ice cube is dropped into a hot, perfectly mixed, insulated cup of coffe.
Develop the equations describing the dynamics of the system. List all the assumptions and define all the terms.
Solution
Besides the conditions indicated in the problem statement, the following
assumptions are made:
1. There are no internal temperature gradients in the ice cube, it remains at
fusion temperature.
2. Entalphy of the liquid phase can be expressed as h = Cpw T .
3. Entalphy of the solid phase can be expressed as h = Cpw T .
4. The physical properties of the coffe are the same as those of water.

An energy balance allows to calculate the rate of fussion of ice:

dMi
Q
U AHT (Mi )(Tc Ti )
=
=
dt

The mass balance for the system is:

dMc
Mi
+
=0
dt
dt
The energy balance for the liquid phase is:
Mi
d(Mc Tc )
=
Cp,w Ti + U AHT (Mi )(Ti Tc )
dt
dt
Where Mi and Ti are the mass and temperature of the solid phase. Mc
and Tc are the mass and temperature of the liquid phase. U is the heat transfer
coefficient, is the heat of vaporization of ice, and AHT (Mi ) is the heat transfer
area, as a function of the mass of ice.
Cp,w

Problem 10
An isothermal, irreversible reaction:
k

A
B
takes place in the liquid phase in a constant-volume reactor. The mixing is not
perfect. Observation of flow patterns indicates that a two-tank system with
back mixing, as shown in Figure ?? below, should approximate the imperfect
mixing.
Assuming F and FR are constant, write the equations describing the system.

Figure 8: Two tank system with back mixing.

Solution
The A species balance for reactor 1 and 2 are:
V1

dCA1
= F (CA0 CA1 ) + FR (CA2 CA1 ) V kCA1
dt

dCA2
= F (CA1 CA2 ) + FR (CA1 CA2 ) V kCA2
dt
Because both F and FR are constant, the total volume in each reactor is
constant.
V2

10

Problem 11
The liquid in a jacketed, nonisothermal CSTR is stirred by an agitator whose
mass is significant compared with the reaction mass. The mass of the reactor
wall and the mass of the jacket wall are also significant. Write the energy
equations for the system. Neglect radial temperature gradients in the agitator,
reactor wall, and jacket wall.
Solution
The CSTR is shown in Figure ??. In writing the energy equations, the
following assumptions are made:

Figure 9: Jacketed non isothermal CSTR.

Reactor fluid and cooling fluid hold up are constant.
Physical properties are constant.
The cooling fluid in the jacket is perfectly mixed.
There are no internal temperature gradients in the agitator, reactor wall
and jacket wall.
There are no heat losses to the environment.

Cp,f Mf

dTf
= F Cp,f (Tf,0 Tf ) Us,f As,f (Tf Ts ) Us,RW As,RW (Tf TRW )
dt
Cp,s Ms

dTs
= Us,f As,f (Tf Ts )
dt
11

Cp,RW MRW

Cp,c Mc

dTRW
= URW,f ARW,f (Tf TRW ) + URW,c ARW,c (Tc TRW )
dt

dTc
= Fc Cp,c (Tc,0 Tc )URW,c ARW,c (Tc TRW )UJW,c AJW,c (Tc TJW )
dt

dTJW
= UJW,c AJW,c (Tc TJW )
dt
Where f denotes properties of the fluid inside the reactor, s propiertes of
the stirrer, RW properties of the reactor wall, c properties of the cooling fluid
and JW properties of the jacket wall.
Cp,JW MJW

Problem 12
The reaction 3A 2B + C is carried out in an isothermal semibatch reactor.
Product B is the desired product. Product C is a very volatile by-product that
must be vented off to prevent a pressure buildup in the reactor. Gaseous C is
vented off through a condenser to force any A and B back into the reactor to
prevent loss of reactant and product.
Assume FV is pure C. The reaction is first order in CA . The relative volatilities of A and C to B are AB = 1.2 and CB = 10. Assume perfect gases
and constant pressure. Write the equations describing the system. List all
assumptions.

Figure 10: Semi batch reactor.

