Aspen Polymers: Spheripol Hi-Impact Polypropylene Model

Aspen Polymers
Spheripol Hi-Impact Polypropylene Model

Version Number: V10
May 2017
Copyright (c) 2016-2017 by Aspen Technology, Inc. All rights reserved.
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Contents
1 Overview ..............................................................................................................5
2 Physical Properties...............................................................................................7
3 Reaction Model...................................................................................................13
4 Process Description............................................................................................17
5 Modeling Approach.............................................................................................19
6 Model Convergence ............................................................................................23
7 Model Predictions ...............................................................................................25
8 Model Results Compared to SRI Mass Balance ...................................................29
9 Model Applications .............................................................................................31
10 Sources ............................................................................................................35
Contents 3
4 Contents
1 Overview
This report documents Aspentech’s sample model illustrating how to simulate

the Spheripol high-impact polypropylene (HiPP) process using Aspen Plus with
Aspen Polymers. The Spheripol process, licensed by LyondellBasell, uses one
or more slurry loop reactors to produce polypropylene homopolymer, followed
by a gas phase reactor producing the ethylene/propylene co-polymer.
The process simulation model can be applied to help improve production
rates, yield, and product quality in existing plants, or to design and scale up
new plants. The physical property parameters in for this model have been
regressed and evaluated as described later in this report. The reaction
parameters and reaction model are representative of a broad range of
catalyst recipes – since there are a broad range of catalyst used in industry,
these parameters should be calibrated to match a specific production line and
product grade. The rate constants in this model are drawn from many
sources, are approximate, and have been tuned to match ‘typical’ plant
conditions.
The process configuration, operating conditions, and equipment sizes are
based on the report Polypropylene Update Supplement C from SRI
Consulting [Process Economics Program Report 128C] (SRI Consulting is now
a division of HIS – go to www.ihs.com to order the report). Some aspects of
the model were drawn from the Spheripol Plant Operation Manual, interviews
with engineers from operating companies, and patent literature. The
underlying reaction model is based on J.B.P. Soares et al, Mathematical
Modelling of the Microstructure of Polyolefins made by Coordination
Polymerization: a Review [Chem. Eng. Sci. 56 (2001) 4131-4153].
1 Overview 5
6 1 Overview
2 Physical Properties
This model includes a number of components as shown below. The model

considers a titanium catalyst on an inert support, with triethyl-aluminum as a
co-catalyst. In the real plant, organic solvents such as hexane are used to
deliver the catalyst to the first reactor – the carrier solvent is essentially inert
and has been ignored to keep the model simple.
Component ID Type Component name Alias
CAT Conventional TITANIUM-TETRACHLORIDE TICL4

TEAL Conventional TRIETHYL-ALUMINUM C6H15AL
PROPENE Conventional PROPYLENE C3H6-2
PROPANE Conventional PROPANE C3H8
ETHENE Conventional ETHYLENE C2H4
ETHANE Conventional ETHANE C2H6
PP Polymer POLY(PROPYLENE) PP
H2 Conventional HYDROGEN H2
C3-SEG Segment PROPYLENE-R C3H6-R
C2-SEG Segment ETHYLENE-R C2H4-R
N2 Conventional NITROGEN N2
STEAM Conventional WATER H2O
MODIFIER Conventional TETRAMETHYLSILANE C4H12SI
The PC-SAFT equation of state is used to characterize the pure component

properties and phase equilibrium. Note that Aspen Plus treats polymers as a
pseudo-liquid when calculating phase equilibrium; this allows the model to
predict the solubility of monomers, solvents, and additives within the polymer
phase. The phase equilibrium between conventional species and the polymer
is characterized through the binary parameters between conventional species
and polymer segments.
The table below documents the pure component parameters for the PC-SAFT
model. The “M”, “U”, and “V” parameters are used to characterize most
conventional species. Additional terms are used to characterize water to
capture its polar nature. The parameters for the catalyst and additives have
been set to keep these components effectively non-volatile.
2 Physical Properties 7
Parameters PCSFAT PCSFAU PCSFAV PCSFTM PCSFTR PCSFTU PCSFTV
Units K K
CAT 20 233.27 3.755

TEAL 20 233.27 3.755
PROPENE 1.9597 207.19 3.536
PROPANE 2.0020 208.11 3.618
ETHENE 1.5930 176.47 3.445
ETHANE 1.6069 191.42 3.521
PP 273.15
H2 0.8285 12.53 2.973
C3-SEG 0.02528 298.64 4.147
C2-SEG 0.04132 267.19 3.475
N2 1.2053 90.96 3.313
STEAM 2 2500 0.03487 2.9291 316.79 2.047
MODIFIER 20 233.27 3.755
Some of the binary parameters for this model are drawn directly from the
Aspen Plus databases. The parameters for hydrogen in ethane, propane, and
propene were regressed against VLE data from the NIST source databank.
The parameters for propane and propene in polymer have been adjusted to
match observed solubility. The PC-SAFT binary parameters are calculated as
Kij = Aij + Bij*(Tref/T) where the temperatures are in degrees K.
Comp i Comp j Source AIJ BIJ Tref
PP PROPENE USER -0.0036 0.0000 298.15 K

