Process Modelling, Simulation and Control for Chemical Engineers.

Solved
problems. Chapter 3: Examples of mathematical models of chemical en-
gineering systems. Version 2.
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. As such, I can’t 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

Changes from Version 1

*Figure references were corrected.
*Equation that describes the system now contains K0 , problem 2.
*A component continuity equation, problem 3.
*Energy balance, domain and boundary condition specifications, problem 5.
*Species mass balances, problem 6.
*Equations for reflux drum, problem 8.
*Energy balances, problem 15.
*Energy balance for condenser and reboiler, problem 17.

Problem 1
A fluid of constant density ρ is pumped into a cone shaped tank of total volume HπR2 /3 (Figure
1). 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:
dV √
= F0 − K h (1)
dt
Denoting by r the radius of the cone of fluid inside the tank, and if θ is the angle formed by the
cone shaped tank and the horizontal, we have:
H h
tan θ = = (2)
R r
The volume of fluid inside the tank is:
hπr2
V = (3)
3

1
Replacing equation (2) into equation (3) we get:
 2
π R
V = h3 (4)
3 H

Equation (4) together with equation (1) 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
W0 = K0 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
resists 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.
(a) Derive the equations describing the system.
(b) 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 side of
him are always balanced. The pressure at the spring side of the cylinder, according to Figure 2,
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 is:

 √
dx W0 K0 RT P0 − P
A = =
dt ρ M P
 p
dx K0 RT P0 − Patm − Ks x/A
A =
dt M Patm + Ks x/A
 p
dx K0 RT P0 − Patm − Ks x/A
=
dt M APatm + Ks x

With initial condition x(t=0) = 0.

2
The steady state piston displacement will be reached when the volume no longer changes:
Ks x
P0 − Patm − =0
A
A(P0 − Patm )
x=
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
A− →B
Derive the equations describing the system.

Figure 3: CSTR.

Solution
The total continuity equation (assuming constant density of the process fluid) is:

dhow
A = F0 − KF (how )3/2
dt
The A component continuity equation is:

d((hw + how )CA )

A = F0 CA0 − KF (how )3/2 CA − kA(hw + how )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 a 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 McCoy’s Liquid Lightning.
Assuming that the concentration of ethanol in the feed, C0 , is constant and 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 is:
dV
= F0
dt

3
The ethanol continuity equation is:
d(V C)
= F0 C0 − kV C
dt
With initial conditions V(t=0) = 0 and C(t=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 w (radians per minute). Assume
Th and Tc are constant along their respective sections of the circumference. The drum lenght
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.
(a) Write the equations describing the system.
(b) What are the appropiate boundary conditions?

Figure 4: Rotating heat exchanger.

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 θ direction is negligible.
3. The thickness is much smaller than the exchanger radius.
In a time interval ∆t, the energy entering and leaving a volume of size d∆θRL is:
Entering:
∆tωRdLρCp Tθ
Leaving:  
dT
∆tωRdLρCp Tθ + ∆θ + 2∆tL∆θRUj (T − Tj )
dθ
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 ∆t∆θRL:
dT
ωdCp ρ = −2Uc (T − Tc )
dθ
dT 2Uc (T − Tc )
=−
dθ ωdCp ρ

4
The analogous energy balance for the heating zone gives:
dT 2Uh (T − Th )
=−
dθ ωdCp ρ
The energy balance for the cooling zone applies in the range θ : [π, 2π], whereas the energy balance
for the heating zone applies in the range θ : [0, π]. Solution of the differential equations gives two
integration constants, which are determined applying the following boundary conditions:

Th (0) = Tc (2π)
Th (π) = Tc (π)

Problem 6
Consider the system that has two stirred chemical reactors separated by a plug flow deadtime
of D seconds. Assume constant holdups (V1 and V2 ), constant throughput (F ), constant den-
sity, isothermal operation at temperatures T1 and T2 , and first order kinetics with simultaneous
reactions:
k
1
A −→ B
k
2
A −→ C

No reactions occurs 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:
dCA1,t
V1 = F CA0 − F CA1,t − k1,T1 V1 CA1,t − k2,T1 V1 CA1,t
dt
CB1,t
V1 = −F CB1,t + k1,T1 V1 CA1,t
dt
CC1,t
V1 = −F CC1,t + k2,T1 V1 CA1,t
dt
The species balances for the second reactor are:
dCA2,t
V2 = F CA1,t−D − F CA2,t − k1,T2 V2 CA2,t − k2,T2 V2 CA2,t
dt
CB2,t
V2 = F CB1,t−D − F CB2,t + k1,T2 V2 CA2,t
dt
CC2,t
V2 = F CC1,t−D − F CC2,t + k2,T2 V2 CA2,t
dt

