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7.1
POLYMERS
BATCH MODULE
MODULE
Contents
4 Contents
Chain Propagation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-8
Chain Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-8
Free-Radical Recombination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-9
Chain Termination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-10
Gel and Glass Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-10
Required Data for the Polymer Reactor Unit . . . . . . . . . . . . . . . . . . . .9-12
User-Added Subroutines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-13
Communicating with PRO/II for Free-Radical Kinetics . . . . . . . .9-13
Using Reactor Unit US21 to Model Free-Radical Systems . . . . . .9-23
Example 9-1: Free-Radical Homopolymerization in a CSTR . . . .9-23
Example 9-2: Free-Radical Homopolymerization in a PFR. . . . . .9-29
Example 9-3: Free-Radical Copolymerization in a CSTR . . . . . . .9-33
Example 9-4: Free-Radical Copolymerization in a PFR . . . . . . . .9-38
6 Contents
Chapter 1
Introduction to Polymers
Terminology
Descriptions of common polymer terms are provided below.
Select SI-SET1 from the drop-down list, and click OK. The units
of measure for all properties will now be in SI units; e.g., tem-
perature in degrees Kelvin, pressure in kilopascals, etc.
Select the desired distribution names from the list boxes in the
first column. If you select Discrete Mol. Wt. Cuts, enter the
molecular weight ranges by clicking Enter Data.... For the vari-
ous moments, specify the number of moments and optionally
enter the names of the moments by clicking Enter Data.... The
From the Category list, select Polymers. All five polymer ther-
modynamic methods are displayed in the Primary Method list.
Select the desired method, and click Add > to include that
method in the simulation.
To change the thermodynamic method to be used for calculat-
ing various properties, click Modify... . The Modification dialog
box appears (Figure 2-7).
POLYMERS
Enter reactor operating and kinetic data in the Real Data for
Unit (RPARM), Integer Data for Unit (IPARM), and Supple-
mental Data for Unit (SUPPLE) sections. See Chapter 8, Incor-
porating User-Added Polymer Reactor Models, for more
information on the data requirements for the polymer reactor.
POLYMERS
Keyword Summary
POLYMERS
SEGMENT DATA
SEGMENT , name/, &
FILL= VANKREVELEN
STRUCTURE(VANKRE) , igroup(n)/
COMPONENT DATA
BATCH
POLYMER i, name/
PCOMPOSITION(M or W) i, X,(), X(), /
MWAVG i, value/
PHASE VLS or LS or S = i, j
Input Description
SEGMENT DATA
SEGMENT , name/, &
FILL= VANKREVELEN
STRUCTURE(VANKRE) , igroup(n)/
All segments must be defined under SEGMENT DATA.
Segment type letter.
name Name of segment .
FILL This keyword is used to activate the van Krevelen
group contribution method.
COMPONENT DATA
POLYMER i, name/
PCOMPOSITION(M or W) i, X,(), X(), /
MWAVG i, value/
POLYMERS
PHASE VLS or LS or S = i, j
All polymer components must be defined as POLYMER components.
i Component number.
name Name of component i (polymer).
It is best to use the group system SS=00. This is due to the fact that
the van Krevelen group contributions have been developed prima-
Example 3-1
The segment structure of polystyrene is constructed using the SS=00
system (the leading zeros are dropped):
SEGMENT DATA
SEGMENT A, STYRENE1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 144(1), 4(1)
COMPONENT DATA
POLYMER 1, POLYSTRENE
PCOMPOSITION 1, 1(A)
Example 3-2
The segment structure of poly(1-pentene) (PP) is constructed using
the SS=00 system. The number of methylene groups in the side
chain (which is equal to 2) is specified using the CC subcode:
SEGMENT DATA
SEGMENT A, PENTENE1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 200015(1), 4(1)
COMPONENT DATA
POLYMER 1, PP
PCOMPOSITION 1, 1(A)
POLYMERS
Example 3-3
The segment structure of poly(phenyl methacrylate) (PPMA) can-
not be constructed using the SS=00 system. Therefore, the SS=01
system is used:
SEGMENT DATA
SEGMENT A, PPMA1, FILL=VANKREVELEN
Example 3-4
The segment structure of poly(p-phenylene terephthalamide)
(Kevlar) is best defined by just one group (522), even though the
repeat unit of Kevlar is composed of two phenyl rings, two C=O
groups, and two N-H groups.
SEGMENT DATA
SEGMENT A, KEVLAR1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 522(1)
COMPONENT DATA
POLYMER 1, KEVLAR
PCOMPOSITION 1, 1(A)
Example 3-5
This example uses the van Krevelen group contribution method to
predict properties of segments for polystyrene (PS),
poly(1-pentene) (PP), poly(phenyl methacrylate) (PPMA), and
poly(p-phenylene terephthalamide) (Kevlar). The polymer proper-
ties are generated from the calculated segment properties by the van
Krevelen method. Segment compositions are provided in the input.
TITLE PROB=HOMOPOLYMER
DIMENSION SI
PRINT INPUT = FULL
$
SEGMENT DATA
SEGMENT A, STYRENE1/B, PENTENE1/C,PPMA1/&
D, KEVLAR1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 144(1), 4(1)/&
B, 200015(1), 4(1)/&
C, 01004(1),01001(1),01012(1),&
01110(1),01238(1),01710(2),&
01708(2)/&
D, 522(1)
COMPONENT DATA
POLYMER 1, PS/&
2, PP/&
3, PPMA/&
4, KEVLAR
PCOMPOSITION 1,1(A)/2,1(B)/3,1(C)/4,1(D)
PHASE VLS = 1,4
MWAVG 1,10000/2,10000/3,10000/4,10000
$
LIBRARY 5, HEXANE
$
POLYMERS
THERMODYNAMIC DATA
METHOD SYSTEM = LIBRARY
$
STREAM DATA
PROP STRM=F1L, TEMP=300, PRES=10, COMP=1,1
PROP STRM=F1S, TEMP=200, PRES=10,
SOLID STREAM=F1S, COMP=1,1
$
PROP STRM=F2L, TEMP=300, PRES=10, COMP=2,1
Example 3-6
This example uses the van Krevelen group contribution method to
predict properties of segments for the copolymer poly(methyl meth-
acrylate-co-vinyl acetate) (PMMACcoVAC), which has 25% vinyl
acetate. The copolymer properties are generated using calculated
segment properties by the van Krevelen method. Segment composi-
tions are provided in the input.
$
SEGMENT DATA
SEGMENT A, MMAC1/B, VAC1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 5(1),252(1),9(1)/B,5(1),250(1),9(1)
$
COMPONENT DATA
POLYMER 1, PMMACcoVAC
PCOMPOSITION 1, 0.75(A),0.25(B)
PHASE VLS = 1
MWAVG 1,10000
$
LIBRARY 2, HEXANE
$
THERMODYNAMIC DATA
METHOD SYSTEM = LIBRARY
$
STREAM DATA
PROP STRM=F1L, TEMP=300, PRES=10, COMP=1,1
PROP STRM=F1S, TEMP=200, PRES=10,
SOLID STREAM=F1S, COMP=1,1
$
UNIT OPERATION
HCUR UID=HC1L
ISO STREAM=F1L, TEMP=200, 400, PRES=10, POIN=20
PROP THERMO
HCUR UID=HC1S
ISO STREAM=F1S, TEMP=200, 300, PRES=10, POIN=20
PROP THERMO
$
Enter the names of the desired segments, and click Enter Data...
for each segment to display the Define van Krevelen Structures
dialog box (Figure 3-3). POLYMERS
POLYMERS
Keyword Summary
Polymer Definition (required)
POLYMER i, name/
PCOMPOSITION(M or W) i, X,(), X(), /
MWAVG i, value/
PHASE VLS or LS or S = i, j
HFUSION(unit) i, value
SOLUPARA(unit) i, value
Input Description
POLYMERS
Note: The MWD must be supplied for the polymer components if the
polymer reactor unit US21 is used.