PP PROPANE USER -0.0083 0.0000 298.15 K
PROPENE PROPANE R-C3-C3ENE -0.0041 0.0093 298.15 K
PROPENE ETHENE R-C2Y-C3Y -0.0057 0.0029 298.15 K
ETHENE N2 APV88 PC-SAFT 0.0750 0.0000 298.15 K
ETHENE ETHANE USER 0.0061 0.0000 298.15 K
H2 ETHANE R-H2-C2H6 -0.8114 0.4055 298.15 K
H2 ETHENE USER -0.8114 0.0000 298.15 K
H2 PROPENE R-H2-C3H6 0.0334 0.0000 298.15 K
H2 PROPANE R-H2-C3H8 -0.1903 -0.0101 298.15 K
Phase equilibrium parameters for propylene/propane, ethylene/ethane, and

propylene/ethylene systems were regressed against data from NIST. Some
representative sets of PXY data are shown in the figures below. The quality of
the phase equilibrium predictions for each of the ethane/propane system was
confirmed against NIST data.
8 2 Physical Properties
Phase Equilibrium Predictions and Data for
Ethylene/Propylene System
P-xy of ETHENE PROPENE
60
55
50
75 C
20 C
45
10 C
40
50 C
35 0C
Pressure bar
30
-10 C
25
20
15
10
0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00
Mole Fraction ETHENE
Phase Equilibrium Data and Predictions for Propylene-

Propane System
P-xy of PROPANE PROPENE
44
87.7 C
42
40
38
36
Pressure bar
76.8 C
34
32
71.1 C
30
28
26
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00
Mole Fraction PROPANE
Phase Equilibrium Data and Predictions for Ethylene-
Ethane System
P-xy of ETHANE ETHYLENE
47.5
45.0
5C
42.5
40.0
37.5
35.0
Pre ssure kg/sqcm
32.5 -10C
30.0
27.5
25.0
-25 C
22.5
20.0
17.5
15.0
12.5
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00
Mole Fraction ETHANE
The parameters for H2 were regressed in order to improve the accuracy of

the hydrogen solubility in the liquid phase. The hydrogen solubility is very
important because hydrogen has a strong influence on the polymerization
reactions.
The figure below is a representative example showing the quality of the fit for
H2 in ethylene at various temperatures. The next set of charts compares the
model predictions against data for H2 in ethane, ethylene, propane, and
propylene. Each chart shows the data at the highest temperatures.
All of the data regression cases are contained within the property
environment of the example files; re-run the regression cases to see a full
summary of these results.
Phase Equilibrium Data and Predictions for
Hydrogen/Ethylene System
P-xy of ETHENE H2
1050
1000 -98 C
950
900
850 -115 C
800
750
700
650
-73.3 C
600
Pressure bar
550
500 -38 C
450
400
350
300
-26 C
250
200
150
100
50
0
0.000 0.075 0.150 0.225 0.300 0.375 0.450 0.525 0.600 0.675 0.750 0.825 0.900 0.975
Mole Fraction ETHENE
Selected Parity Plots – Hydrogen Solubility in Light Olefins
H2 in Ethane H2 in Ethylene
H2 in Propane H2 in Propylene
3 Reaction Model
Many different polymerization catalyst formulations can be used within the