Solution
Assumptions:

12

 The liquid phase is composed of only A and B, whereas the gas phase is
composed only of C.
There is no change of volume due to mixing in the liquid phase.
The mole balances for the liquid phase are:
d(VL CA )
= 3kVL CA
dt
d(VL CB )
= 2kVL CA
dt
The mole balance for the gas phase are:
FV P
P dVG
= kVL CA
RT dt
RT
The additivity of volumes permit to write an additional relation between the
concentrations of A and B:
1=

MB
A
VL CA M
VA + VB
CA M A
CB MB
A + VL CB B
=
=
+
VL
VL
A
B

Finally the sum of the volume of the gas and the liquid phase must equal
the volume of the reactor:
VL + VG = VR
This five equations allows to solve the five variables: CA , CB , VL , VG and
FV .

Problem 13
Write the equations describing a simple version of the pretroleum industrys
important catalytic cracking operation. There are two vessels as shown in Figure
??. Component A is fed to the reactor where it reacts to form product B while
depositing component C on the solid fluidized catalyst.
A B + 0.1C
Spent catalyst is circulated to the regenerator where air is added to burn off C.
C+OP
Combustion products are vented overhead, and regenerated catalyst is returned
to the reactor. Heat is added or removed from the regenerator at a rate Q.
Your dynamic mathematical model should be based on the following assumptions:
1. The perfect-gas law is obeyed in both vessels.
13

2. Constant pressure is mantained in both vessels.

3. Catalyst holdups in the reactor and in the regenerator are constant.
4. Heat capacities of reactants and products are equal and constant in each
vessel. Catalyst heat capacity is also constant.
5. Complete mixing occurs in each vessel.

Figure 11: Reactor regenerator system.

Solution
Assumptions:
Reactions are first order with respect to reactants, both in gas phase (Cj )
and in solid phase (xj ).
Reactions occur in the surface of the catalyst, the rate of reaction is proM a
portional to jc j , where aj is the surface/volume ratio for the catalyst.
The mass balance equations for reactor are:
VG,1

M1
dCA
= F0 CA0
a1 k1 CA F1 CA
dt
c
VG,1

M1

dCB
M1
=
a1 k1 CA F1 CB
dt
c

dX1
M1
= w(X2 X1 ) + 0.1
a1 k1 CA
dt
c
14

The energy balance for reactor is:

(M1 Cp,c + VG,1 1 Cp,1 )

dT1
= F0 0 Cp,1 T0 F1 1 Cp,1 T1 + wCp,c (T2 T1 )
dt
M1

a1 k1 CA 1
c

The mass balance equations for the regenerator are:

M2
VG,2

M2
dX2
= w(X1 X2 )
a2 k2 CO X2
dt
c

M2
dCO
= Fa COa F2 CO
a2 k2 CO X2
dt
c
VG,2

M2
dCP
=
k2 CO X2 F2 CP
dt
c

The energy balance for the regenerator is:

(M2 Cp,c + VG,2 2 Cp,2 )

dT2
= Fa a Cp,2 Ta F2 2 Cp,2 T2 + wCp,c (T1 T2 )
dt
M2

a2 k2 CO X2 2 + Q
c

Where Cp,1 is the heat capacity of reactants and products at vessel 1, and
Cp,2 is the heat capacity of reactants and products at vessel 2.

Problem 14
Flooded condensers and flooded reboilers are sometimes used on distillation
columns. As shown in Figure ??, a liquid level is held in the condenser, covering
some of the tubes. Thus a variable amount of heat transfer area is available
to condense the vapor. Column pressure can be controlled by changing the
distillate (or reflux) drawnoff rate.
Write the equations describing the dynamics of the condenser.
Solution
Assumptions:
The dynamic of the fluid in the shell side is negligible.
The heat transferred to the cooling water is due to heat of condensation
alone.
The area available for heat transfer is proportional to the volume of the
tubes not occupied by the condensing fluid.

15

Figure 12: Flooded condenser.

The volumetric balance of fluid inside the shell and the energy balance for
the cooling water are:




dV
VT V AT U
(Tw,out + Tw,in )
=
T
RD
dt
VT

2
Fw w Cp,w (Tw,out Tw,in ) = Fc
Where VT and AT are the total volume and total heat transfer area of the
shell side, V is the volume of condensed fluid inside the shell, and FC is the rate
of fluid condensation.