Problem 7
Consider the isothermal hydraulic system sketched in Figure 6. 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:

ρ = ρ0 + β(P − P0 )

5
where ρ0 , β, and P0 are constants, ρ 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.
(a) Derive the differential equation that gives the pressure P in the tank as a function of time and
W1 .
(b) Find the steadystate value of tank pressure P .

Figure 6: Hydraulic system.

Solution
A mass balance for the tank gives:
dρ
V = 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
Vβ = W1 −
dt R2 + R3

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 wich 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 in 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
can’t be neglected.

Solution
The inverted batch distillation column is shown in Figure 7. 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 are perfectly mixed.
The mole conservation equations (both total and by component) for the Nth tray are:

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

6
 Figure 7: Inverted batch distillation column.

The energy conservation equation for the Nth tray is:

d(MN 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 + F xF
dt
dMD
= VN T − R + F
dt
The energy conservation equation for the reflux drum is:
d(MD hD )
= VN T HN T − RhD + F hF + QD
dt
The mole conservation equations (both total and by component) for the reboiler are:
d(MR xR )
= L1 x1 − VR yR − P xR
dt
dMR
= L1 − VR − 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 + Vj−1 yj−1 − Vj yj
dt
dMj
= Lj+1 − Lj + Vj−1 − Vj
dt

7
Finally, the energy conservation equation for the jth tray is:
d(Mj hj )
= Lj+1 hj+1 − Lj hj + Vj−1 Hj−1 − 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 bassis), H is the entalphy of the gas phase (in a molar
basis), P is the product flow, and F is the feed. 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 assumptions and define all 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 − λ.
4. The physical properties of the coffe are the same as those of water.
An energy balance allows to calculate the rate of fusion of ice:
dMi Q U AHT (Mi )(Tc − Ti )
= =
dt λ λ
The mass balance for the system is:
dMc dMi
+ =0
dt dt
The energy balance for the liquid phase is:
d(Mc Tc ) dMi
Cp,w =− 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, λ is the heat of fusion of ice,
and AHT (Mi ) is the heat transfer area, as a function of the mass of ice.

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 8, should
approximate the imperfect mixing.
Assuming F and FR are constant, write the equations describing the system.

Solution
The A species balance for reactor 1 and 2 are:
dCA1
V1 = F (CA0 − CA1 ) + FR (CA2 − CA1 ) − V1 kCA1
dt
dCA2
V2 = F (CA1 − CA2 ) + FR (CA1 − CA2 ) − V2 kCA2
dt
Because both F and FR are constant, the total volume in each reactor is constant.

8
 Figure 8: Two tank system with back mixing.

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 9. In writing the energy equations, the following assumptions are
made:
• Reactor fluid and cooling fluid holdup 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.

Figure 9: Jacketed non isothermal CSTR.

The energy balances are:

dTf
Cp,f Mf = F Cp,f (Tf,0 − Tf ) − Us,f As,f (Tf − Ts ) − Uf,rw Af,rw (Tf − Trw )
dt

9
 dTs
Cp,s Ms = Uf,s Af,s (Tf − Ts )
dt

dTrw
Cp,rw Mrw = Uf,rw Af,rw (Tf − Trw ) − Urw,c Arw,c (Trw − Tc )
dt

dTc
Cp,c Mc = Fc Cp,c (Tc,0 − Tc ) + Urw,c Arw,c (Trw − Tc ) − Uc,jw Ac,jw (Tc − Tjw )
dt

dTjw
Cp,jw Mjw = Uc,jw Ac,jw (Tc − Tjw )
dt
Where f denotes properties of the fluid inside the reactor, s properties of the stirrer, rw properties
of the reactor wall, c properties of the cooling fluid and jw properties of the jacket wall.

Problem 12
The reactions 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 build up 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 αAB = 1.2 and αCB = 10. Assume perfect gases and constant pressure. Write the equations
describing the system. List all assumptions.

Figure 10: Semi batch reactor.

