EH2207GG

DESIGN PROJECT I (SEPT 2018)

PRODUCTION OF 35,000 METRIC TONNES OF POLYETHYLENE PER YEAR

CHAPTER 5: SIMULATION
GROUP MEMBERS

AHMAD NABIL HISYAMUDDIN BIN MAT RIPIN 2016250392

NIK NUR AINAN RASYIDAH BINTI ABD RAHIM 2015209454
MUHAMAD NAZMI BIN AHMAD 2015238636
FARRAH KHALIDAH BINTI NOR WAHID 2016250472
AIMAN HAZIM BIN MOHD ZAIDI 2015283876

SUPERVISOR:
PROF MADYA DR AYUB MD SOM

FACULTY OF CHEMICAL ENGINEERING

UNIVERSITI TEKNOLOGI MARA
SHAH ALAM
Table of Contents
5.1 EQUIPMENT SELECTION.......................................................................................................... 3
5.1.1 CSTR-1 and CSTR-2 .............................................................................................................. 3
5.1.2 Flash tank ................................................................................................................................ 3
5.2 SELECTED PHYSICAL PROPERTIES/ PROPERTY METHOD PACKAGE ..................... 4
5.2.1 POLYCSF ................................................................................................................................ 4
5.3 BUILT-IN ATTRIBUTE GROUP ................................................................................................ 4
5.3.1 Ziegler–Natta selection ........................................................................................................... 4
5.4 SIMULATION PROCEDURE ...................................................................................................... 5
5.5 SIMULATION PROCESS ............................................................................................................. 7
5.6 Simulation Results .......................................................................................................................... 8
References .................................................................................................................................................. 10
 Chapter 5

Process Simulation

5.1 EQUIPMENT SELECTION

Selection of equipment consideration only be made for modeling of polymerization process

where other equipment have been neglected since the yield of polymer product only have to be
simulated from justified temperature, pressure, composition of reactant and selected catalyst.
Modelings of polymerization of Ethylene into Polyethylene only include set of reactor and
separator for simulation in Aspen Plus.

5.1.1 CSTR-1 and CSTR-2

Purpose of selection of CSTR-1 and CSTR-2 is to ease the modeling of the fluidized
bed reactor according to Polymers Plus: Polymer Process Modeling User Guide where
polymerization process of Ethylene into Polyethylene will take place. Involvement of
CSTR-1 will works for gas phase while CSTR-2 works more on polymer phase. Production
of high density Polyethylene follows the Ziegler–Natta polymerization where Ziegler–
Natta catalyzed systems will apply in this reactor. Ziegler–Natta transition metal titanium-
based catalysts specifically Titanium-Tetrachloride (TiCl4) are used for the reactor (Malah,
2017).

5.1.2 Flash tank

After polymerization of Ethylene has completed, remaining unreacted monomer

will be separated or removed by flash tank to obtain polymer products only. Supposedly
 flash tank operations only are used for separating liquid and vapour component with the
principle of flash distillation. Since this process separates only solid polymer and unreacted
gas, flash tank can be considered for modeling the separation between polymer and
unreacted gas (Malah, 2017).

5.2 SELECTED PHYSICAL PROPERTIES/ PROPERTY METHOD PACKAGE

5.2.1 POLYCSF

Selection of thermodynamic properties of polymer systems is to define the

properties in process modeling involving polymerization where it will determine the
thermodynamic properties of polymer product which is Polyethylene. Thermodynamic
properties offered in Aspen Plus given in package of property methods where it includes
the methods of calculations involving polymerization process or route of process
calculation. Property method that has been selected for this polymerization simulation is
POLYCSF where it is use in perturbed-chain statistical associating fluid theory equation
of state for thermodynamic property calculations. This property method able to deal with
the set of calculation involving fugacity coefficient, enthalpy, entropy, Gibbs free energy,
density (Malah, 2017).