Problem 15
When cooling jackets and internal cooling coils do not give enough heat transfer
area, a circulating cooling system is sometimes used. Process fluid from the
reactor is pumped through an external heat exchanger and back into the reactor.
Cooling water is added to the shell side of the heat exchanger at a rate Fw
as set by the temperature controller. The circulation rate through the heat
exchanger is constant. Assume that the shell side of the exchanger can be
represented by two perfectly mixed lumps in series and that the process fluid
flows countercurrent to the water flow, also through two perfectly mixed stages.
The reaction is irreversible and first-order in reactant A.
k

A
B
The contents of the tank are perfectly mixed. Neglect reactor and heat exchanger metal.
Derive a dynamic mathematical model of the system.
Solution

16

Figure 13: Circulating cooling system.

Figure 14: Lumps in series.

The system can be represented as shown in Figure ??.
Assumptions:
1. The volume of fluid contained in each lump, for both tubes and shell side,
is constant.
2. For both tubes and shell side, the volume of lumps are equal to each other.
3. Density and specific heat are independent of concentration of A and B.
Mass balances for the reactor:


d(V CA )
Ea
= F0 CA0 F CA CA V K exp
dt
RT

17



d(V CB )
Ea
= F CB + CA V K exp
dt
RT
Energy balance for the reactor:


d(V T )
Ea
= F0 T0 + FC (T2 T ) F T CA V K exp

dt
RT
Energy equations for shell side:
VS

dTw,1
= Fw w Cp,w (Tw,0 Tw,1 ) U A(Tw,1 T2 )
dt

dTw,2
= Fw w Cp,w (Tw,1 Tw,2 ) U A(Tw,2 T1 )
dt
Energy equations for tubes side:
VS

Vt

dT1
= FC Cp (T T1 ) U A(T1 Tw,2 )
dt

Vt

dT2
= FC Cp (T1 T2 ) U A(T2 Tw,1 )
dt

Problem 16
A semibatch reactor is run at constant temperature by varying the rate of
addition of one of the reactants, A. The irreversible, exothermic reaction is first
order in reactants A and B.
k
A+B
C
The tank is initially filled to its 40 percent level with pure reactant B at a
concentration CB0 . Maximum cooling-water flow is begun, and reactant A is
slowly added to the perfectly stirred vessel.
Write the equations describing the system. Without solving the equations,
try to sketch the profiles of FA , CA , and CB with time during the batch cycle.
Solution
The mass balances for each species are:
d(V CA )
= FA CA0 kCA CB V
dt
d(V CB )
= kCA CB V
dt
d(V CC )
= kCA CB V
dt
The energy equation is:
Cp

d(V T )
= kCA CB V + Q
dt
18

Figure 15: Semibatch reactor.

Figure 16: Guessed profiles.

The guessed profiles are shown in Figure ??.
CA remains relatively low whereas the cuantity of B that remains is great
enought to react with the incoming A, when B is consumed A starts to grow in
concentration, also, later in time the effect of dillution because of the C that is
being produced is reduced. CB diminishes at first because the product C that
accumulates in the tank dilutes it, after that continues to diminish because of
the accumulation of A. FA is low at the begining because the rate of reaction is
high, after that, more A is added to compensate for the consumption of B, also
the cooling system can manage a greater volume of reaction mixture because of
the lower reaction rate.

Problem 17
Develop a mathematical model for the three-column train of distillation columns
shown in Figure ??. The feed to the first column is 400 kg mol/h and contains
four components (1, 2, 3 and 4), each at 25 mol %. Most of the lightest component is removed in the distillate of the first column, most of the next lightest in
the second column distillate and the final column separates the final two heavy
components. Assume constant relative volatilities throught the system: 1 ,
2 and 3 . The condensers are total condensers and the reboilers are partial.

19

Trays, column bases and reflux drums are perfectly mixed. Distillate flow rates
are set by reflux drum level controllers. Reflux flows are fixed. Steam flows
to the reboilers are set by temperature controllers. Assume equimolal overflow,
negligible vapor holdup, and negligible condenser and reboiler dynamics. Use a
linear liquid hydraulic relationship

n + Mn Mn
Ln = L

n and M
n are the initial steady state liquid rate and holdup and is a
where L
constant with units of seconds.