Solution
Assumptions:
• 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

10
The mole balance for the gas phase are:
P dVG FV P
= kVL CA −
RT dt RT
The additivity of volumes permit to write and additional relation between the concentrations of A
and B:

VA + VB VL CA M A MB
ρA + VL CB ρB MA MB
1= = = CA + CB
VL VL ρA ρB
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 petroleum industry’s important catalytic
cracking operation. There are two vessels as shown in Figure 11. 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 +O →P

Combustion products are vented overhead, and regenerated catalyst is returned to the reactor.
Heat is added to 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.
(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.

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 proportional to Mj aj /ρj ,
where aj is the surface/volume ratio for the catalyst.
The mass balance equations for the reactor are:
dCA M1
VG,1 = F0 CA0 − a1 k1 CA − F1 CA
dt ρc
dCB M1
VG,1 = a1 k1 CA − F1 CB
dt ρc
dx1 M1
M1 = w(x2 − x1 ) + 0.1 a1 k1 CA
dt ρc

11
 Figure 11: Reactor regenerator system.

The energy balance for the reactor is:

dT1 M1
(M1 Cp,c + VG,1 ρ1 Cp,1 ) = F0 ρ0 Cp,1 T0 − F1 ρ1 Cp,1 T1 + wCp,c (T2 − T1 ) − a1 k1 CA λ1
dt ρc
The mass balance equations for the regenerator are:
dCO M2
VG,2 = Fa COa − F2 CO − a2 k2 CO x2
dt ρc
dCP M2
VG,2 = k2 CO x2 − F2 CP
dt ρc
dx2 M2
M2 = w(x1 − x2 ) − a2 k2 CO x2
dt ρc
The energy balance for the regenerator is:
dT2 M2
(M2 Cp,c + VG,2 ρ2 Cp,2 ) = Fa ρa Cp,2 Ta − F2 ρ2 Cp,2 T2 + wCp,c (T1 − T2 ) − a2 k2 CO x2 λ2 + Q
dt ρ
Where Cp,1 is the heat capacity of reactants and products at reactor, and Cp,2 is the heat capacity
of reactants and products at regenerator.

Problem 14
Flooded condensers and flooded reboilers are sometimes used on distillation columns. In Figure
12, 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) drawoff 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 condensed fluid.

12
 Figure 12: Flooded condenser.

The volumetric balance of fluid inside the shell and the energy balance for the cooling water are:
   
dV V T − V AT U Tw,out + Tw,in
= T− −R−D
dt VT ρλ 2
Fw ρw Cp,w (Tw,out − Tw,in ) = Fc ρλ

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 this system.

Figure 13: Circulating cooling system.

13
Solution
The system can be represented as shown in Figure 14.
Assumptions:
• The volume of fluid contained in each lump, for both tubes and shell side, is constant.
• For both tubes and shell side, the volume of lumps are equal to each other.
• Density ans specific heat are independent of concentration of A and B.

Figure 14: Lumps in series.

Mass balances for the reactor:

 
d(V CA ) Ea
= F0 CA0 − F CA − CA V K exp −
dt RT
 
d(V CB ) Ea
= −F CB + CA V K exp −
dt RT
Energy balance for the reactor:
 
d(V T ) CA V K Ea
= F0 T0 + Fc (T2 − T ) − F T − exp − λ
dt ρCp RT
Energy balances for shell side:
dTw,1 UA
Vs = Fw (Tw,0 − Tw,1 ) − (Tw,1 − T2 )
dt ρw Cp,w
dTw,2 UA
Vs = Fw (Tw,1 − Tw,2 ) − (Tw,2 − T1 )
dt ρw Cp,w
Energy balances for tube side:
dT1 UA
Vt = Fc (T − T1 ) − (T1 − Tw,2 )
dt ρCp
dT2 UA
Vt = Fc (T1 − T2 ) − (T2 − Tw,1 )
dt ρCp

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.

14
 Figure 15: Semibatch reactor.

Solution
The mass balances for each species are:
d(V CA )
= FA CA0 − kCA CB V
dt
d(V CB )
= −CA CB V
dt
d(V CC )
= kCA CB V
dt
The energy balance is:
d(V T )
ρCp = −kCA CB V λ + Q
dt
The guessed profiles are shown in Figure 16. CA remains relatively low whereas the quantity of B
that remains is great enought to react with the incoming A, when B is consumed A starts to grow
in concentration, also due to the reduced dilution effect of C that is being produced in smaller
quantity. CB diminishes because of the product C that is produced dilutes it, and also because of
the accumulation of A. FA is low at the beginning 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.