Spheripol process. The application example includes representative rate
constants based on a wide range of sources. The example uses a Ziegler
catalyst with four types of active sites (reaction model ZN-S4). A single-site
reaction model (ZN-S1) is also available as a template, however this model is
not referenced by any of the reactor blocks.
The maximum number of active sites (MAX-SITES) for the catalyst has been
estimated to match the reactor productivity reported in the SRI report
(Polypropylene Update C, 2001). This parameter depends on the level of
doping on the catalyst support (e.g., the ratio of active species to inert
species) and to a lesser degree on the way the catalyst has been prepared.
Exposure to moisture or other poisons can reduce the apparent maximum
sites of a particular batch of catalyst. The theoretical upper limit is the weight
% of active catalyst on the support / molecular weight of the active species.
Assuming a doping level of 3 wt%, the upper limit of MAX-SITES is about
1.6E-4 kmol/kg. The estimated value of 9.0E-5 implies about 60% of the
titanium sites are available for reactions.
The reaction model has been set up to simulate co-polymerization of ethylene
and propylene. For each site, there are four types of propagation rate
constants to consider, corresponding to the four possible combinations of
active end groups and monomers. The predicted conversion of propylene to
polypropylene in the loop reactors is strongly influenced by the propagation
rate constants, as well as the catalyst and co-catalyst concentration. The
predicted ethylene weight fraction in the product is influenced by the cross-
propagation and ethylene homo-propagation rate constants. Ethylene homo-
propagation is expected to be significantly faster than propylene homo-
polymerization.
The reaction model considers activation by co-catalyst (TEAL) and activation
by hydrogen. The activation reactions are assumed to be equal for all site
types. Spontaneous activation is not considered in this example, but it could
be easily added to the model if needed. The co-catalyst activation reaction
controls the predicted influence of TEAL on the conversion rate.
The model considers three modes of chain transfer; spontaneous chain
transfer, transfer to hydrogen, and transfer to monomer. Each of these
reactions have been assumed to be independent of the active site type. The
chain transfer reactions strongly influence the predicted melt index (and
weight-average molecular weight) of the polymer. The chain transfer to
hydrogen reaction is very critical since hydrogen is used to control melt index
in the plant. These reaction rates can be tuned to match the observed
MI/hydrogen relationship for a given grade of polymer.
3 Reaction Model 13
The reaction considers spontaneous site deactivation, with the same rate
constants used for all types of sites. The site deactivation reaction influences
the predicted catalyst productivity (kg conversion/kg catalyst) in each of the
reactors. Higher deactivation rates will reduce the productivity in the
downstream reactors.
The catalyst is assumed to be relatively stereospecific. Atactic propagation
reactions are included. These rate constants can be manipulated to match the
observed atactic fraction in the product.
The free-radical model includes a wide range of additional reactions which can
be applied as needed. For example, the model can consider short-chain
branching generated by the addition of butene or hexene, or long-chain
branching resulting from chain transfer to polymer or other side reactions.
14 3 Reaction Model
Summary of Reactions
Class Reaction Reactants Products
Activation by Co-Catalyst 1) Act-Cocat (1) Cps[Cat] + Teal ➜ Po
2) Act-Cocat (2) Cps[Cat] + Teal ➜ Po
Activation by Hydrogen 5) Act-H2 (1) Cps[Cat] + H2 ➜ Po
6) Act-H2 (2) Cps[Cat] + H2 ➜ Po
Initiation 9) Chain-Ini (1) Po ➜ P1[C3-Seg]
10) Chain-Ini (1) Po ➜ P1[C2-Seg]
Propagation 17) Propagation (1) Pn[C3-SEG] + PROPENE ➜ Pn+1[C3-Seg]
18) Propagation (1) Pn[C3-SEG] + ETHENE ➜ Pn+1[C2-Seg]
19) Propagation (1) Pn[C2-SEG] + PROPENE ➜ Pn+1[C3-Seg]
Chain Transfer to Monomer 33) Chat-Mon (1) Pn[C3-Seg] + Propene ➜ Dn + P1[C3-Seg]
34) Chat-Mon (1) Pn[C3-Seg] + Ethene ➜ Dn + P1[C2-Seg]
35) Chat-Mon (1) Pn[C2-Seg] + Propene ➜ Dn + P1[C3-Seg]
3 Reaction Model 15
Summary of Reactions, Continued
Class Reaction Reactants Products
Chain Transfer to Hydrogen 49) Chat-H2 (1) Pn[C3-Seg] + H2 ➜ Dn + Po
50) Chat-H2 (1) Pn[C2-Seg] + H2 ➜ Dn + Po
Spontaneous Chain Transfer 57) Chat-Spon (1) Pn[C3-Seg] ➜ Dn + Po
58) Chat-Spon (1) Pn[C2-Seg] ➜ Dn + Po
Spontaneous Deactivation 65) Deact-Spon (1) Po/Pn ➜ Csd[+ Dn
66) Deact-Spon (2) Po/Pn ➜ Csd[+ Dn
Atactic Propagation 69) Atact-Prop (1) Pn[C3-Seg] + Propene ➜ Pn+1[C3-Seg]
70) Atact-Prop (2) Pn[C3-Seg] + Propene ➜ Pn+1[C3-Seg]
The rate constants used in the model are representative examples only. The
specific nature of the catalyst has a strong influence on the catalyst yield (kg
polymer / kg catalyst) and the stereo-specificity (atactic fraction). This
implies the propagation rate constants depend on the nature of the catalyst
and the electron donors used within the catalyst. The model must be
calibrated against plant or lab data before it is used to design a new plant or
to optimize and existing plant.
A very basic calibration procedure can be considered:
1 Adjust overall propagation rates to match observed conversions
2 Adjust chain transfer rates to match observed melt index
o Use data for different MI grades to determine chain transfer to
hydrogen rates