Figure 17: Train of distillation columns.

Solution
With negligible dynamics for condenser and reboiler, only the tray holdups
must be considered, the equations are analogous for every column i, component
j and stage l.
Mass balance for feed stage:
dMN F,j,i
= Fi zj,i +LN F +1,i xN F +1,j,i LN F,i xN F,j,i +VN F 1,i yN F 1,j,i VN F,i yN F,j,i
dt
Mass balance for top stage:
dMN T,j,i
= RixR,j,i LN T,i xN T,j,i + VN T 1,i yN T 1,j,i VN T,i yN T,j,i
dt
Mass balance for first stage:
dM1,j,i
= L2,i x2,j,i L1,i x1,j,i + VB,i yB,j,i V1,i y1,j,i
dt
20

Mass balance for an intermediate (l) stage:

dMl,j,i
= Ll+1,i xl+1,j,i Ll,i xl,j,i + Vl1,i yl1,j,i Vl,i yl,j,i
dt
Energy balance for condenser:
VN T,i Cp,N T lv = Qc
Energy balance for reboiler:
VB,i Cp,B lv = QB
This equations, together with the equilibrium expressions and the relation
between the hold up and the flux from the tray, constitute the dynamic model
of the distillation column train.

Problem 18
The rate of pulp lay-down F on a paper machine is controlled by controlling
both the pressure P and the height of slurry h in a feeder drum with crosssectional area A. F is proportional to the square root of the pressure at the exit
slit. The air vent rate G is proportional to the square root of the air pressure
in the box P . Feedback controllers set the inflow rates of air G0 and slurry F0
to hold P and h. The system is isothermal.
Derive a mathematical model describing the system.

Figure 18: Paper machine.

Solution
The mass balance for the liquid zone is:
p
dh
= F0 KF hgs + P
dt
The mass balance for the gas zone is:
A

21


d((H h)P )
= KG P P + G0 P0
dt
Where H is the total height of the feeder drum, and s is the density of the
slurry.
A

Problem 19
A wax filtration plant has six filters that operate in parallel, feeding from one
common feed tank. Each filter can handle 1000 gpm when running, but the
filters must be taken off-line every six hours for a cleaning procedure that takes
ten minutes. The operation schedule calls for one filter to be cleaned every hour.
How many gallons a day can the plant handle? If the flow rate into the feed
tank is held constant at this average flow rate, sketch how the liquid level in the
feed tank varies over a typical three-hour period.
Solution
The average capacity is calculated considering that in a 1 hour period, 5
filters operate during 60 minutes, and the remaining filter operates during 50
minutes.
C=

1000[gpm](5 60[min] + 50[min])

= 5833[gpm]
60[min]

This capacity, over a day of activity, gives a processing capacity for the plant
of 8400000 gallons. Every hour, during the first 10 minutes of operation, the
capacity of the plant is only 5000 gpm (5 filters are operating), so an excess of
8333 gallons accumulate at the feed tank, the excess is processed over the next
50 minutes, when the capacity of the plant is 6000 gpm.
The feed tank level variation over a three hour period is sketched in Figure
??.

Figure 19: Feed tank liquid level variation.

22

Problem 20
Alkylation is used in many petroleum refineries to react unsaturated butylenes
with isobutane to form high octane iso-octane (alkylate). The reaction is carried
out in a two liquid phase system: sulfuric acid / hydrocarbon.
The butylene feed stream is split and fed into each of a series of perfectly
mixed tanks (usually in one large vessel). This stepwise addition of butylene
and the large excess of isobutane that is used both help to prevent undesirable
reaction of butylene molecules with each other to form high boiling, low octane
polymers. Low temperature (40 [F]) also favors the desired iC4 /C4= reaction.
The reaction is exothermic. One method of heat removal that is often used
is autorefrigeration: the heat of vaporization of the boiling hydrocarbon liquid
soaks up the heat of reaction.
The two liquid phases are completely mixed in the agitated sections, but
in the last section the two phases are allowed to separate so that the acid can
be recycled and the hydrocarbon phase sent off to a distillation column for
separation.
Derive a dynamic mathematical model of the reactor.