5.3 BUILT-IN ATTRIBUTE GROUP

5.3.1 Ziegler–Natta selection

Built-in attribute group offered in Aspen Plus depends on user selection. Referring
the catalyst in the reactor which is Ziegler–Natta catalyst, built-in attribute group that has
been selected is Ziegler–Natta selection where it will estimates several attributes of
polymer including number and weight average molecular weight, number and weight of
degree of polymerization, and polydispersity in both Ethylene and Polyethylene based on
Polymers Plus: Polymer Process Modeling User Guide. It must also be specified for the
 HDPE selection where it will estimate such attributes related to HDPE polymerization
related to Ziegler–Natta catalyst. Attribute estimate for the polymerization estimated is
CPSFLOW (Mole flow of potential sites) CPSFRAC (Mole fraction of potential sites)
CDSFLOW (Mole flow of dead sites) CDSFRAC (Mole fraction of dead sites) CVSFLOW
(Mole flow of vacant sites) and CVSFRAC (Mole fraction of vacant sites). These set of
attributes will calculate the multisite Ziegler–Natta catalyst.

Figure 5.1: Polyethylene Simulation (Malah, 2017).

5.4 SIMULATION PROCEDURE

First, the feed will be grouped into a feed stream and directly involves in the process with
a total component of seven which are Titanium Tetrachloride (TiCL4), Triethyl – Aluminium
(C6H15Al), Ethylene (C2H4), Hydrogen (H2), n-Hexane (C6H14), High Density Polyethylene
(HDPE) and C2H4 – R. These components were extracted into properties section of the Aspen Plus
to setup and initiate the reaction.

Next, the polymers were setup. C2H4-R will act as a segment for polymerization process.
Segments are the structural units of a polymer or oligomer and are specified independently from
these components. Their structure is fixed throughout a simulation. Segments typically correspond
to the monomers used to grow the polymer. Then, the polymer ID were determined and it was
HDPE. The Built-in attribute group would be Ziegler-Natta selection. The reason for this selection
is that the process uses Ziegler-Natta as our catalyst which is the TiCL4 itself. For the site-based
species, the catalyst is TiCL4 and the number of set type is 4 and maximum sites concentration is
0.0001. After that, the method of filtration is polymer and the base method is POLYPSCF.

Next, the equipments and flow materials line were placed in the flowsheets and connected.
After that, comes the tricky part which is reaction determination. The catalyst reaction would be
Ziegler-Natta reaction since the catalyst itself is a Ziegler-Natta catalyst. The species is determine
in the table below.

Table 5.1 Components and their Role

Components Role
Titanium Tetrachloride Catalyst
Triethyl – Aluminium Co-catalyst
Ethylene Monomers
Hydrogen Hydrogen
n-Hexane Solvent
High Density Polyethylene Polymer
C2H4 – R Segment

Then, the rate constant of the reaction were determine for every components. Component
attributes would be MIXED and the component is TiCL4 with attributes of CAPSFLOW.
 5.5 SIMULATION PROCESS

First, all of the parameters required were filled in according to the mass balance and energy
balance. The feed including monomers and catalyst were reacted with CSTR to initiate a pre-
polymerization process between ethylene and co-monomer which is n-hexane. The process is used
to grow the feed by reacting with monomers.

Then, the product from the first CSTR entered into the second CSTR. This time
polymerization process really reacted in here according to the rate constant implemented before.

After the polymerization process, flash tank were used to separate catalyst with monomers
and product which is HDPE.

5.5.1 Justification

There’s some major discard on our equipment from our process flow diagram on the
simulation. The reason are when we do the simulation on Aspen Plus, the simulation will not
converge even with our best efforts. So, we take our own alternatives to simplify the process to
increase the chance of the process to converge. In our desperate attempts, we look up to an example
as a guide to our simulations and it seems to be very effective.
 5.6 Simulation Results

After several attempts on the simulation, we fail to get the results that we were hoping for.
The reason are because we did not have any knowledge about Aspen Plus since we have inadequate
expertise in our faculty. We are fairly disappointed with the results that we get. Lastly, the real
failure is that the unknown parameter isn’t enough to get the results we wanted.

Figure 5.2 Errors on missing unknown parameters

Figure 5.3 The full scale of the simulation on Aspen Plus
References
Malah, K. (2017). Aspen Plus: chemical engineering applications. Hoboken, New Jersey: John
Wiley & Sons Inc.

Polymers Plus: Polymer Process Modeling User Guide. AspenTech.