Figure 16: Guessed profiles.

Problem 17
Develop a mathematical model of the three column train of distillation columns sketched in Figure
17. 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 throughout the system: α1 , α2 , and

15
α3 . The condensers are total condensers and the reboilers are partial. 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:
Mn − M n
Ln = Ln +
β
where Ln and M n are the initial steady state liquid rate and holdup and β is a constant with unit
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
= Ri xR,j,i − LN T,i xN T,j,i + VN T −1,i yN T −1,j,i − VN T,i yM 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
Mass balance for intermediate stage:
dMl,j,i
= Ll+1,i xl+1,j,i − Ll,i xl,j,i + Vl−1,i yl−1,j,i − Vl,i yl,j,i
dt
Energy balance for condenser:
VN T,i λlv,N T,i = Qc,i
Energy balance for reboiler:
VB,i λlv,B,i = QB,i
This equations, together with the equilibrium expressions and the relation between the holdup and
the flux from the tray, constitute the dynamic model of the distillation column train.

16
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 cross sectional 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 . Feeback controllers set the inflow rates of air G0 and slurry F0
to hold P and h. The system is isothermal. Derive a dynamic mathematical model describing the
system.

Figure 18: Paper machine.

Solution
The mass balance for the liquid zone is:
dh p
A = F0 − KF hgρs + P
dt
The mass balance for the gas zone is:
d((H − h)P ) √
A = G0 P0 − KG P P
dt
Where H is the total height of the feeder drum, and ρs is the density of the slurry.

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 clening procedure that takes ten minutes. The operating 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.
1000[gpm](5 ∗ 60[min] + 50[min])
C= = 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 19.

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 Figure 19: Feed tank liquid level variation.

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 /C4n 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.
k
iC4 + C4= −→
1
iC8
k
C4= −→
2
polymer

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

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 Figure 20: Alkylation process.

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:

d(V1 ρM,1 Cp,M,1 T1 )

= (F0 ρCp T0 )iC4 + (F0 ρCp T0 )C4= + (F ρCp T0 )Ac
dt
+ (F0 ρCp T0 )HC − FV,1 λlv − k1 V1 CiC4 CC4= λ1
− k2 V1 C4= λ2 − F1 ρM,1 Cp,M,1 T1

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The mass balances for the intermediates steps (j=2, 3, 4) are:

d(Vj CiC4 )
= Fj−1 CiC4 − k1 Vj CiC4 CC4= − Fj CiC4
dt
d(Vj CC4= )
= Fj−1 CC4= − k1 Vj CiC4 CC4= − k2 Vj C4= − Fj CC4=
dt
d(Vj CiC8 )
= Fj−1 CiC8 + k1 Vj CiC4 CC4= − Fj CiC8
dt
d(Vj Cpoly )
= Fj−1 Cpoly + k2 Vj C4= − Fj Cpoly
dt
d(Vj CAc )
= Fj−1 CAc − Fj CAc
dt
d(Vj CHC )
= Fj−1 CHC − Fj CHC − FV,j
dt
In the intermediate steps mass balances before, the concentration that appears multiplying each
flow Fj corresponds to the concentration of the respective component in vessel j.
The energy balance for stage j is:

d((V ρM Cp,M T )j )
= (F ρM Cp,M T )j−1 − k1 Vj CiC4 CC4= λ1 − k2 Vj C4= λ2
dt
− (F ρM Cp,M T )j − FV,j λlv,j

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 stage j.
ρM,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 reversible reactions:
1 k
Benzene + HN O −→ Nitrobenzene + H2 O
2 k
Nitrobenzene + HN O −→ Dinitrobenzene + H2 O
3 k
Dinitrobenzene + HN O −→ 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 (98w%). Assume constant density and complete miscibility.

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Solution
A sketch of the reactor is shown in Figure 21. The total and species mass conservation equations
are:
dV
= F0 + F1 − F
dt
d(V CHN O )
= F1 CHN O,1 − F CHN O
dt
− V (k1 CHN O CB + k2 CHN O CN B + k3 CHN O CDN B )
d(V CB )
= F0 − V k1 CB CHN O − F CB
dt
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

Figure 21: Benzene nitration process.

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