o Fine tune the model with chain transfer to monomer / spontaneous
chain transfer rates
3 Adjust maximum sites and deactivation rates to match observed changes
in productivity between successive reactors
4 Adjust ratios between propagation rates at different sites to match
polydispersity index or measured molecular weight distributions
5 Adjust atactic propagation rates to match measured atactic fraction
16 3 Reaction Model
4 Process Description
The Spheripol impact copolymer process consists of two large slurry loop
reactors followed by a gas phase fluidized bed reactor. The loop reactors are
usually used to produce polypropylene homopolymer, although it is possible
to feed small amounts of ethylene to the loop reactors to produce random
copolymer grades.
The gas-phase reactor is used to produce copolymer (EPR – ethylene
propylene rubber) containing as much as 50 weight % ethylene. The gas
phase reactor produces about 20 weight % of the overall polymer by mass,
implying the final impact copolymer may contain as much as 10 weight %
ethylene.
The catalyst and co-catalyst are suspended in organic oil to ensure accurate
metering to the reactors. As noted previously, the oil content is ignored in the
model since the flow rate is very small and the solvent is essentially inert in
the process.
The catalyst mixture is metered into fresh liquid propylene feed and passed to
a small pre-polymerization reactor (R-101) operating at 20 C and 35 bar with
a residence time of under 30 minutes. Only about 2% of the fresh propylene
is directed to the pre-polymerizer; most of the fresh monomer flows directly
to the loop reactors. The pre-polymerizer generates a ‘shell’ of polymer
around the fine catalyst particles, which rapidly fragment as the polymer
grows around the active sites. The gentle conditions of the pre-polymerizer
prevents generation of catalyst fines.
The polymer/monomer slurry flows by pressure difference to the first slurry
loop reactor, R-102. Additional monomer and hydrogen are also fed to the
reactor. The hydrogen concentration is carefully controlled in order to
maintain the desired polymer melt index. The polymer from R-102 flows by
pressure gradient to the second loop reactor, R-103, where additional
monomer and hydrogen are fed.
4 Process Description 17
Process Flow Diagram – Spheripol High-Impact
Polypropylene Co-Polymer Process
Each of the loop reactors operate at high pressures up to 45 bar (to keep the
hydrogen soluble), at temperatures ranging from 60-80 C. The solid polymer
is kept suspended by continuous flow through an axial pump inside the pipe
loop. The circulation rate through the loop is much higher than the feed rate,
making each of these reactors behave as ideal CSTRs. Each reactor has a
residence time of approximately one hour. Although the reactors are equally
sized, the first reactor produces more polymer than the second reactor due to
the continuous deactivation of the active catalyst sites.
The slurry from R-103 flows through a heated line to flash drum V-105
operating at about 18 bar. A portion of the overhead vapor is purged to
remove propane which would otherwise accumulate in the recycle loop
(polymer grade propylene may contain as much as 0.5 weight % propane).
The recycle propane returns to the propylene feed drum. Most plants have a
bypass to direct recycle propane directly to the second loop reactor, which
allows better independent control of hydrogen concentration in each of the
two loop reactors.
The polymer from V-105 flows downstream to the gas-phase reactor R-104,
which is fluidized by the recycle gas stream. Fresh ethylene, propylene, and
hydrogen are fed directly to R-104. A small portion of the recycle gas is
purged to remove ethane and propane. The gas loop is compressed and
cooled to remove the heat of reaction from the system.
Polymer leaving the fluidized bed reactor flows to a series of purge bins. The
first purge bin is fed with steam, which strips away residual hydrocarbons and
which poisons the catalyst to stop the reaction. The second purge bin uses
nitrogen to remove most of the remaining residual monomer.
18 4 Process Description
5 Modeling Approach
The pre-polymerizer and each of the loop reactors are represented as ideal
CSTRs using a two-phase flash. The slurry is treated as a pseudo-
homogeneous liquid phase. If the reactor is operated above the bubble point
the model will predict the formation of the vapor phase. The high circulation
rates inside each of these reactors justifies this approach.
The gas-phase fluidized bed reactor is also represented as a CSTR. The
solubility of light gasses in the polymer is taken into consideration by the
phase equilibrium algorithm in Aspen Plus. The gas phase is assumed to be
homogeneous within the bed.
A custom model library “Polymer.apm” is used to include appropriate loop
reactor and gas phase reactor icons for the CSTR model. This library file is
included inside the Aspen Plus compound file to ensure portability between
users.
In the real process, flow controllers are used to maintain a constant rate of
fresh feed to each reactor. This control action is emulated in the model using
FSPLIT block V-104, which represents the propylene feed vessel. The
specifications, shown below, force 2 weight % of the propylene to go to the
pre-polymerization reactor (R-101) and 57 weight % of the propylene to go to
the first loop reactor (R-102). The mass flow rate of propylene to the gas-
phase reactor is specified directly in V-104.
Feed Specifications in FSPLIT Block V-104
A design specification “Makeup” is used to manipulate the fresh propylene

