Process Systems Engineering

Prof. Davide Manca – Politecnico di Milano

Exercise 5

Simulation of HDA plant in

UniSim®

Lab assistants: Roberto Totaro – Salman Nazir

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 Level 1
BATCH PROCESS CONTINUOUS PROCESS

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 Level 2

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 Level 3

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Defining EP4
The economic potential of the fourth level is defined as:

EP4 = EP3 − € separation section

with EP4 in [M€/y].

• If the potential of the fourth level is greater than zero, the process may
be economically attractive; vice versa, the process is definitely not
economically interesting.

• Remarks: The cost of the flash is considered to be negligible, because it

is much lower than that of a distillation column.

• To calculate EP4, we must measure all the pieces of equipment for the
separation of the products from light and heavy products.
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Cost
Equipment costs are the sum of two contributions:
• the fixed costs of investment;
• operating costs.

In the calculation of EP4, the cost of columns and heat exchangers (i.e. reboilers
and condensers, but also the furnace and other important process to process heat
exchangers) is taken into account.
For the sake of simplicity, we will assume the same depreciation period for all the
process units which is the one assumed for the EP3 assessment that it is 5 years
due to the mechanical and thermal stresses on the compressor.

The investment costs are the sum of the physical costs of the material used for the
construction of the equipment and processing costs (i.e. welds, ...).

The operating costs are dependent on the operating conditions, by the

consumption of electrical energy and utilities (i.e. compressed air, oil, ...).

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Problem!
• To find the costs of investment and operation of a column it is necessary
to know the diameter and the number of trays required for the separation.
• In this phase, the hypothesis of ideal separation of the components is
removed (as was introduced in the calculation of EP2). It is therefore
necessary to introduce the tray efficiencies in the separator section.

To simplify this complex operation you can simulate the system

through a process simulator (UniSim®)!

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 Level 4

REACTION SECTION

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 Level 4

SEPARATION SECTION

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 TOLUENE RECYCLE

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 HYDROGEN RECYCLE

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 First steps

Until flash

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 First steps

Until flash

First attempt from Matlab results

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 First steps

Until flash

Heating to inlet reactor temperature

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 First steps

Until flash

Adiabatic PFR
Input: Length and Diameter values
First attempt from Matlab results

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 First steps

Until flash

Lamination to 32 bar

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 First steps

Until flash

Cooling to 35 °C

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 First steps

Until flash

Adiabatic flash to achieve

an initial separation

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 First steps

Until flash

Splitting ratio SR from

Matllab results

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 First steps

Until flash

Compression to 37 bar

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 First steps

Until flash

Selectivity = 𝟎𝟎, 𝟗𝟗𝟗𝟗

𝑯𝑯
Inlet ratio to reactor 𝑻𝑻𝑻𝑻𝑻𝑻
𝟐𝟐,𝒊𝒊𝒊𝒊
= 𝟓𝟓
𝒊𝒊𝒊𝒊

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 Data recap
Initial values of the material flows F1 and F2:
• From Matlab results corresponding to the optimal value of xv;

Heat exchanger:
• Tout = 600-750°C;

PFR:
• Values of H, D [m] from Matlab results corresponding to the optimal value of xv;

Valve:
• Pout = 32 bar;

Heat exchanger:
• Tout = 35 °C;

Adiabatic flash:
• The operative conditions are set by the valve and the heat exchanger; no other
input is needed
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 Data recap
Splitter:
• Splitting ratio SR corresponding to the optimal value of xv;

Compressor:
• Pout = 37 bar;

Mixer:
• Set outlet to the lowest inlet;

Adjust 1:
• Target variable: Inlet ratio to the reactor
• Adjustable variable : F1 flow-rate

Adjust 2:
• Target variable: Selectivity
• Adjustable variable: Tube length

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UniSim – Setting the simulation
To set up a simulation with UniSim® you must do the following:

• Select all the components inside the system.

• Select the equation of state to use.

• Select the kinetic scheme.

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UniSim – Chemical composition
Once you set a new simulation, you must do the followings:

• In the window "Simulation Basis Manager" can be entered by selecting the tab
"Components", add new components to the simulation by pressing the "View ...".
• You can search for a single component within the UniSim database in three
ways:
o By name in the database.
o Through the real name of the chemical species.
o Through its chemical formula

• Once you have selected the component of interest, press the button “Add
Pure”.
• Once you have entered all the chemical species of interest, close the window.