Reference
C. Tsonopoulos and Z. Tan, 1993, The Critical Constants of Normal
Alkanes from Methane to Polyethylene II. Application of the Flory
Theory, Fluid Phase Equilibria, 83:127-138.
SEGMENT DATA
SEGMENT A, STYR1, FILL=VANKREVLEN
STRUCTURE(VANKRE) A,144(1),4(1)
COMPONENT DATA
LIBID 2, STYRENE/3,EBZN/4,BOBZ, BANK=SIMSCI
POLY 1, PSTYR
PCOMPOSITION 1,1(A)
PHASE VLS=1
MWAVG 1,31000
THERMODYNAMIC DATA
METHOD SYSTEM=ALM, TRANSPORT=PURE, DIFFUSIVITY=DATA,
KVAL(VLE)
ALME 3,A, 0.022,11.02
ALMC A,1.338
DIFFUSIVITY(L)
DIFDATA(K) 1,2,1E-8
DIFDATA(K) 1,3,5E-8
DIFDATA(K) 1,4,1E-9
UNIT OPERATIONS
PCSTR UID=REACTOR_1, NAME=1st PS REACTOR
FEED F1
PRODUCT P1
IPARM =1,1,1,0,79,0,1,1,1,3,1,2,0,3,4,0,0,0,0,0,0
RPARM =69900,200,0,0,0,355,0,0.5,0,0,0,0,1,0,0,0,0,0
SUPPLEMENTAL =1,1.58E15/128870/0/0/1.05E7/29540/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/1.05E7/29540/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/1.26E9/7030/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0
FLASH UID=F2
FEED P1
PRODUCT V=V2, L=L2
ISO TEMPERATURE=400, PRESSURE=0.666
CONTROLLER UID=CN1
SPEC STREAM=L2,FRACTION(WT), COMP=2,4, VALUE=0.02
VARY FLASH=F2, TEMP
CPARAMETER IPRINT, NOSTOP
WFEV UID=WFE1
FEED L2
PRODUCT L3,V3
IPARM =1,,,1,,2,4
RPARM =3,0.75,0.2,,,,,,,,500,,,,,,,,,0.0001,1E-5,400
END
Select the desired distribution names from the list boxes in the
first column.
For Discrete Mol. Wt. Cuts, enter the molecular weight ranges
by clicking Enter Data.... The Molecular Weight Distribution
dialog box appears (Figure 4-4).
Figure 4-4: Molecular Weight Distribution Data Dialog Box
Keyword Summary
Stream Polymers (optional)
MWD(PA or PB or PC or PAA or PBB or PCC or PAB or PAC or PBC or DA
or DB or DAA or DBB, L or S, M or WT), COMPONENT = i, j,
DATA = value1, value2, ..., {STREAM = sid}
MMWD(PA or PB or PC or PAA or PBB or PCC or PAB or PAC or PBC or
DA or DB or DAA or DBB, L or S, unit), COMPONENT = i, j,
DATA = value1, value2, ..., {STREAM = sid}
PCFRAC(L or S, M or WT) COMPONENT = i, j, DATA = value1, value2,
value3, value4, value5, value6, value7, value8, value9, value10,
value11, value12, value13, {STREAM = sid}
MBCL(P or D, L or S, unit) COMPONENT = i, j, DATA = value1, value2, ...,
{STREAM = sid}
MTTB(P or D, L or S, unit) COMPONENT = i, j, DATA = value1, value2, ...,
{STREAM = sid}
MDSD COMPONENT = i, j, DATA = value1, value2, ..., {STREAM = sid}
PSD COMPONENT = i, j, DATA = value1, value2, ..., {STREAM = sid}
GENERAL COMPONENT = i, j, DATA = value1, value2, ...,
{STREAM = sid}
Polymer-specific data in the stream data section include composi-
tions of polymer components in the streams. This input is the same
as that for the regular components. Polymer solids in streams are
also specified using the same input as regular or low molecular
weight solids, i.e., using the SOLID and PSD statements.
Values of moments of distributions of polymer components with
respect to various parameters can be input as attributes. The
moments are defined in Chapter 4. For distributions that are func-
tions of the topology of the polymer, moments of live chains P and
dead chains D can be input for polymer components in the liquid (L)
and solid (S) phase in the stream.
You can provide data for either the molecular weight distribution
POLYMERS
MWAVG 1, 8578.6
$ POLYMER COMPONENT ATTRIBUTES
ATTRIBUTE COMPONENT = 1, KINETICS = FR, &
MWD = 1000, 2000, 5000, 7000, 10000, 15000, 20000, &
MMWD = MU0, MU1, MU2, MU3
THERMODYNAMICS DATA
METHODS SYSTEM = ALM
KVALUE
ALMC A, 1.338/B, 1.441
ALME 2,A, 0.022,11.02/2,B, 0.010, 16.36
STREAM DATA
UNIT OPERATION
FLASH UID=FEED
FEED FEED
PRODUCT V=V1, L=L1
ISOT TEMP(K)=298.15, PRES(ATM)=1
END
SEGMENT DATA
SEGMENT A, STY1/B, MMAC1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 146(1), 4(1)/B, 5(1), 252(1), 9(1)
POLYMERS
COMPONENT DATA
POLYMER 1, PScoVAC
PCOMPOSITION 1, 0.7(A), 0.3(B)
LIBRARY 2, BENZENE
PHASE VLS = 1
MWAVG 1, 11276
THERMODYNAMICS DATA
STREAM DATA
PROP STRM=FEED, TEMP(K)=300, PRES(ATM)=1, &
COMP(WT,KG/MIN)=100/20
$ POLYMER FEED STREAM ATTRIBUTES
$ COMPONENT 1 (TWO SEGMENTS A AND B)
MMWD(PA,L) COMP = 1,DATA = 0.1,10,2500,1000000,STREAM = FEED
MMWD(PB,L) COMP = 1,DATA = 0.2,20,3500,2000000,STREAM = FEED
MMWD(PAA,L) COMP = 1,DATA = 0.3,30,4500,3000000,STREAM = FEED
MMWD(PBB,L) COMP = 1,DATA = 0.4,40,5500,4000000,STREAM = FEED
MMWD(DA,L) COMP = 1,DATA = 0.5,50,6500,5000000,STREAM = FEED
MMWD(DB,L) COMP = 1,DATA = 0.6,60,7500,6000000,STREAM = FEED
MMWD(DAA,L) COMP = 1,DATA = 0.7,70,8500,7000000,STREAM = FEED
MMWD(DBB,L) COMP = 1,DATA = 0.8,80,9500,8000000,STREAM = FEED
PCFRAC(L,WT)COMP=1,DATA= 0.1,0.2,0.0,0.05,0.05,0.0,0.0,0.0,&
0.0,0.1,0.1,0.1,0.1, NORM, STREAM=FEED
BCL(P,L) COMP = 1, DATA = 1, 1000, 100000, STREAM=FEED
MTTB(P,L) COMP = 1, DATA = 50,45000,3500000, STREAM=FEED
MBCL(D,L) COMP = 1, DATA = 5, 5000, 500000, STREAM=FEED
MTTB(D,L) COMP = 1, DATA = 20,40000,7000000, STREAM=FEED
MDSD COMP = 1, DATA = 30, 30, 40, STREAM=FEED
PSD COMP = 1, DATA = 0.3, 0.7, STREAM=FEED
GENERAL COMP = 1, DATA = 100,200,300, STREAM=FEED
UNIT OPERATION
FLASH UID=FEED
FEED FEED
PRODUCT V=V1, L=L1
ISOT TEMP(K)=300, PRES(ATM)=1
POLYMERS
END
POLYMERS
Click Enter Data... under Additional Data to supply the data for
that chain type. If Discrete Mol. Wt. Cuts (MWD) is selected,
supply the molecular weight fractions (Figure 5-5).