feed rate to meet the target feed flow rate to the second slurry reactor (R-
103). The target set point is specified in the calculator block “Setup” as user-
defined parameter 3. This parameter and other model parameters are
initialized in the calculator block “SETUP” which will execute first in the
calculation sequence. This technique makes it easy to specify many process
specifications in one place (the calculator model) while also providing a
mechanism to manipulate these specifications through sensitivity studies
and/or optimization studies using the model.
5 Modeling Approach 19
Design Specification Connectivity – Slurry Reactors
The design specifications “R1HC” and “R2HC” represent the hydrogen

composition controllers for the two slurry reactors, “R-102” and “R-103”
respectively. The set-points for these controllers are also defined as
parameters as noted below. Each of these design specifications manipulates
the hydrogen make-up stream to each of the two slurry reactors. The purge
mass flow rate rate is specified in the flow splitter block “B5”.
Summary of User-Defined Parameters in the Model

Parameter Description Initial
Value
1 First slurry reactor hydrogen composition set-point,

40
mass PPM
2 Second slurry reactor hydrogen composition set-point,
40
mass PPM
3 Feed flow rate to second slurry reactor, lb/hr 35,000
4 Mass ratio ethylene/(ethylene+propylene) in gas phase
0.5
reactor recycle loop
5 Not used -
6 Gas phase slurry reactor hydrogen composition set-
40
point, mass PPM
The control scheme for the gas-phase reactor is also represented using design
specifications. The design specification “FCGPR” represents the feed flow
controller for the gas phase reactor; it manipulates the ethylene make-up rate
to maintain the target ethylene content in the reactor feed gas (parameter
#5).
The recycle gas circulation rate is set directly in flow splitter “B3”; the purge
gas is calculated to close the mass balance around the gas phase reactor.
20 5 Modeling Approach
Design specification “GPR-H2” represents the gas phase reactor hydrogen
composition controller. The set-point for this reactor is defined as parameter
#6.
In the real process, the reactor operates adiabatically; heat is removed by a
heat exchanger downstream of the recycle gas compressor. Although Aspen
Plus can simulate an adiabatic reactor, the model is more robust when the
temperature is specified. The design specification “GPR-TC” is used to
emulate a temperature controller around the reactor; it manipulates the
exchanger heat duty until the calculated reactor duty is negligible.
Design Specification Connectivity – Gas-Phase Reactors
5 Modeling Approach 21
22 5 Modeling Approach
6 Model Convergence
The recycle loops around the slurry reactors and the gas phase reactors are
both challenging to solve numerically. In each case, user-defined convergence
loops are used to ensure the model runs robustly.
Convergence block CV-1 resolves the recycle stream “C3-RECYC” using the
Wegstein method. An acceleration parameter (-50) is used to speed up the
convergence. Note that the initial specifications of stream C3-RECYC may
need to be reconciled if large changes are made to the model, otherwise the
model may not converge. This convergence block uses a component list
“LIGHTS” to limit the number of component flow rates that are manipulated
and tested by the convergence algorithm. This component list excludes
polymer and catalyst, which are not expected in the vapor phase. This
component list should be extended if additional volatile components are
added to the model.
Convergence block CV-3 uses the Broyden method to concurrently converge
the gas recycle stream “GPR-REC” and the three design specifications
associated with the gas phase reactor. This block also uses a Wegstein
acceleration parameter of -50 to speed up the convergence, and it references
the component list “LIGHTS” to avoid manipulating and testing the polymer
and catalyst flow rate and component attribute values in the tear stream.
The design specifications not explicitly mentioned above are converged by
automatically-generated SECANT convergence blocks.
The global flash tolerance for the model is tightened from the default value
(1E-4) by a factor of ten to 1E-5. This reduces noise introduced by the flash
calculations and helps improve tear stream and design specification
convergence in the model.
The tuning parameters for each of the reactor models have been optimized to
make the model as robust as possible. Each of the reactor models uses
Newton’s method with “component based scaling” and a limiting scale factor
of 1E-7. These options force the reactor models to tightly converge the live
polymer component attributes associated with the catalyst and polymer,
which can become very low due to deactivation reactions. The Newton “line
search” stabilization method is applied in each reactor model because past
experience has shown that this option reduces the number of iterations
required to reach a solution when simulating Ziegler-Natta polymerization
reactions.
6 Model Convergence 23
24 6 Model Convergence
7 Model Predictions
The HIPP model makes a number of predictions in addition to the full mass
and energy balance of the plant. The table below highlights some of the
polymer properties tracked in the model through component attributes. Note
that the Ziegler-Natta reaction models in Aspen Polymers allows consideration
of man y more attributes including long and short-chain branching, dyad flow
rates for copolymers, average run length for copolymers, terminal, pendant,
and internal double bonds, and so on. See the Aspen Polymers documentation
for a complete list of available attributes and for notes on how to include
these attributes and related reactions in the model.
Selected Polymer Component Attributes

Attribute ID Description
SFLOW Segment molar flow rates

SFRAC Segment mole fractions (relative to total molar flow of all
segments)
DPN Number average chain length
DPW Weight average chain length
PDI Polydispersity index
MWN Number average molecular weight (kg/kmol)
MWW Weight average molecular weight (kg/kmol)
LPFRAC Fraction of live polymer
ATFRAC Atactic fraction
The next table shows the catalyst component attributes tracked in the model.
The dead site fraction (CDSFRAC) is particularly important since it tracks the
fraction of the catalyst that has become deactivated.
Selected Catalyst Component Attributes