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UniSim – Equation of state
• In the window "Simulation Basis Manager" it is possible adding new equations of
state to model the system by selecting the tab "Fluid Pkgs".

• Once you have identified the equation of state of interest, select it.

o We recommend using the equation of state for vapor-liquid equilibrium called

“RKS”.

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UniSim – Kinetic Scheme
• It can be done, in the window "Simulation Basis Manager", by selecting the tab
"Reactions", add a set of chemical reactions.
• Using the button "Add Rxn ..." you can enter a single reaction in the kinetic
scheme: at this point you need to select the typology (kinetics, equilibrium,
conversion ...).
• Once you open the new window, in the menu "stoichiometry" insert chemical
species taking part in the reaction, accompanied by their stoichiometric
coefficients (those of the reactants are negative). Then make sure that the mass
balance is satisfied.
• Within the tab "Basis" select the main component, the phase in which the
reaction takes place and, if the reaction is conversion, the expression of the
latter property.
• If the reaction is kinetic, enter the pre-exponential term and the activation energy
in the tab "Parameters".
• Once you've entered all the reactions, add the package thermodynamic by
selecting the "Add to FP."

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UniSim – Kinetic Scheme
It is possible to fit the kinetic scheme in two different ways:
• Reactions to conversion: it is necessary to provide conversion of the reactions
with respect to the main reagent (toluene and benzene respectively for the first
and the second reaction) calculated by Matlab™ at 4 different temperatures.
Once we are inside the simulation environment, it will be necessary to use a
reactor conversion.

• Reaction kinetics: You must provide the kinetic parameters of the reactions.
Once we are inside the simulation environment, it will be necessary to use a
reactor PFR. Because of non-ideality of the reaction mixture, the conversion will
be less than that calculated by Matlab ™; it will be therefore appropriate to resize
the reactor to meet the specifications.

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UniSim – Simulation environment
After completing all the above steps, you can enter in the simulation by pressing the
"Enter Simulation Environment".

At this point you can provide to build the plant.

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Flowsheet HDA
Riciclo gassoso
Compressore
Spurgo
Quench
Fornace

Scambiatore
Flash

Idrogeno fresco
Reattore
Cooler

Fuel

Toluene fresco
Metano

Colonna del prodotto

Colonna del riciclo

Benzene Toluene
Stabilizer

Difenile

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Some tips
• It would be better to start from the values of the first attempt of the streams of the
process, identified in the calculation of EP2. Thus simulating the first mixer
accounting only for the fresh streams (F1 and F2), it is better accounting also for
the recycling stream in the gaseous phase (R) and the recycling stream of
toluene in the liquid phase (T).

• The feed ratio of 5:1 can be controlled by means of two operations: the
"Spreadsheet", i.e. a spreadsheet where you can import the compositions of the
two main components in the stream exiting the first mixer and then calculate the
ratio, and the operator "Adjust ", capable of acting on a dependent variable (the
hydrogen feed), in order to reach the specified value of the objective function
(the cell of the Spreadsheet where it is calculated the ratio between hydrogen
and toluene).

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Flash
• Downstream of the flash, the vapor phase is re-circulated to the reactor after
purging.

• The composition of the flow coming out of the flash depends ONLY on the
temperature and the molar fraction of hydrogen in the vent. This stream is
heated to T = 93.35 °C and laminated to 3.6 bar to be sent to the distillation
columns.

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Distillation column
Downstream of the flash, the liquid phase is sent to the distillation section to
separate further the components and reach specific purity of benzene (purity
99.97% molar).

We have to design some columns to operate the separation between four different
phases:
• Benzene (main product)
• light products (i.e. methane and hydrogen, burnt to produce energy)
• Toluene (to be recycled to the reactor)
• Biphenyl (to be burnt to produce energy)

You need to design a section separation, while working to minimize costs.

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Designing section separation
You need to separate four components: there are 5 different options!

However, there are guidelines to help you select the most appropriate sequence:

1. Remove the CORROSIVE components as soon as possible (the columns in

carbon steel cost more).
2. Remove components and REACTIVE MONOMERS.
3. Remove PRODUCTS streams and recycling as DISTILLATES in order to have
purified streams that do not degrade the quality of the product and of the
reactants.
4. In the case in which PRODUCTS and recycle are located at bottom of the
column, it is better to take them in the vapor phase and then condense them for
the same reason of point 3.