Figure 5-5: Discrete Mol. Wt. Cuts Dialog Box
ply the values for the moments for the selected chain type and
the chain type fraction (PCFRAC) (Figure 5-6). Data can be sup-
plied for liquid and/or solid phase.
Keyword Summary
PRINT , PWRATE, PCONV
PWRATE This optional keyword specifies that the rate (on a weight
basis) of the total polymer component be printed in the
Stream Component Rates section of the output report.
PCONV This optional keyword disables the polymer characterization
conversion utility that converts one characterization (e.g. the
POLYMERS
Typical Usage
TITLE
DIME METRIC
PRINT RATE=WT, INPUT=ALL,PWRATE,PCONV
the input.
Typical Usage
SEGMENT DATA
SEGMENT A, IB1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 16(1), 4(1)
COMPONENT DATA
LIBID 1,BENZENE
POLYMER 2, PIB
PCOMPOSITION 2, 1(A)
MW 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=ALM
METHOD Statement
METHOD SYSTEM(VLE or VLLE)=ALM, PHI=IDEAL, {HENRY},
or
POLYMERS
Table 7-2 lists values of c for ALMC, and e1, and e2 for ALME
BATCH
Typical Usage
SEGMENT DATA
SEGMENT A, IB1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 16(1),4(1)
STRUCTURE(UNIFAC) A, 0900(2),0901(1),0903(1)
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
PCOMPOSITION 2, 1(A)
MWAVG 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=UNFV
Note: When using the UNFV method for polymer systems, UNIFAC
structural groups must be defined for the polymer segments via a
STRUCTURE(UNIFAC) statement under SEGMENT DATA. For more
information on non-polymer components, see Section 1.9, UNIFAC
Structural Groups, of the SIMSCI Component and Thermodynamic Data
Input Manual.
TITLE PROB=UNFV
DIMENSION SI
PRINT INPUT=FULL, RATE=WT, FRACTION=WT
$
SEGMENT DATA
SEGMENT A, IB1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 16(1), 4(1)
STRUCTURE(UNIFAC) A, 0900(2),0901(1),0903(1)
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
PCOMPOSITION 2, 1(A)
MWAVG 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=UNFV
$
STREAM DATA
PROPERTY STRM = F1, TEMP = 400, PRES =10, &
COMP = 1, 0.9/2, 0.1
$
UNIT OPERATION
FLASH UID=FL1, NAME=FL1, KPRINT
FEED F1
PRODUCT V=V1, L=L1
ISO TEMP = 400, PRES = 10
POLYMERS
$
END
Typical Usage
SEGMENT DATA
SEGMENT A, IB1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 16(1), 4(1)
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
PCOMPOSITION 2, 1(A)
MWAVG 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=FLORY
METHOD Statement
METHOD SYSTEM(VLE or VLLE)=FLORY, PHI=IDEAL,{HENRY},
or
METHOD KVALUE(VLE and/or LLE or VLLE)=FLORY,
PHI=IDEAL, {HENRY},
SYSTEM Selects a combination of compatible thermodynamic
POLYMERS
Cyclohexane 0.456
n-Pentane 0.683 30.58
Methyl PMMA Toluene 0.465
Methacrylate
i -Propylene i -PP Dichloromethane 2.182
Decene-1 PD Toluene 0.451
The SAFT and PHSC equations of state are especially useful for
polymer solutions and polymer blends. They are also uniquely
applicable to high-pressure polymer-supercritical solvent systems.
They are characterized by a much higher accuracy of VLE and LLE
correlation than any of the existing thermodynamic models for
polymer systems.
Typical Usage
SEGMENT DATA
SEGMENT A, IB1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 16(1), 4(1)
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
PCOMPOSITION 2, 1(A)
MW 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=SAFT or PHSC
Table 7-7 lists values of the SAFT and PHSC EOS parameters for
common solvents. Table 7-8 lists values of the SAFT and PHSC
EOS parameters for some homopolymer segments. Table 7-9 lists
values of the SAFT EOS binary parameter for some homopolymer
segment-solvent pairs.
Table 7-7: SAFT and PHSC EOS Parameters for Solvents
POLYMERS
Normal Alkanes
Methane 1 190.3 3.700 1 182.1 4.126
Ethane 1.941 191.4 3.238 1.694 206.3 3.916
Propane 2.696 193.0 3.162 2.129 219.0 3.998
Butane 3.458 195.1 3.093 2.496 231.3 4.085
Pentane 4.091 200.0 3.088 3.149 226.0 3.995
Hexane 4.724 202.7 3.083 3.446 235.6 4.084
Heptane 5.391 204.6 3.067 4.255 225.9 3.947
Octane 6.045 206.0 3.063 5.055 219.6 3.850
Nonane 6.883 203.6 3.063 5.748 217.3 3.804
Decane 7.527 205.5 3.020 6.616 212.7 3.723
Undecane 7.057 215.4 3.754
Dodecane 8.921 205.9 3.032 7.712 214.8 3.733
Tridecane 7.986 218.3 3.794
Tetradecane 9.978 209.4 3.076 9.023 213.7 3.682
Pentadecane 9.851 211.3 3.662
Hexadecane 11.209 210.7 3.068 10.168 214.2 3.703
Heptadecane 10.834 213.7 3.680
Octadecane 11.110 216.5 3.698
Nonadecane 11.659 216.1 3.718
Eicosane 13.940 211.3 3.043 12.925 212.1 3.633
Branched and Cyclic Alkanes
Isobutane 2.397 226.2 4.155
Isopentane 2.777 236.7 4.182
Neopentane 2.526 233.7 4.351
2,2-Dimethylbutane 2.849 247.7 4.368
2,3-Dimethylbutane 2.998 247.1 4.278
POLYMERS
Table 7-8: SAFT and PHSC Equation-of-State Parameters for Homopolymer Segments
Segment Name Homopolymer SAFT PHSC
Name r /kB(K) () r /kB(K) ()
Ethylene HDPE 0.0510 216.2 3.043 0.04938 324.1 3.825
POLYMERS
POLYMERS
References
[1] S. H. Huang and M. Radosz, 1990, Equation of State for Small,
Large, Polydisperse, and Associating Molecules, Ind. Eng. Chem.
Res., 29:2284-2294.
[2] Y. Song, T. Hino, S. M. Lambert, and J. M. Prausnitz, 1996, Liq-
uid-Liquid Equilibria for Polymer Solutions and Blends, Including
Copolymers, Fluid Phase Equilibria, 117:69-76.
[3] C. S. Wu and Y. P. Chen, 1994, Calculation of Vapor-Liquid
Equilibria of Polymer Solution Using the SAFT Equation of State,
Fluid Phase Equilibria, 100:103-119.
LIBRARY 1, BENZENE
POLYMER 2, PVAC
PCOMPOSITION 2, 1.0(A)
PHASE VLS = 2
MWAVG 2, 48000
THERMODYNAMIC DATA
METHOD SYSTEM (VLLE) = PHSC
KVALUE
EPSI 1, 291.6/A, 292.6
POLYMERS
0 = Q f f c p T f Qc p T UA j ( T Tj )
f
* *
+ ( H aa )Vk paa [ A ]P + ( H ba V )k pba [ A ]Q
+
* *
+ ( H ab )Vk pab [ A ]P + ( H bb )Vk pbb [ A ]Q
* *
+ ( H aa )Vk paa [ A ]P + ( H ba V )k pba [ A ]Q
+
* *
+ ( H ab )Vk pab [ A ]P + ( H bb )Vk pbb [ A ]Q
the form:
2
dP u
------- = 4f ---------
dz 2D i
*
* k tpaa P ( n + m )D n, m, b-1, 1
( A' 1, s + A' 0, s )P n, m, b, 1 +
k tpba Q * ( n + m )D n, m, b-1, 1
Reference
1. Ray, W. H. (1972), On the Mathematical Modeling of Poly-
merization Reactors, J. Macromol. Sci. Revs. Macromol.