Attribute ID Description
CPSFRAC Potential site fraction

CDSFRAC Dead site fraction (from catalyst de-activation)
CVSFRAC Fraction of vacant sites (for each site type)
Note: Live catalyst sites are tracked through polymer attribute LSEFLOW.
The sample model includes a user subroutine, UPSPPP.F (User Prop-Set
Properties for PolyPropylene), with correlations to estimate measured
properties of the polymer based on the fundamental properties tracked by the
model. The subroutine currently includes two different melt flow rate (MFR)
7 Model Predictions 25
correlations and a third correlation to report the weight fraction of ethylene
(see table below). These properties can be referenced within sensitivity
and/or optimization studies, included in the stream report, or reported in unit
operation reports.
The property set subroutine has been pre-compiled into a dynamic link
library, USERPP.DLL, referenced by the model. The dynamic link library and
FORTRAN source code are both included inside the compound file (the .APWZ)
file. These can be extracted by dragging the compound file into WINZIP or
most other file compression tools, or by opening the “Edit Compound File”
dialog from the File menu on the Aspen Plus ribbon.
User Property-Set Correlations Included in UPSPPP.F

Property Set Description Equation
ID
ହ.଻ଶସଷି௟௢௚భబ(ெ ௐ ௐ )
MFR Melt flow rate (dg/min) ൬ ൰
‫ = ܴܨ ܯ‬10 ଴.ଶ଻଻ଷ
Polypropylene Handbook
equation
షఱ∗ெ ௐ
MFR-1 Melt flow rate (dg/min) ‫ = ܴܨ ܯ‬279.4 ∗ ݁(ିଵ.ଷଶ∗ଵ଴ ௐ)
Equation of He et al, 2003

C2WF Ethylene weight fraction in ߣ஼ଶ ∗ ‫ ܯ‬஼ଶ
‫ܥ‬2ܹ ‫= ܨ‬
polymer ߣ஼ଶ ∗ ‫ ܯ‬஼ଶ + ߣ஼ଷ ∗ ‫ ܯ‬஼ଷ
MWW = weight-average molecular weight of polymer, kmol/kg
ߣ஼ଶ = flow rate of ethylene repeat unit (SFLOW of C2-SEG), kmol/sec
‫ ܯ‬஼ଶ = molecular weight of ethylene repeat unit
ߣ஼ଷ = flow rate of propylene repeat unit (SFLOW of C2-SEG), kmol/sec
‫ ܯ‬஼ଷ = molecular weight of propylene repeat unit
The model also tracks and reports the molecular weight distribution (MWD) of
the polymer. The cumulative MWD can be viewed for any stream. The reactor
results also include the MWD curves of the locally produced polymer, as
shown below. The reactor results show the MWD of produced at each type of
catalyst site, as well as the composite molecular weight distribution.
26 7 Model Predictions
Molecular Weight Distribution Prediction for Gas Phase
Reactor
Block R-104: Local Molecular Weight Distribution
0.50
0.45
Distribu tion Moments

0.40
MWN = 191409.54 191580.37
MWW = 507914.20 504296.35
PDI = 2.6535 2.6323
Area = 1.0020
0.35
0.30
Composite
Site1
Weight fraction
Site2
0.25 Site3
Site4
0.20
0.15
0.10
0.05
0.00
10 1000 100000 1.e+7
Molecular weight
The polymer density, heat capacity, and other properties can be reported
using the standard features of Aspen Plus.
7 Model Predictions 27
28 7 Model Predictions
8 Model Results Compared to
SRI Mass Balance
The table below compares the model predictions to the mass balance table
reported by SRI Consulting (SRI Report 128C, 2001). The stream numbers
refer to the flowsheet in the SRI report. The second table below shows the
mass balance predicted by the Aspen Polymers Spheripol model. These
results demonstrate that the Aspen Plus predictions are quite reasonable.
Spheripol Plant Mass Balance – SRI Report 128C

Prepoly Prepoly Propene R-102 R-103 R-102 Poly to Recycle R-103 Propene Ethene R3 PP
Feed Out Feed Feed Feed Product R-104 Product to R3 to R3 Overhead Product
Mass Flows kg/hr 3 4 5 6 7 8 9 11 14 15 16 17 24
Propylene 904 763 23,460 21,596 14,985 10,211 2,088 14,604 16,994 578 219,241
Ethylene 2,575 83,632
Propane 9 9 237 1,137 789 1,146 239 1,662 1,934 6 35,055
Ethane 26 5,976
N2 2 13,919
H2 0.3 0.5 0.5 0.5 8 515
Catalyst
TEAL
Oil
Steam 80
Polymer 154 12,303 20,497 20,505 25,621
Total 914 927 23,697 22,733 15,774 23,660 22,824 16,266 39,433 584 2,610 358,338 25,701
mass Fracs kg/hr 3 4 5 6 7 8 9 11 14 15 16 17 24

