University of Rome “La Sapienza”

Department of Chemical Engineering Materials Environment

Exam preparation (Part II)

Dr. Eng. Giorgio Vilardi

• Exercises
 Exercises - E09
An aqueous solution at 25°C, coming from food processing, is heated and then
subjected to a flash at about 0.5 atm of absolute pressure. The aromas and part of the
water vaporize and are then separated in the subsequent distillation which operates at
approximately the same pressure as the flash. The block diagram is the following (From
Prof.ssa Mazzarotta booklet)

fragrances

H2O+fragrances
Heating
Storing
(75°C)

H2O H2O
 Exercises - E09
The purpose of the process is the recovery of precious aromas/fragrances from their
aqueous solution: the process works under vacuum, to avoid thermal degradation of the
aromas. The column should recover and purify the aromas so, presumably, the stripping
section will have many more sieves than the rectifying section. Since water needs to be
vaporized at the bottom, one could think of eliminating the reboiler and sending steam
from the low pressure network directly into the column, but, since the system can carry
impurities, mixing it with fragrances is not advisable.

Both the flash and the column operate under vacuum: if no valves are placed between
the two equipment, it will be sufficient to maintain the vacuum in the column. The
aromas will be obtained as a distillate in the vapor phase (more volatile than water),
using a vacuum pump (the ejector must be avoided since the distillate will mixed with
the drive steam).

At the bottom of the distillation column, water at a pressure of slightly over 0.5 ata is at
a temperature of about 82 ° C: it can therefore be used to preheat the water and aroma
solution coming from the storage tank. However, it is necessary to provide for an
additional exchanger, heated with lps, which ensures that the water-aroma mixture
reaches exactly the temperature expected for the flash.
 Exercises - E09
A pump is required to send the solution from the tank to the flash vessel, passing
through the heat exchangers, while the water-aroma mixture that comes out of the flash
in the gaseous phase will pass directly into the distillation column without the necessity
of other fluid machines.

The solution coming out of the storage tank is moved by a pump and sent at a constant
flow rate to the flash vessel: the regulation valve is placed downstream of the heat
exchangers and immediately before the flash vessel; given the modest pressure
gradient, it is not necessary to install an expansion valve. The storage tank will be
equipped with minimum and maximum level alarms: since the flow rates treated will
presumably be modest, it has been assumed that the tank is filled manually when
necessary.

In the first heat exchanger, which recovers heat from the outgoing residual current of
the column, no control is necessary to maximize the heat recovery. The temperature of
the water-aroma mixture downstream of the exchanger heated with lps is controlled by
acting on the flow of lps.
 Exercises - E09

Water to be lps
treated

Solution
 Exercises - E09
In the flash vessel, the liquid is separated from the vapor phase generated due to the
fluid expansion: the level is controlled by acting on the flow of water taken from the
bottom. The pressure of the vessel is the same as that of the column, except for the
pressure drops in the pipeline that connects the two equipment, and it is therefore
sufficient to control its value in the column so that it remains uniquely fixed also in the
flash (where it will be slightly larger).

c.w.

fragrances
Water to be treated

lps
 Exercises - E09
The control of the entity of the separation in the column is carried out based on the
temperature on the "pilot" sieve placed in the stripping section, acting on the heating
steam flow to the reboiler, sending, at the same time, the reflux at constant flow. The
pressure in the column is adjusted by acting on the by-pass of the vacuum pumps that
take the aromas as distillate (in the vapor phase) from the reflux drum. The level is
controlled by acting on the flow of c.w. sent to the condenser. The level at the bottom of
the column is controlled by acting on the residue outlet.

Wastewat lps

c.w.
aromas
wastewat

lps
 Exercises - E09
The final scheme is (this is simplified, the students should report also the transmitters
and then the controllers).

Wastewat lps
solution
Wastewat lps

c.w.

fragrance
wastewater
c.w.
aromas
lps
wastewat

lps
 Exercises - E09
The second part of the exercise consists of designing the flash vessel that operates at
0.5 atm and 75°C. First of all, the vapor flowrate and the liquid flowrate are 100 kg/h and
700 kg/h. The density of liquid phase at 0.5 atm and 75°C is 975 kg/m 3 whereas that of
vapor phase can be calculated by the ideal EOS considering an average molar fraction
of the aroma equal to 0.3 and average molar mass of 200 kg/kmol.