Chem., C(8):1 56.
POLYMERS
k
k
k paa [ A ] [ k, l ] + k pba [ A ]
i i, l
i
l
l
( A' 1, s + A' 0, s ) [ k, l ] + l j
k + l, j
j
POLYMERS
linear copolymer
Type I, Type II and Type III stepwise polymerization
Ideal CSTR (steady-state, well mixed, constant volume reactor)
Ideal PFR (steady-state, plug flow, constant diameter reactor)
* k *
* iaa
2 Initiation of monomer A by I a I a + A> P1, 0, 0, 1
* k *
* iab
3 Initiation of monomer B by I a I a + B> Q 0, 1, 0, 1
* * f k
b db *
4 Decomposition of initiator B to form I b I b > 2I b
* k *
* iba
5 Initiation of monomer A by I b I b + A> P1, 0, 0, 1
* k *
* ibb
6 Initiation of monomer B by I b I b + B> Q 0, 1, 0, 1
* * c dc
f k *
7 Decomposition of initiator C to form I c I c >2I c
* k *
* ica
8 Initiation of monomer A by I c I c + A> P1, 0, 0, 1
* k *
* icb
9 Initiation of monomer B by I c I c + B> Q 0, 1, 0, 1
k *
10 Spontaneous initiation of A to form A
* ra A>
spa
pa A (see note a at end of table) a
k *
11 Spontaneous initiation of B to form B
* rb B>
spb
pb B (see note a at end of table)
k *
12 Thermal decomposition of A to form R a
* pa A>
tha
pa R a (see note a at end of table)
k *
13 Thermal decomposition of B to form R b
* pb B>
thb
pb R b (see note a at end of table)
k *
* dOa
14 Initiation of monomer A by O2 to form R a O 2 + A>2R a
k *
* dOb
15 Initiation of monomer B by O2 to form R b O 2 + B>2R b
k *
*
POLYMERS
dpa
16 Peroxide decomposition to form R a RO 2 + A>2R a
k *
* dpb
17 Peroxide decomposition to form R b RO 2 + B>2R b
* k
* ra
18 Peroxide production by R a R a + O 2 >RO 2 + inert products
* k
* rb
19 Peroxide production by R b R b + O 2 >RO 2 + inert products
* k *
* rbb
21 Reinitiation of monomer B by R b R b + B> Q 0, 1, 0, 1
Propagation Reactions
* * k
paa *
22 Monomer A added to P P n, m, b, t + A> P n + 1, m, b, t
* * k
pba *
23 Monomer A added to Q Q n, m, b, t + A> P n + 1, m, b, t
* * k
pab *
24 Monomer B added to P P n, m, b, t + B> Q n, m + 1, b, t
* * k
pbb *
25 Monomer B added to Q Q n, m, b, t + B> Q n, m + 1 , b , t
* * * k *
26 Transfer from P to solvent to form S
tsa
P n, m, b, t + S> D n, m, b, t + S
* * * k *
27 Transfer from Q to solvent to form S
tsb
Q n, m, b, t + S> D n, m, b, t + S
* k *
* rsa
28 Reinitiation of monomer A by S S + A> P1, 0, 0, 1
* k *
* rsb
29 Reinitiation of monomer B by S S + B> Q 0, 1, 0, 1
* * * k *
30 Transfer from P to modifier to form T
txa
P n, m, b, t + T x > D n, m, b, t + T x
* * * k *
31 Transfer from Q to solvent to form T
txb
Q n, m, b, t + T x > D n, m, b, t + T x
* k *
* rta
32 Reinitiation of monomer A by T T x + A> P1, 0, 0, 1
* k *
* rtb
33 Reinitiation of monomer B by T T x + B> Q 0, 1, 0, 1
* * * k *
34 Transfer from P to initiator A to form I a
tiaa
P n, m, b, t + I a > D n, m, b, t + I a
POLYMERS
* * * k *
35 Transfer from Q to initiator A to form I a
tiba
Q n, m, b, t + I a > D n, m , b, t + I a
* k *
* riaa
36 Reinitiation of monomer A by I a I a + A> P1, 0, 0, 1
* k *
* riab
37 Reinitiation of monomer B by I a I a + B> Q 0, 1, 0, 1
* * * k *
39 Transfer from Q to initiator B to form I b
tibb
Q n, m, b, t + I b > D n, m , b, t + I b
* k *
* riba
40 Reinitiation of monomer A by I b I b + A> P1, 0, 0, 1
* k *
* ribb
41 Reinitiation of monomer B by I b I b + B> Q 0, 1, 0, 1
* * * k *
42 Transfer from P to initiator C to form I c
tiac
P n, m, b, t + I c > D n, m, b, t + I c
* * * k *
43 Transfer from Q to initiator C to form I c
tibc
Q n, m, b, t + I c > D n, m, b, t + I c
* k *
* rica
44 Reinitiation of monomer A by I c I c + A> P1, 0, 0, 1
* k *
* ricb
45 Reinitiation of monomer B by I c I c + B> Q 0, 1, 0, 1
* * * k *
46 Transfer from P to monomer A to form A
maa
P n, m, b, t + A> D n, m, b, t + A
* * * k *
47 Transfer from Q to monomer A to form A
mba
Q n, m, b, t + A> D n, m , b, t + A
* k *
* rmaa
48 Reinitiation of monomer A by A A + A> P1, 0, 0, 2
* k *
* rmab
49 Reinitiation of monomer B by A A + B> Q 0, 1, 0, 2
* * * k *
50 Transfer from P to monomer B to form B
mab
P n, m, b, t + B> D n, m, b, t + B
* * * k *
51 Transfer from Q to monomer B to form B
mbb
Q n, m, b, t + B> D n, m , b, t + B
* k *
* rmba
52 Reinitiation of monomer A by B B + A> P1, 0, 0, 2
* k *
* rmbb
53 Reinitiation of monomer B by B B + B> Q 0, 1, 0, 2 POLYMERS
* * * k *
54 Transfer from polymer P to form P
tpaa
P n, m, b, t + D r, q, x, t > D n, m, b, t + P r, q, x + 1, t
with rate constant ktpaa
* * * k *
55 Transfer from polymer P to form P
tpba
Q n, m, b, t + D r, q, x, t > D n, m, b, t + P r, q, x + 1, t
with rate constant ktpba
* * * k *
57 Transfer from polymer P to form P
tpbb
Q n, m, b, t + D r, q, x, t > D n, m, b, t + Q r, q, x + 1, t
with rate constant ktpbb
Termination Reactions
* * * * caa
k
58 Combination of P and P P n, m, b, s + P r, q, x, t > D n + r, m + q, b + x, max ( s, t )
* * * * cba
k
59 Combination of Q and P Q n, m, b, s + P r, q, x, t > D n + r, m + q, b + x, max ( s, t )
* * * * cab
k
60 Combination of P and Q P n, m, b, s + Q r, q, x, t > D n + r, m + q, b + x, max ( s, t )
* * * * cbb
k
61 Combination of Q and Q Q n, m, b, s + Q r, q, x, t > D n + r, m + q, b + x, max ( s, t )
* * * * k
daa D n, m, b, s D n, m, b, 2 D r, q, x, t D r, q, x, 2
62 Disproportionation of P and P P n, m, b, s + P r, q, x, t > -------------------- + -------------------- + ----------------- + ------------------
2 2 2 2
* * * * k
dba D n, m, b, s D n, m, b, 2 D r, q, x, t D r, q, x, 2
63 Disproportionation of Q and P Q n, m, b, s + P r, q, x, t > -------------------- + -------------------- + ----------------- + ------------------
2 2 2 2
* * * * k
dab D n, m, b, s D n, m, b, 2 D r, q, x, t D r, q, x, 2
64 Disproportionation of P and Q P n, m, b, s + Q r, q, x, t > -------------------- + -------------------- + ----------------- + ------------------
2 2 2 2
* * * * k
dbb D n, m, b, s D n, m, b, 2 D r, q, x, t D r, q, x, 2
65 Disproportionation of Q and Q Q n, m, b, s + Q r, q, x, t > -------------------
- + -------------------- + ----------------- + ------------------
2 2 2 2
* * k
66 Termination of P by inhibitor
za
P n, m, b, t + I n > D n, m, b, t + Y
* * k
67 Termination of Q by inhibitor
zb
Q n, m, b, t + I n > D n, m, b, t + Y
*
+ R*
k
* * P n, m, b, 1 >D
bta
68 Beta-scission of P to form R n, m, b, t
*
+ R*
k
* * Q n, m, b, 1 >D
btb
69 Beta-scission of Q to form R n, m , b, t
POLYMERS
* k *
* rra
70 Reinitiation of monomer A by R R + A> P 1, 0, 0, 1
* k *
* rrb
71 Reinitiation of monomer B by R R + B> Q 0, 1, 0, 1
Side Reactions
*
+ H*
k
* * Q n, m, b, t >D
ttb
73 Thermal degradation of Q to form H n, m, b , t
* k *
* kha
74 Reinitiation of monomer A by H H + A> P 1, 0, 1, 0
* k *
* khb
75 Reinitiation of monomer B by H H + B> Q 0, 1, 0, 1
* * * k
bnaa *
76 Terminal double bond from P and P P n, m, b, s + D r, q, x, 2 > P n + r, m + q, b + x + 1, 2
with rate constant kbnaa
* * * k
bnba *
77 Terminal double bond from P and P P n, m, b, s + D r, q, x, 2 > P n + r, m + q, b + x + 1, 2
with rate constant kbnba
* * * k bnab *
78 Terminal double bond from P and P P n, m, b, s + D r, q, x, 2 > P n + r, m + q, b + x + 1, 2
with rate constant kbnab
* * * k
bnbb *
79 Terminal double bond from P and P P n, m, b, s + D r, q, x, 2 > P n + r, m + q, b + x + 1, 2
with rate constant kbnbb
a. Values for and are currently fixed internally at 2.0 and 1.1, respectively. In future releases, and will accept
user-specified values.