Propylene 99.01% 82.38% 99.00% 95.00% 95.00% 43.16% 9.15% 89.78% 43.09% 98.99% 61.18%
Ethylene 98.63% 23.34%
Propane 0.99% 0.98% 1.00% 5.00% 5.00% 4.84% 1.05% 10.22% 4.90% 1.01% 9.78%
Ethane 0.99% 1.67%
N2 0.09% 3.88%
H2 0.001% 0.003% 0.003% 0.001% 0.30% 0.14%
Catalyst
TEAL
Oil
Steam 0.31%
Polymer 16.64% 52.00% 89.80% 52.00% 99.69%
8 Model Results Compared to SRI Mass Balance 29

Spheripol Plant Mass Balance – Aspen Plus HIPP Model
Prepoly Prepoly Propene R-102 R-103 R-102 Poly to Recycle R-103 Propene Ethene R3 PP
Feed Out Feed Feed Feed Product R-104 Product to R3 to R3 Overhead Product
Mass Flows kg/hr FD-PRE2 P-R101 PROPENE FD1-LP1 FD2-LP2 P-R102 P-V105 C3-RECYC P-R103 C3-R104 ETHENE V-R104 POLYMER
Propylene 790 294 25,651 22,522 15,626 10,159 2,974 13,861 17,142 574 173,539 7
Ethylene 3,217 170,881 0.5
Propane 13 13 129 360 250 373 109 503 622 9 11,709 0.5
Ethane 16 2,064
N2 10
H2 0.9 0.7 1.2 14
Catalyst 0.3 0.3 0.3 0.3
TEAL 12 12 12 12
Oil
Steam 59
Polymer 496 12,303 21,796 20,505 25,581
Total 803 803 25,780 22,883 15,876 22,847 24,891 14,365 38,281 583 3,233 358,207 25,670
mass Fracs kg/hr FD-PRE2 P-R101 PROPENE FD1-LP1 FD2-LP2 P-R102 P-V105 C3-RECYC P-R103 C3-R104 ETHENE V-R104 POLYMER
Propylene 98.43% 36.63% 99.50% 98.42% 98.42% 44.46% 11.95% 96.49% 44.78% 98.46% 48.45% 0.03%
Ethylene 99.51% 47.70% 0.00%
Propane 1.57% 1.57% 0.50% 1.57% 1.57% 1.63% 0.44% 3.50% 1.62% 1.54% 3.27% 0.00%
Ethane 0.49% 0.58%
N2 0.04%
H2 0.00% 0.00% 0.008% 0.004%
Catalyst 0.00% 0.00% 0.00% 0.00%
TEAL 0.05% 0.05% 0.03% 0.05%
Oil
Steam 0.23%
Polymer 61.80% 53.85% 87.56% 53.56% 99.65%
MFR 0.187 2.05 2.37 2.37 1.97

C2frac 7.7%
30 8 Model Results Compared to SRI Mass Balance

9 Model Applications
Models help provide detailed process understanding. They capture complex

relationships between equipment operating conditions, recipes, and product
properties.
Aspen Plus includes a number of tools that can be applied to identify and
quantify process improvement opportunities. The Sensitivity tool is used to
evaluate the influence of one or more process variables (model inputs) on any
number of model predictions.
The example model includes a number of sensitivity studies which can be re-
activated. The table below summarizes these studies. Selected results are
summarized in the figures below.
Sensitivity Studies Included in the Sample Model

Study Description
ID
S-1 Evaluate influence of H2 feed concentration on R-102 slurry reactor

polymer melt flow rate and slurry solids content
S-2 Evaluate influence of H2 feed concentration to gas phase reactor
S-3 Evaluate influence of ethylene feed concentration on gas phase reactor
S-4 Evaluate influence of propylene recycle rate and temperature in R-102
Sensitivity study “S-1” demonstrates the strong influence of the hydrogen

concentration on the polymer molecular weight and melt flow index. When
the hydrogen concentration increases, chain transfer to hydrogen reactions
tend to reduce the polymer molecular weight. Note that the slurry solids
content is virtually unchanged; this shows that hydrogen has minimal impact
on the polymer conversion.
9 Model Applications 31
Influence of Hydrogen Concentration on MFR and Slurry
Solids Content
Sensitivity Results Curve
3.6 0.560
3.4 0.558
3.2
0.556
3.0
0.554
2.8
0.552
Solid Fraction
MFR DG/MIN
2.6
2.4 0.550
2.2 0.548
2.0
0.546
1.8
0.544 R-102 Polymer MFR DG/MIN
1.6
1.4 0.542 Solid Fraction in R-102
1.2 0.540
30 35 40 45 50 55 60
H2 Mass PPM in Feed to R-102
Sensitivity study “S-3” evaluates the influence of the ethylene composition in

the gas-phase reactor (GPR). The simulation results indicate that increasing
the ethylene concentration in the feed results in higher conversion, higher
ethylene content in the polymer, and a lower overall melt flow ratio.
32 9 Model Applications
Influence of Ethylene Content on Gas Phase Reactor
Product
Sensitivity Results Curve
2.12 0.077 17.4
2.11 0.076
17.3
2.10
0.075
2.09 17.2
0.074
2.08
2.07 0.073 17.1