Students should do the calculation, considering a vertical vessel and a residence time
of 5 min.
 Exercises - E09
An organic liquid is oxidized with air: the reaction is very exothermic and is carried out in
a bubble column reactor in which the air is fed in excess to ensure the necessary
mixing. The reaction heat is absorbed by using a thermal oil that works in a closed
cycle: the oil removes the heat from the reactor and transfers it to demineralized water
under pressure, returning to the initial temperature. The water vaporizes, producing
mps. The block diagram is the following

oil
mps
Organic
liquid Oxidizied
Bubble liquid Steam
column production
reactor
Air
Demineralized/
degassed w.
oil
 Exercises - E09
The main problem is to ensure the reactor the correct operating conditions. Assuming
that the inlet reactants are already at the reaction pressure and temperature, these
same conditions must be maintained in the reactor. The enthalpy of reaction is high,
and the liquid heat transfer coefficient in a bubble column reactor is not very high, due
to low Re number: the reactor cooling will then be carried out using an external heat
exchanger, to which a current of liquid coming from the reactor, once cooled, will be
recirculated to the reactor itself. This flowrate should be high, so that the temperature
variation of the current will be limited and this returns to the reactor at a temperature not
too lower than that in the reactor. The conversion of the reaction could be checked with
a continuous composition analyzer; if this is not possible, it will be necessary to adjust
the flowrates of the reagents to the predetermined value, or by a ratio controller.

The thermal oil operates in a closed circuit, therefore an expansion tank must be
provided to allow the oil volume to vary according to the variation in its density between
the conditions in which the circuit is loaded (cold oil, larger density) and those in which it
operates (hot oil, lower density). The expansion tank and the oil circulation pump will be
installed in the point where the oil is at a temperature closest to the ambient one; if the
oil is not volatile or dangerous, one’s can use an expansion tank that works at
atmospheric pressure, placed in a high place where the circuit can be kept flooded.
 Exercises - E09
The conversion of the reaction was controlled by acting on the flowrates of the reactants
which were adjusted, independently of each other, to a constant value, since the air is
fed in excess. As for the air, the flow control is carried out after the recirculation and
supply currents have mixed and the signal acts on a valve placed on the flow of fresh
reagent. The pressure of the reactor is in fact controlled by acting on the flow of excess
air, which is recirculated by a centrifugal compressor: the valve is placed upstream of
the compressor.

Organic
liquid

Air
 Exercises - E09
The reactor will be 70-80% full of liquid and the level control will act on the flow of
outgoing liquid; a pump was not foreseen, because the reactor works at a high
pressure. The reactor temperature is controlled by acting on the flow of thermal oil sent
to the exchanger; on the other hand, the flow rate of liquid that is recirculated to the
reactor was not controlled, leaving it to be the maximum that the pump is able to supply
based on the head of the circuit.

Steam grid

Demin. water
Oxidized liquid
 Exercises - E09
The thermal oil will be moved by a pump, located downstream of the cooler where
exchanges heat with demineralized water, producing mps; the expansion vessel is
connected in parallel to the circuit just before the pump. No level control has been
designed for the tank (there will be only max/min alarms not showed): the level value
depends on the thermal expansion of the oil (in piping and vessel) between the
temperature at which it is filled the circuit and the operating one, and does not depend,
on the other hand, on the flowrate of circulating thermal oil (regulated basing on the
reaction enthalpy to be removed).

Steam grid

Demin. water
Oxidized liquid
 Exercises - E09
To vary the amount of heat removed from the reactor by varying the flowrate of the oil,
the temperature of the oil entering the exchanger must be controlled. This temperature
will depend, in turn, on the heat exchange between the oil and the demineralized water,
carried out in a reboiler. The temperature of the oil will be controlled by varying the
pressure (and therefore the temperature) at which vaporization occurs in the vaporizer,
which is achieved by acting on the flow of steam coming out of the vaporizer. A level
control in the vaporizer will ensure that there is always water above the tube bundle,
acting on the inlet demineralized water flow.

Steam grid

Demin. water
Oxidized liquid
 Exercises - E09
An aqueous mixture from a fermenter (fermentation broth) is subjected to stripping with
steam: an aqueous mixture with the products of interest (acetone, ethanol and butanol)
is recovered from the top while an aqueous solution with the impurities (acetic acid,
butyric acid, etc.) at the bottom. The overhead mixture is then subjected to distillation to
recover the most volatile product (acetone), while from the bottom a mixture of water,
ethanol and butanol is obtained which must be subjected to other separations (not
reported). Boiling points of acetone and butanol are 56 and 118 ° C at atmospheric
pressure, respectively. The block diagram is the following

H2O+C3H6O+C4H10O+EtOH
Broth

Atmospheric distillation

Water+impurities lps
H2O+C4H10O+EtOH
 Exercises - E09
It is assumed that both the stripping column and the distillation column operate at
atmospheric pressure; stripping will work at just over 100 ° C (steam is used which must
not condense in the column); the distillation column works between about 56 ° C at the
top (condensation with industrial water or air) and slightly under 118 ° C at the bottom
(reboiler with lps). No heat exchanges and nor condensation are required: the stream
will enter the distillation column under the conditions of slightly superheated steam.