Free-Radical Initiation
Some organic molecules contain unstable double bonds that can be
induced to undergo thermal disassociation to form free-radicals.
The radical center is an atom possessing an unpaired electron, and it
is this unpaired electron that attacks the double bond present in the
monomer. Because the parent organic initiator molecule is con-
sumed by the reaction, the term initiator rather than catalyst is
appropriate. Up to three initiators may be used in the free-radical
simulation. Each initiator is characterized by its molecular weight,
its decomposition kinetic rate data, and its recombination efficiency.
The activity of each initiator is set through its preexponential factor
POLYMERS
Chain Propagation
The reactive center continues to add monomer to the growing or live
chain, thereby increasing the molecular weight of the polymer mol-
ecule. The mechanisms are given in the following steps:
REACTION STEP(22): PROPAGATION OF P* WITH MONOMER A KPAA
REACTION STEP(23): PROPAGATION OF Q* WITH MONOMER A KPBA
REACTION STEP(24): PROPAGATION OF P* WITH MONOMER KPAB
REACTION STEP(25): PROPAGATION OF Q* WITH MONOMER B KPBB
Chain Transfer
The reactive center is very active and, as such, can react with other
chemical species in the reaction mixture. The reactive center can be
transferred to other polymer, monomer, or solvent molecules. The
original live polymer chain is now inactive or dead, but the reactive
site remains active on some other molecule.
RNX STEP(26): TRANSFER FROM P* TO SOLVENT TO FORM S* KTSA
RNX STEP(27): TRANSFER FROM Q* TO SOLVENT TO FORM S* KTSB
POLYMERS
Free-Radical Recombination
These radicals recombine with the monomer to form new primary
polymer radicals, which then generate a new polymer. Some kinetic
models assume that the active radical recombines instantaneously
so that it is the radical formation step that is rate limiting. This
assumption is not made here. Kinetic data for each free-radical
resulting from a transfer reaction must be input in the order in
which the radical participates in the polymerization.
The following recombination steps are present in the kinetic
scheme:
RXN STEP(20): REINITIATION OF MONOMER A BY RA* KRAA
RXN STEP(21): REINITIATION OF MONOMER B BY RB* KRBB
RXN STEP(28): REINITIATION OF MONOMER A BY S* KRSA
RXN STEP(29): REINITIATION OF MONOMER B BY S* KRSB
RXN STEP(32): REINITIATION OF MONOMER A BY T* KRTA
RXN STEP(33): REINITIATION OF MONOMER B BY T* KRTB
RXN STEP(36): REINITIATION OF MONOMER A BY IA** KRIAA
RXN STEP(37): REINITIATION OF MONOMER B BY IA** KRIAB
RXN STEP(40): REINITIATION OF MONOMER A BY IB** KRIBA
RXN STEP(41): REINITIATION OF MONOMER B BY IB** KRIBB
RXN STEP(44): REINITIATION OF MONOMER A BY IC** KRICA
RXN STEP(45): REINITIATION OF MONOMER B BY IC** KRICB
RXN STEP(48): REINITIATION OF MONOMER A BY A* KRMAA
RXN STEP(49): REINITIATION OF MONOMER B BY A* KRMAB
RXN STEP(52): REINITIATION OF MONOMER A BY B* KRMBA
RXN STEP(53): REINITIATION OF MONOMER B BY B* KRMBB
POLYMERS
References
1. Kumar, V.R. and S.K. Gupta, Optimal Parameter Estimation
for Methyl Methacrylate Polymerization, Polymer, 32:3233-
3243 (1991).
2. Baillagou, P.E. and D.S. Soong, Molecular Weight Distribu-
tion of Products of Free-Radical Nonisothermal Polymerization
User-Added Subroutines
An outline of the keyword input syntax for user-added unit opera-
tions such as the polymer reactor unit US21 is given below. IPARM
and RPARM arrays are used to pass information on the component
and reactor configuration from the keyword file to the user-added
subroutine. The SUPPLE array is used to supply kinetics data.