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Designing section separation
Following the guidelines, we can draw the following conclusions:

Delete first corrosive components and use stainless steel for separating hydrogen
and methane through a column (Stabilizer) to remedy the corrosion of the metal by
hydrogen.

To separate benzene, toluene and biphenyl you can proceed in two different ways:
1. Separate first Benzene from Toluene + Biphenyl and then from Toluene;
2. First separate Benzene + Toluene from Biphenyl and then the Benzene from
Toluene.
You choose the first option because Benzene is the most abundant compound.

Furthermore, using the first solution, the main product (benzene) and the recycled
stream to the reactor (toluene) will be separated as distillates of the columns, thus
resulting streams can much more easily purified as compared to the solution in
which they were obtained at bottom of the column.

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Column stabilizer
The stabilizer is made up of five real stages (3 trays) and its “feed tray” is 2nd. The
pressure on the first plate is 3.5730 atm.

Remarks:
It is possible to employ a partial condenser, as it is not necessary to obtain the light
product in liquefied form (condensable): the refrigerant to be used is water, as it is
economical fluid and which does not create safety problems or corrosion. The inlet
temperature is 30 °C, whereas the maximum recommended output temperature is
38 °C. Despite this limitation, it is the needed to recover the maximum possible
benzene in the liquid.

Additional data (indicative):

• flow head (overhead flow) = 36.180 kmol/h;
• kettle reboiler duty = 1.5 ⋅ 106 kcal/h and T estimated as 137 °C;
• estimation of the reflux ratio L/D = 0.61900.

The liquid stream exiting the stabilizer is cooled to T = 87.08°C and laminated to 1
bar.

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Product column
For the design of the second column the specifications assigned at the top are:

• purity of the recovered benzene 99.97% molar;

• recovery of 99.5% with respect to benzene fed.

The column operates at atmospheric pressure and with a total condenser. For
the calculation of the efficiency of the column, we use the formula:

0.5
E0 =
(µFα )
0.25

where µF is the viscosity of liquid feed to the bubble point measured in cP

(centipoise - we recommend a value of 0.3 cP) andα is relative volatility of the
two species to be separated.

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Product column
The design of the product column should be entirely done by the student.

The column should be sized by methods other than McCabe and Thiele because it
is not ideal (e.g. Fenske). It is possible to assume a reflux ratio 1.3 times the
minimum ratio.

To choose the number of trays you have to analyze the temperature and
concentration profiles in column (Output - Generate Plot).

The choice will have to take into account that the lowering of number of trays
involves an increase in the duties.

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Recycling column
You are required to recover:
• Top product at 99.5% of the toluene fed;
• Bottom product at 99.5% of biphenyl fed.

The real stages are 20 (18 trays) and the “feed tray” is at 14th stage
(numbered from the top). The efficiency of the column is computed with the
formula previously presented.

Additional data (indicative):

• head pressure of 1 atm;
• flow rate of tail (bottom) 5 kmol/h;
• flow head (overhead) 108 kmol/h;
• kettle reboiler duty of 0.919⋅106 kcal/h and T estimated at 191.5 °C;
• condenser to the bubble point with duty of -0.8827⋅106 kcal/h and T estimated
at 110 °C;
• it is advisable to operate with a recycle ratio of not less than 1.5 times the
minimum. Estimated reflux ratio L/D = 0.012.
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Efficiency concept
The efficiency is related to the mass transfer, which depends on the geometry and
the design of the trays by the flow rate, from the paths followed by the currents,
from the composition.

You can define:

The efficiency of the column:
Nid
η= N
real

Basically you assign a unique value of efficiency to the entire column. Is it okay for
a preliminary design? In fact the concept of efficiency is too articulated in order to
be confined to a single parameter for the whole column.

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Concept of efficiency
• The “local efficiency”: identifies the efficiency of a point on the plate, good for
large diameter columns.

• The “tray efficiency” : also known as the Murphree efficiency. The calculation
assumes a perfect mixing on the plate. For multi-component mixtures must be
assigned an efficiency of tray for each of the components themselves.

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Suggestions
• You have to assess if it is possible to operate with only two columns to separate:
the benzene in the top in the first and in the second biphenyl in the bottom,
recycling the residual toluene fraction. Specify the reasons for the impossibility of
such a solution.

• Identify and design the best separation section.

• Perform the short-cut design of the column of the product (NOT using UniSim) in
order to determine the minimal number of plates and the real one, and the
optimal feed point.

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