In the stripping column a concentration control is placed on the outgoing liquid stream (it
is necessary to check that the compounds of interest have been removed) and the
stripping vapor flowrate is adjusted. The pressure is adjusted by acting on the outgoing
gaseous flow: this proceeds towards the distillation column moved by a fan. The level in
the stripping column is controlled by acting on the flowrate of the liquid leaving the
bottom. The regulation of the column is the “classic” one: the separation is controlled by
means of a temperature control on a pilot tray in the stripping section which acts on the
lps flow to the reboiler, while the reflux is controlled at a constant flow rate. The column
pressure is controlled by acting on the flow of industrial water to the overhead
condenser. The level in the reflux accumulator is controlled by acting on the flow rate of
the outgoing distillate; the level at the bottom of the column is controlled by acting on
the outgoing residue flow rate.
 Exercises - E09

Broth

c.w.

lps

H2O+im
purities
H2O+C4H10O
Acetone
+EtOH

lps
 Exercises - E09
Students should perform the design of the distillation column, considering the ideal case
and estimating the relative volatility as geometric average between light key component
(acetone) and heavy key component (1-butanol) calculated as vapor pressure ratio at
the top (1 atm) and the bottom (1.2 atm). The density of vapor phase can be considered
equal to that of acetone at 80%mol and water at 20%mol (use the ideal EOS to
calculate it, the molar mass of acetone is 58.08 kg/kmol and that of water is 18.02
kg/kmol) whereas the vapor molar flowrate is 400 kmol/h. Consider a D/F=1/3 and a
light key mole fraction (x) of overhead equal to 0.9 and of bottom equal to 0.03.
 Exercises - E09
An organic mixture consisting of acetone and toluene is subjected to extraction with
water, to recover acetone. The extracted phase is separated by distillation: the acetone
is recovered at the top, while the water, which contains traces of acetone and toluene,
is recovered from the bottom and recirculated upon extraction. At a pressure of 1 atm,
the boiling temperature of acetone is 56 ° C. The block diagram is the following

(Refined)
C7H8+traces of Solvent
acetone and water Acetone+traces of
recirculation
water

Extractive column Distillation

Water+Acetone+traces
of C7H8 (Extract)
Acetone+ C7H8
 Exercises - E09
Basing on the involved products, it is assumed that both columns operate at
atmospheric pressure; the extraction will work at about 40 ° C, a temperature that can
be reached by cooling the recycled solvent with industrial water, while for distillation,
condensation will be carried out with industrial water and steam will be sent at low
pressure to the reboiler. The solvent is dispersed in the extraction column (assuming
that it is the one with the greatest volumetric flow rate) and a packed column is used
(the dispersed phase enters the packings). Given the flammable nature of the products,
the extraction column will be filled with an inert material (nitrogen).
 Exercises - E09
On the basis of what is indicated in the text, the concentration control on the refined is
set, which acts on the solvent flowrate. The pressure is controlled by acting on the input
/ purge of nitrogen in the top. The level at the interface between the heavy and light
phase is controlled by acting on the output of the heavy phase (extract): the controller
acts in cascade with a flow controller placed before the distillation column. The level at
the interface between the light phase and nitrogen is controlled by acting on the flow of
the outgoing light (refined) phase.

water N2

c.w.

Acetone+ C7H8

Refined
 Exercises - E09
The separation in the distillation column is controlled based on the temperature of a
pilot tray in the stripping section, and acts on the lpsin the reboiler, while the reflux is
controlled at a constant flow rate. The pressure is controlled by acting on the water flow
to the condenser and the levels of the backflow accumulator and the bottom of the
column are controlled by acting on the outgoing distillate and residue flow rates. The
solvent recovered from distillation is cooled by preheating the extract fed to the same
column, is then brought to the temperature at which the extraction column works by
means of an additional exchanger.

c.w. c.w.

Acetone+tra
ces of water

lps
 Exercises - E09

water N2

c.w.
c.w.
c.w. c.w.