$
REACTION STEP(33): REINITIATION OF MONOMER B BY T* KRTB
$ SUPPLE(129) = PREEXPONENTIAL FACTOR (L/GMOL/SEC)
$ SUPPLE(130) = ACTIVATION ENERGY (J/GMOL)
$ SUPPLE(131) = VOLUME COEFFICIENT (J/GMOL/ATM)
$ SUPPLE(132) = REFERENCE PRESSURE (ATM)
$
REACTION STEP(34): TRANSFER FROM P* TO INITIATOR A TO FORM IA** KTIAA
$ SUPPLE(133) = PREEXPONENTIAL FACTOR (L/GMOL/SEC)
$ SUPPLE(134) = ACTIVATION ENERGY (J/GMOL)
$ SUPPLE(135) = VOLUME COEFFICIENT (J/GMOL/ATM)
$ SUPPLE(136) = REFERENCE PRESSURE (ATM)
$
REACTION STEP(35): TRANSFER FROM Q* TO INITIATOR A TO FORM IA** KTIBA
$ SUPPLE(137) = PREEXPONENTIAL FACTOR (L/GMOL/SEC)
$ SUPPLE(138) = ACTIVATION ENERGY (J/GMOL)
$ SUPPLE(139) = VOLUME COEFFICIENT (J/GMOL/ATM)
$ SUPPLE(140) = REFERENCE PRESSURE (ATM)
$
REACTION STEP(36): REINITIATION OF MONOMER A BY IA** KRIAA
$ SUPPLE(141) = PREEXPONENTIAL FACTOR (L/GMOL/SEC)
$ SUPPLE(142) = ACTIVATION ENERGY (J/GMOL)
$ SUPPLE(143) = VOLUME COEFFICIENT (J/GMOL/ATM)
$ SUPPLE(144) = REFERENCE PRESSURE (ATM)
$
REACTION STEP(37): REINITIATION OF MONOMER B BY IA** KRIAB
$ SUPPLE(145) = PREEXPONENTIAL FACTOR (L/GMOL/SEC)
$ SUPPLE(146) = ACTIVATION ENERGY (J/GMOL)
$ SUPPLE(147) = VOLUME COEFFICIENT (J/GMOL/ATM)
$ SUPPLE(148) = REFERENCE PRESSURE (ATM)
$
REACTION STEP(38): TRANSFER FROM P* TO INITIATOR B TO FORM IB** KTIAB
$ SUPPLE(149) = PREEXPONENTIAL FACTOR (L/GMOL/SEC)
$ SUPPLE(150) = ACTIVATION ENERGY (J/GMOL)
$ SUPPLE(151) = VOLUME COEFFICIENT (J/GMOL/ATM)
$ SUPPLE(152) = REFERENCE PRESSURE (ATM)
$
REACTION STEP(39): TRANSFER FROM Q* TO INITIATOR B TO FORM IB** KTIBB
$ SUPPLE(153) = PREEXPONENTIAL FACTOR (L/GMOL/SEC)
$ SUPPLE(154) = ACTIVATION ENERGY (J/GMOL)
$ SUPPLE(155) = VOLUME COEFFICIENT (J/GMOL/ATM)
$ SUPPLE(156) = REFERENCE PRESSURE (ATM)
$
POLYMERS
$
REACTION STEP(50): TRANSFER FROM P* TO MONOMER B TO FORM B* KMAB
$ SUPPLE(197) = PREEXPONENTIAL FACTOR (L/GMOL/SEC)
$ SUPPLE(198) = ACTIVATION ENERGY (J/GMOL)
$ SUPPLE(199) = VOLUME COEFFICIENT (J/GMOL/ATM)
$ SUPPLE(200) = REFERENCE PRESSURE (ATM)
$
$
REACTION STEP(59): TERMINATION BY COMBINATION OF Q* AND P* KCBA
$ SUPPLE(233) = PREEXPONENTIAL FACTOR (L/GMOL/SEC)
$ SUPPLE(234) = ACTIVATION ENERGY (J/GMOL)
$ SUPPLE(235) = VOLUME COEFFICIENT (J/GMOL/ATM)
$ SUPPLE(236) = REFERENCE PRESSURE (ATM)
$
on this statement.
5. The polymer CSTR is modeled as two US21 units in series.
6. Data on the reaction component types involved in the reaction
and the isothermal reactor operating conditions are provided on
the IPARM and RPARM statements.
$ IPARM( 6) = N/A
$ IPARM( 7) = BASIS FOR KINETIC RATE CONSTANTS REQ
$ = 1 FOR VOLUME BASIS
$ = 2 FOR WEIGHT BASIS
$ IPARM( 8) = N/A
$ IPARM( 9) = HIGH PRESSURE KINETIC RATE CONSTANT REQ
$ = 0 NO PRESSURE COEFFICIENTS
$ = 1 INCLUDE PRESSURE COEFFICIENTS
$ IPARM(10) = GEL AND GLASS EFFECT CORRELATION OPT
$ ( DEFAULT = 0 )
$------------------------------------------------------------
IPARM 1,1,1,0,0, 0,1,0,1,3, 1,2,0,3,4, 0,0,0,0,0,0
$------------------------------------------------------------
$ IPARM(11) = POLYMER COMPONENT
$ IPARM(12) = MONOMER A COMPONENT
$ IPARM(13) = MONOMER B COMPONENT (OR 0)
$ IPARM(14) = SOLVENT COMPONENT (OR 0)
$ IPARM(15) = INITIATOR A COMPONENT
$ IPARM(16) = INITIATOR B COMPONENT (OR 0)
$ IPARM(17) = INITIATOR C COMPONENT (OR 0)
$ IPARM(18) = TRANSFER AGENT COMPONENT (OR 0)
$ IPARM(19) = INHIBITOR COMPONENT (OR 0)
$ IPARM(20) = O2 COMPONENT (OR 0)
$ IPARM(21) = PEROXIDE COMPONENT (OR 0)
$------------------------------------------------------------
$ RPARM( 1) = HEAT OF POLYMERIZATION (Haa) , J/GMOL
$ RPARM( 2) = CSTR VOLUME, LITER
$ RPARM( 3) = NONISOTHERMAL REACTOR JACKET TEMPERATURE, K
$ RPARM( 4) = NONISOTHERMAL CSTR JACKET AREA, M2
$ RPARM( 5) = NONISOTHERMAL REACTOR OVERALL HTC, J/SEC/M2/K
$ RPARM( 6) = REACTOR TEMPERATURE, K,
$ = OPERATING TEMPERATURE OF ISOTHERMAL CSTR/PFR
$ = TEMPERATURE ESTIMATE FOR NONISOTHERMAL CSTR
$ RPARM( 7) = CSTR PRESSURE DROP (kPa), (DEFAULT=0.0)
$ RPARM( 8) = DECOMPOSITION EFFICIENCY FACTOR
$ FOR 1ST INITIATOR
$ RPARM( 9) = DECOMPOSITION EFFICIENCY FACTOR
$ FOR 2ND INITIATOR (OR 0)
$ RPARM(10) = DECOMPOSITION EFFICIENCY FACTOR
$ FOR 3RD INITIATOR (OR 0)
$ RPARM(11) = PFR LENGTH, M
$ RPARM(12) = PFR DIAMETER, CM
$ RPARM(13) = FEED STREAM LIVE CHAIN A FRACTION
POLYMERS
tant to note:
1. Van Krevelen structural groups (from Appendix A) are given
for the polymer polystyrene, and the FILL=VANKREVELEN key-
word is used to specify that van Krevelen prediction methods
be used for polymer properties.
2. The kinetics type and the molecular weight distribution are pro-
vided on the ATTRIBUTE statement. The distribution given will
result in the creation of 21 polymer pseudocomponents
(1MW10 through 1MW500000).
3. Names are defined for the first three moments of molecular
weight distribution (MMWD) on the ATTRIBUTE statement.
These moments will be calculated by the US21 unit, but will be
printed in the stream report output only if the names are given
on this statement.
4. The polymer PFR is initially heated by the reactor jacket up to
an initiation temperature, after which the PFR is cooled by the
reactor jacket.
5. Data on the reaction component types involved in the reaction
and the nonisothermal reactor operating conditions are pro-
vided on the IPARM and RPARM statements.
6. Data for the free-radical kinetics for the polymerization reac-
tion are taken from Table 9-4 and are provided in the US21
units via the SUPPLE data statement.
7. The product from the reactor unit is flashed isothermally in unit
PRODUCT to remove volatiles.
Table 9-4: Kinetic Rate Parameters for Ethylene Polymerization
Step Rate Prefactor Prefactor Activation Volume Reference
Constant ko Units Energy Coefficient Pressure
(J/gmol) (J/gmol/atm) (atm)
1 KDA 2.5000e14 1/sec 125520 0.6276 1.0
2 KIAA 2.5000e14 m3/kmol/sec 125520 0.6276 1.0
POLYMERS
KVALUE
CHI A,3 ,0.5
STREAM DATA
PROP STRM=Feed_1, TEMP(K)=363.15, PRES(ATM)=2400.0, *
COMP(WT,KG/MIN)=0.0/1244.7/12.45/1.12
UNIT OPERATION
US21 UID=REACTOR_1, NAME=HDPE PFReactor
FEED Feed_1
PROD Prod_1
$------------------------------------------------------------
FLASH UID=PRODUCT
FEED PROD_1
PRODUCT V=VAPOR, L=POLYMER_MELT
ISOT TEMP(K)=363.15, PRES(ATM)=2400
printed in the stream report output only if the names are given
on this statement.