Percent Conversion in GPR
EThylene Mass Fraction
2.06 0.072
17.0
MFR DG/MIN
2.05
0.071
2.04 16.9
0.070
2.03
16.8
2.02 0.069
2.01 0.068 16.7

MFR DG/MIN
2.00
0.067 C2WF UNITLESS
1.99 16.6
Conversion
0.066
1.98
16.5
0.065
1.97
1.96 0.064 16.4

0.450 0.453 0.456 0.459 0.462 0.465 0.468 0.471 0.474 0.477 0.480 0.483 0.486 0.489 0.492 0.495 0.498
Ethylene Mass Fraction in Feed to GPR
Sensitivity studies like these can be used to find conditions to produce new
product grades. The sensitivity study “S-4” is set up as a parametric study
manipulating the reactor temperature and propylene recycle rate. The study
shows that a particular target melt flow rate (2.0 in this example) can be met
at several different temperatures. However, at higher temperatures the
conversion may too high, making the slurry density too high to pump (the
slurry density must be kept below 650 g/L). The slurry density can be kept
lower by increasing the propylene recycle rate. By operating the reactor at
higher temperatures and higher recycle rates it is possible to make the
desired product without violating the slurry density constraint.
These studies demonstrate some of the many ways process models can be
used to better understand complex plant behaviors and to use that
understanding to improve the process.
9 Model Applications 33
Influence of Propylene Recycle Rate and Hydrogen
Concentration in Slurry Reactor R-102
At a temperature of 71 C and recycle rate of 20,000 kg/hr both constraints
are met
34 9 Model Applications
10 Sources
Aspen Plus help files.

Aspen Polymers V8.4 Unit Operations and Reaction Models (2013).
This reference manual is available from AspenTech support web site.
Mathematical Modelling of the Microstructure of Polyolefins Made by
Coordination Polymerization: a Review, Jaoa B.P. Soares, Chemical
Engineering Science 56 (2001) 4131-4153.
Molecular Structure of High Melt Strength Polypropylene and its Application to
Polymer Design, Chunxia He, Stephane Costeux, Paula Wood-Adams, and
John M. Dealy, Polymer 44 (2003), p 7181-7188.
Polypropylene Handbook, 2nd ed. Nello Pasquini (Ed.)., Hanser Gardner
Publications (2005).
Polypropylene Update Supplement C. SRI Consulting (2001). This private
report can be purchased from IHS Markit (https://www.ihs.com/index.html).
Spheripol Plant Operation Manual. Private Report.
10 Sources 35
36 10 Sources

Aspen Polymers: Spheripol Hi-Impact Polypropylene Model

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Spheripol Hi-Impact Polypropylene Model

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6 Model Convergence ............................................................................................23

7 Model Predictions ...............................................................................................25

8 Model Results Compared to SRI Mass Balance ...................................................29

9 Model Applications .............................................................................................31

This report documents Aspentech’s sample model illustrating how to simulate

This model includes a number of components as shown below. The model

CAT Conventional TITANIUM-TETRACHLORIDE TICL4

The PC-SAFT equation of state is used to characterize the pure component

CAT 20 233.27 3.755

PP PROPENE USER -0.0036 0.0000 298.15 K

Phase equilibrium parameters for propylene/propane, ethylene/ethane, and

Phase Equilibrium Data and Predictions for Propylene-

The parameters for H2 were regressed in order to improve the accuracy of

Many different polymerization catalyst formulations can be used within the

Feed Specifications in FSPLIT Block V-104

A design specification “Makeup” is used to manipulate the fresh propylene

The design specifications “R1HC” and “R2HC” represent the hydrogen

Summary of User-Defined Parameters in the Model

1 First slurry reactor hydrogen composition set-point,

Design Specification Connectivity – Gas-Phase Reactors

Selected Polymer Component Attributes

SFLOW Segment molar flow rates

Selected Catalyst Component Attributes

CPSFRAC Potential site fraction

User Property-Set Correlations Included in UPSPPP.F

Equation of He et al, 2003

Distribu tion Moments

Spheripol Plant Mass Balance – SRI Report 128C

mass Fracs kg/hr 3 4 5 6 7 8 9 11 14 15 16 17 24

8 Model Results Compared to SRI Mass Balance 29

MFR 0.187 2.05 2.37 2.37 1.97

30 8 Model Results Compared to SRI Mass Balance

Models help provide detailed process understanding. They capture complex

Sensitivity Studies Included in the Sample Model

S-1 Evaluate influence of H2 feed concentration on R-102 slurry reactor

Sensitivity study “S-1” demonstrates the strong influence of the hydrogen

Sensitivity study “S-3” evaluates the influence of the ethylene composition in

2.07 0.073 17.1

2.01 0.068 16.7

1.96 0.064 16.4

Aspen Plus help files.

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