Acetone+ C7H8

Acetone+tra
ces of water

lps
Refined Acetone+tra
ces of water
 Exercises - E09
Dimethylether (DME) is produced by the reversible dehydration reaction of methanol

The methanol (fresh + recirculated), heated and vaporized, is fed to a tubular catalytic
reactor at a pressure of 13 atm and at a temperature of 355 ° C. Consider a flowrate of
methanol fed to the reactor of 600 kmol/h. The reaction is exothermic and the reactor is
cooled by BFW (Boiler Feed Water), producing steam, to maintain the outlet
temperature at 375 ° C. The conversion per step is 83.6% molar. The effluent stream
from the reactor, consisting of DME and water produced by the reaction and of the
methanol that does not reacted, is fed to a distillation separation train (two columns).
The separated methanol is recirculated to the reactor. The conditions of the fresh
methanol feed (99% mol methanol and 1% mol water) are 1 atm and 50 ° C. Pay
attention to possible thermal recoveries! The block diagram of the process is shown in
the figure.

DME

Feed
Distillation MeOH
MeOH conditioning+r
train
eaction

water
 Exercises - E09
The students should draw the simplified PFD with at least FBC (remember to draw both
sensor-transmitters and controllers) and should design the PFR, considering a first-
order irreversible reaction with respect to partial pressure of methanol (simplified case),
with k0=500, Ea=350 kJ/mol (remember to estimate both volume and vessel diameter,
considering it as an empty cylindrical vessel; in the calculation of the diameter,
remember to avoid, if possible, gas velocity larger than 25-30m/s, to reduce pressure
drops through the catalytic bed, that is not considered in the calculation to simplify it,
and for the optimal L/D use a value >6 and <25).
 Exercises - E09
A stream consisting of pentane, hexane and heptane must be separated into the
individual constituents using an indirect scheme, i.e. by removing the heptane in a first
column and then separating the pentane from hexane in a second column, as shown in
the block diagram. On pressure of 1 atm the boiling temperatures of the compounds
are: pentane = 36.1 ° C; hexane = 68.7 ° C and heptane 98.4 ° C. The block diagram is
the following

Pentane+hexane Pentane

Feed
Distillation Distillation

heptane Hexane
 Exercises - E09
The first column could operate at atmospheric pressure or slightly higher (depending on
the composition of the distillate), while the second will have to work at a pressure higher
than atmospheric in order to be able to use industrial water as a coolant to the
condenser; lps can be used in the reboilers for both columns. One’s can think that the
first column may work at a higher pressure than the second, to take the distillate in the
vapor phase from the first column to the second one, without the necessity of a
compressor. If Heat recovery from the two residues can be performed (the residues are
sent to storage), therefore it is necessary a total condenser in the first column and the
distillate is pre-heated before entering the second column.
 Exercises - E09
The regulation adopted is the "classic" one of the distillation columns: verification of
separation by controlling the temperature on the pilot tray which acts on the lps to the
reboiler, keeping the reflux flow rate constant (the head product purity can be also
controlled by a second pilot tray with inferential control on T, but it depends on the feed
characteristics and on the purity wanted in the distillate); pressure control acting on the
flow of industrial water to the condenser, and level control that acts on flowrate of the
residue. A pump is needed to feed the distillate from the first column to the second; the
level control placed on the reflux accumulator of the first column acts in cascade with a
flow controller, in order to avoid sudden variations in the flowrate fed to the second
column. The distillate stream is first preheated with the residue from the second column
(hexane) and therefore with that of the first column (heptane) which is at a higher
temperature; the control valve is located downstream of the exchangers and
immediately before the entrance to the second column. The exchangers are not
regulated, in order to allow maximum heat recovery; the regulation valves placed on the
residual streams of the first and second column are positioned downstream of the
exchangers.
 Exercises - E09

C6 C7

c.w. c.w.
feed

lps C5+C6 C5
lps
 Exercises - E09
Students should design the second distillation column, considering a x of overhead of
0.98 (ideal binary distillation, do not consider impurities of C7, heptane), a D/F of 0.25, a
vapor phase molar flowrate of 300 kmol/h and the operative pressure equal to 2 atm
(pay attention to the vapour pressure calculated at top and bottom for the geometric
average to estimate relative volatility, consider 30 trays and a pressure drop between
trays of 8 mbar). The average density of vapor phase is calculated by ideal EOS,
considering a mixture of 25%mol C5 and 75%mol C6.