5. Data on the reaction component types involved in the reaction
and the isothermal reactor operating conditions are provided on
the IPARM and RPARM statements.
$ IPARM( 6) = N/A
$ IPARM( 7) = BASIS FOR KINETIC RATE CONSTANTS REQ
$ = 1 FOR VOLUME BASIS
$ = 2 FOR WEIGHT BASIS
$ IPARM( 8) = N/A
$ IPARM( 9) = HIGH PRESSURE KINETIC RATE CONSTANT REQ
$ = 0 NO PRESSURE COEFFICIENTS
$ = 1 INCLUDE PRESSURE COEFFICIENTS
$ IPARM(10) = GEL AND GLASS EFFECT CORRELATION OPT
$ ( DEFAULT = 0 )
$------------------------------------------------------------
IPARM 2,0,2,0,0, 0,1,0,1,0, 1,2,3,4,5, 0,0,0,0,0,0
$------------------------------------------------------------
$ IPARM(11) = POLYMER COMPONENT
$ IPARM(12) = MONOMER A COMPONENT
$ IPARM(13) = MONOMER B COMPONENT (OR 0)
$ IPARM(14) = SOLVENT COMPONENT (OR 0)
$ IPARM(15) = INITIATOR A COMPONENT
$ IPARM(16) = INITIATOR B COMPONENT (OR 0)
$ IPARM(17) = INITIATOR C COMPONENT (OR 0)
$ IPARM(18) = TRANSFER AGENT COMPONENT (OR 0)
$ IPARM(19) = INHIBITOR COMPONENT (OR 0)
$ IPARM(20) = O2 COMPONENT (OR 0)
$ IPARM(21) = PEROXIDE COMPONENT (OR 0)
$------------------------------------------------------------
$ RPARM( 1) = HEAT OF POLYMERIZATION (Haa) , J/GMOL
$ RPARM( 2) = CSTR VOLUME, LITER
$ RPARM( 3) = NONISOTHERMAL REACTOR JACKET TEMPERATURE, K
$ RPARM( 4) = NONISOTHERMAL CSTR JACKET AREA, M2
$ RPARM( 5) = NONISOTHERMAL REACTOR OVERALL HTC, J/SEC/M2/K
$ RPARM( 6) = REACTOR TEMPERATURE, K,
$ = OPERATING TEMPERATURE OF ISOTHERMAL CSTR/PFR
$ = TEMPERATURE ESTIMATE FOR NONISOTHERMAL CSTR
$ RPARM( 7) = CSTR PRESSURE DROP (kPa), (DEFAULT=0.0)
$ RPARM( 8) = DECOMPOSITION EFFICIENCY FACTOR
$ FOR 1ST INITIATOR
$ RPARM( 9) = DECOMPOSITION EFFICIENCY FACTOR
$ FOR 2ND INITIATOR (OR 0)
$ RPARM(10) = DECOMPOSITION EFFICIENCY FACTOR
$ FOR 3RD INITIATOR (OR 0)
$ RPARM(11) = PFR LENGTH, M
$ RPARM(12) = PFR DIAMETER, CM
$ RPARM(13) = FEED STREAM LIVE CHAIN A FRACTION
POLYMERS
linear copolymer
Type I, Type II and Type III stepwise polymerization
Ideal CSTR (steady-state, well mixed, constant volume reactor)
Ideal PFR (steady-state, plug flow, constant diameter reactor)
k
C , + B Q
icb, j
j 0,1, j
k
P +BQ
pab,j
n,m,j n,m+1,j
6 monomer A propagation at site j on catalyst
k
Q + A P
pba, j
n,m, j n+1,m, j
7 monomer B propagation at site j on catalyst
k
Q + BQ
pbb, j
n,m, j n,m+1, j
Chain Transfer Reactions
8 transfer to monomer A at site j on catalyst
k
P +AD +P
maa,j
n,m, j n,m 1,0,j
9 transfer to monomer B at site j on catalyst
k
P + BD +Q
mab, j
n,m, j n,m 0,1, j
10 transfer to monomer A at site j on catalyst
k
Q + P
mba, j
+ A D
n,m, j n,m 1,0, j
11 transfer to monomer B at site j on catalyst
k
Q + BD +Q
mbb,j
n,m,j n,m 0,1,j
POLYMERS
k
P +S D +P
tsa, j
n,m, j n,m 1,0, j
k
Q +Q
tsb, j
BATCH
+ S D
n,m, j n,m 0,1, j
14 transfer to modifier at site j on catalyst
k
P (a)
+H
tha,j
D +P
n,m,j n,m 1,0,j
15 transfer to modifier at site j on catalyst
k
Q +H (b) thb, j
D +Q
n,m, j n,m 0,1, j
16 transfer to cocatalyst at site j on catalyst
k
P D +C,
tac, j
+ Z
n,m, j n,m j
17 transfer to cocatalyst at site j on catalyst
k
Q +C,
tbc, j
+ Z D
n,m, j n,m j
18 spontaneous transfer at site j on catalyst
k
P + C,
za, j
D
n,m, j n,m j
19 spontaneous transfer at site j on catalyst
k
Q + C,
zb, j
D
n, m, j n, m j
Termination Reactions
20 spontaneous termination of site j on catalyst
k
C , D
spt, j
j j
POLYMERS
Chain Termination
The current model presented in Table 10-1 provides for spontane-
ous and thermal termination of the active site. Once a site has been
market dead through these reactions, the mechanism does not allow
the site to be regenerated, rather that site is carried around as dead
catalyst.
C
j
k
act
k k
ica icb
P
1,0 C* Q
0,1
j
k
spt
k k
paa pbb
D
j
k k
za zb
k k
tac tbc
k k
pab k k pba
tda tdb
Pn, m D n, m Q n, m
k k
maa mbb
k k k k
paa tsa tsb pbb
k k
tha thb
k k
mab mba
User-Added Subroutines
An outline of the keyword input syntax for user-added unit opera-
tions such as the polymer reactor unit US21 is given below. IPARM
POLYMERS
RPARM, and SUPPLE are quite lengthy. These headers are given on
the next page and do not appear in the example problems.
The homogeneous multi-site catalyst model developed here allows
for a maximum of four (N=4) distinct reaction sites generated from
a maximum of 2 catalysts or 2 catalyst-cocatalyst pairs. Each type
of reaction site is assumed to be unique kinetically; therefore, each
type of site has a unique set of kinetic rate parameters assigned to it
through the SUPPLE data vector.
The catalyst(s) or catalyst-cocatalyst pair(s) flow rate is set in the
STREAM DATA section. The first catalyst contains N types of
sites, and the second catalyst (if present) contains up to 4 N types
of sites. The relative amount and state of each type of reaction site
is described by a set of 3 numbers given sequentially in the RPARM
vector.
The site fraction gives the relative portion of that type of site to all
of the types of sites present on that particular catalyst. Since the
possible states for each type of site can be activated, inactive, or
dead, the second and third entries convey what portion of the type
of site is activated and inactive, respectively. The fraction of dead
sites is then calculated internally by difference.
From a processing standpoint, it is preferable to have a single cata-
lyst exhibiting polymerization characteristics of a single type of cat-
alyst site throughout the reaction process. In this case IPARM(4)
and IPARM(5) would be set to 1 and 0, respectively. The site frac-
tion defined in RPARM(22) would then be set to 1.0, there is only
one type of site. Now if the catalyst was pre-activated upstream of
the reactor inlet such that 95% of the available sites were reactive,
RPARM(23) and RPARM(24) would be 0.05 and 0.95, respectively.