Figure 20: Alkylation process.

k

1
iC4 + C=
4 iC8

2
C=
4 polymer

Solution
Assumptions:
The reactions are first order with respect to reactants.
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 Only the solvent hydrocarbon is evaporated (This requires a fresh feed of

hydrocarbon for compensate for the quantity that is evaporated).
The mass balances for the first stage are:
d(V1 CiC4 )
= F0,iC4 k1 V1 CiC4 CC4= F1 CiC4
dt
d(V1 CC4= )
= F0,C4= k1 V1 CiC4 CC4= k2 V1 C4= F1 CC4=
dt
d(V1 CiC8 )
= k1 V1 CiC4 CC4= F1 CiC8
dt
d(V1 Cpoly )
= k2 V1 C4= F1 Cpoly
dt
d(V1 CAc )
= F0,Ac F1 CAc
dt
d(V1 CHC )
= F0,HC F1 CHC FV,1
dt
The energy balance for stage 1 is:
V1 M,1 Cp,M,1 T1
= F0,iC4 iC4 Cp,iC4 T0,iC4 + F0,C4= C4= Cp,C4= T0,C4=
dt
+ F0,Ac Ac Cp,Ac T0,F0,Ac + F0,HC HC Cp,HC T0,HC
FV,1 HC lv k1 V1 CiC4 CC4= 1 k2 V1 C4= 2
F1 M,1 Cp,M,1 T1
The mass balances for the intermediates steps (j = 2, 3, 4):
d(Vj CiC4 )
= Fj1 CiC4 k1 Vj CiC4 CC4= Fj CiC4
dt
d(Vj CC4= )
= Fj1 CC4= k1 Vj CiC4 CC4= k2 Vj C4= Fj CC4=
dt
d(Vj CiC8 )
= Fj1 CiC8 + k1 Vj CiC4 CC4= Fj CiC8
dt
d(Vj Cpoly )
= Fj1 Cpoly + k2 Vj C4= Fj Cpoly
dt
d(Vj CAc )
= Fj1 CAc Fj CAc
dt

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d(Vj CHC )
= Fj1 CHC Fj CHC FV,j
dt
In the intermediate steps mass balances before, the concentration that appears multiplying each flow Fi correspond to the concentration of the respective
component in the vessel i.
The energy balance for stage j is:
Vj M,j Cp,M,j Tj
= Fj1 M,j1 Cp,M,j1 Tj1 k1 Vj CiC4 CC4= 1
dt
k2 Vj C4= 2 Fj M,j Cp,M,j Tj FV,j HC lv
Where:
F0,iC4 : Feed of isobutane.
F0,C4= : Feed of unsaturated butylenes.
F0,Ac : Recirculated flow of acid.
F0,HC : Feed of solvent hydrocarbon.
FV,j : Flow of hydrocarbon that is evaporated in each step.
M,j : Density of the mixture at stage j.
Cp,M,j : Heat capacity of the mixture at stage j.

Problem 21
Benzene is nitrated in an isothermal CSTR in the sequential irreversible reactions:
k1
Benzene + HNO
Nitrobenzene + H2 O
k

2
Nitrobenzene + HNO
Dinitrobenzene + H2 O

3
Dinitrobenzene + HNO
Trinitrobenzene + H2 O

Assuming each reaction is linearly dependent on the concentrations of each

reactant, derive a dynamical mathematical model of the system. There are
two feed streams, one pure benzene and one concentrated nitric acid (98wt %).
Assume constant density and complete miscibility.
Solution
A sketch of the reactor is shown in Figure ??.
The total and species mass conservation equations are:
dV
= F0 + F1 F
dt
d(V CHN O )
= F1 CHN O,1 V (k1 CHN O CB +k2 CHN O CN B +k3 CHN O CDN B )F CHN O
dt
d(V CB )
= F0 V k1 CB CHN O F CB
dt
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Figure 21: Benzene nitration process.

d(V CN B )
= V (k1 CHN O CB k2 CHN O CN B ) F CN B
dt
d(V CDN B )
= V (k2 CHN O CN B k3 CHN O CDN B ) F CDN B
dt
d(V CT N B )
= V k3 CHN O CDN B F CT N B
dt

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