POLYMERS
TypeISites
- inactive
- activated
- dead TypeIISites
- inactive TypeIVSites
TypeIIISites - activated - inactive
- inactive - dead - activated
- activated - dead
dead
$
$ IPARM( 1) = REACTOR TYPE REQ
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 2) = REACTOR THERMAL CONDITION FLAG REQ
$ = 0 FOR NONISOTHERMAL REACTOR
$ = 1 FOR ISOTHERMAL REACTOR
$ IPARM( 3) = KINETICS TYPE REQ
$ = 6 FOR HOMOGENEOUS ZN HOMOPOLYMERIZATION
Constant (J/gmol)
1 kact 9.999E09 (L/gmol/sec) 20000.
2 kica 1.611E10 (L/gmol/sec) 20502.
3 kicb 1.056E09 (L/gmol/sec) 25940.
4 kpaa 1.611E10 (L/gmol/sec) 20502.
5 kpba 4.722E10 (L/gmol/sec) 25940.
6 kpab 7.222E08 (L/gmol/sec) 20502.
7 kpbb 1.056E09 (L/gmol/sec) 25940.
8 kmaa 5.833E04 (L/gmol/sec) 14540.
9 kmba 8.167E02 (L/gmol/sec) 19986.
10 kmab 9.917E02 (L/gmol/sec) 14540.
11 kmbb 2.722E04 (L/gmol/sec) 19986.
12 ktsa 0.000E00 (L/gmol/sec) 0.
13 ktsb 0.000E00 (L/gmol/sec) 0.
14 ktha 0.000E00 (L/gmol/sec) 0.
15 kthb 0.000E00 (L/gmol/sec) 0.
16 ktac 5.833E05 (L/gmol/sec) 14540.
17 ktbc 9.917E03 (L/gmol/sec) 14540.
18 kza 5.000E10 (sec^-1) 46420.
19 kzb 1.361E12 (sec^-1) 51860.
20 kspt 4.722E04 (sec^-1) 25104.
21 ktda 4.722E04 (sec^-1) 25104.
22 ktdb 4.722E04 (sec^-1) 25104.
Note: The heats of polymerization for this system (- Haa), (-Hba), (-Hab), and
(-Hbb) are 94800, 89650, 89650, and 84750 joule/gmol, respectively.
References
1. Kim, Kee Jeong and Kyu Yong Choi, Continuous Olefin
POLYMERS
$
ATTRIBUTE COMP= 1, KINE= ZN, *
MWD= 50000, 100000, 150000, 200000, 250000,*
300000, 350000, 400000, 500000, 600000,*
MMWD= psi0, psi1, psi2
$
THERMO DATA
METHOD SYSTEM=FLORY
KVALUE
CHI A,3, 0.5 $MONOMER-SOLVENT INTERACTIONS
COMP(WT,KG/MIN)=0.0/0.8/0.2/ 1.0E-7/0.01
$
UNIT OPERATION
US21 UID=REACTOR1, NAME=PE CSTReactor
FEED Feed_1
PROD Prod_1
$------------------------------------------------------------
$ IPARM( 1) = REACTOR TYPE REQ
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 2) = REACTOR THERMAL CONDITION FLAG REQ
$ = 0 FOR NONISOTHERMAL REACTOR
$ = 1 FOR ISOTHERMAL REACTOR
$ IPARM( 3) = KINETICS TYPE REQ
$ = 6 FOR HOMOGENEOUS ZN HOMOPOLYMERIZATION
$ = 7 FOR HOMOGENEOUS ZN COPOLYMERIZATION
$ IPARM( 4) = SITES ( 4 MAX ) ON 1ST CATALYST (=N) REQ
$ IPARM( 5) = SITES (4-N MAX) ON 2ND CATALYST (=M OR 0)
$ IPARM( 6) = N/A
$ IPARM( 7) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$
$ IPARM(11) = POLYMER COMPONENT REQ
$ IPARM(12) = MONOMER A COMPONENT REQ
$ IPARM(13) = MONOMER B COMPONENT (OR 0)
$ IPARM(14) = SOLVENT COMPONENT (OR 0)
$ IPARM(15) = MODIFIER COMPONENT (OR 0)
$ IPARM(16) = 1ST CATALYST COMPONENT REQ
$ IPARM(17) = 1ST COCATALYST COMPONENT (OR 0)
$ IPARM(18) = 2ND CATALYST COMPONENT (OR 0)
$ IPARM(19) = 2ND COCATALYST COMPONENT (OR 0)
$------------------------------------------------------------
IPARM 1,0,6,1,0, 0,0,0,0,0, 1,2,0,3,0, 4,5,0,0
$------------------------------------------------------------
$
$ RPARM( 1) = HEAT OF POLYMERIZATION (Haa) , J/GMOL
$ RPARM( 2) = CSTR VOLUME, LITER
$ RPARM( 3) = NONISOTHERMAL REACTOR JACKET TEMPERATURE, K
$ RPARM( 4) = NONISOTHERMAL CSTR JACKET AREA, M2
$ RPARM( 5) = NONISOTHERMAL REACTOR OVERALL HTC, J/SEC/M2/K
$ RPARM( 6) = REACTOR TEMPERATURE, K,
POLYMERS
is important to note:
1. Van Krevelen structural groups (from Appendix A) are given
for the polymer polyethylene, and the FILL=VANK keyword is
used to specify that van Krevelen prediction methods be used
for polymer properties.
2. The molecular weight distribution is provided on the
ATTRIBUTE statement. The distribution given will result in the
PHASE VLS=1
$
SPGR 6, 1.6 / 7, 1.4 / 8, 1.6 / 9, 1.4
NBP(K) 6, 450.0 / 7, 450.0 / 8, 450.0 / 9, 450.0
SOLUPARA 6, 10.0 / 7, 10.0 / 8, 10.0 / 9, 10.0
$
ENTHALPY (L,K,J/G,WT) CORRELATION= 1, DATA= *
1, 400, 200,-457.7994, 1.76/*
2, 400, 200,-457.7994, 1.76/*
3, 400, 200,-457.7994, 1.76/*
4, 400, 200,-457.7994, 1.76/*
5, 400, 200,-457.7994, 1.76/*
6, 400, 200,-457.7994, 1.76/*
7, 400, 200,-457.7994, 1.76/*
8, 400, 200,-457.7994, 1.76/*
9, 400, 200,-457.7994, 1.76
$
DENSITY (L,K,G/LIT,WT) CORRELATION= 1, DATA= *
1, 400, 200, 900/*
2, 400, 200, 905/*
3, 400, 200, 910/*
4, 400, 200, 915/*
5, 400, 200, 920/*
6, 400, 200, 925/*
7, 400, 200, 930/*
8, 400, 200, 935/*
9, 400, 200, 940
$
VP(Pa) CORRELATION= 20, DATA=6, 400, 200, 0.0, 1.0/*
7, 400, 200, 0.0, 1.0/*
8, 400, 200, 0.0, 1.0/*
9, 400, 200, 0.0, 1.0
$
LATENT (KCAL/K,WT) CORRELATION= 15, *
DATA=6, 400, 200, 8730800., 0.3526000/*
7, 400, 200, 8730800., 0.3526000/*
8, 400, 200, 8730800., 0.3526000/*
9, 400, 200, 8730800., 0.3526000
$
ATTRIBUTE COMP= 1, KINE= ZN, *
MWD= 50000, 100000, 150000, 200000, 250000,*
300000, 350000, 400000, 500000, 600000,*
MMWD= psi0, psi1, psi2
POLYMERS
$
THERMO DATA
METHOD SYSTEM=FLORY
KVALUE
CHI A,4,0.5 / B,4,0.5 $MONOMER-SOLVENT INTERACTION
$
STREAM DATA
PROP STRM=Feed_1, TEMP(K)=180.15, PRES(ATM)=35.0, *
$
COMP(WT,KG/MIN)= 0.0/0.2/0.8/0.1/0.1/ *
FEED Feed_1
PROD Prod_1
$------------------------------------------------------------
$ IPARM( 1) = REACTOR TYPE REQ
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 2) = REACTOR THERMAL CONDITION FLAG REQ
$ = 0 FOR NONISOTHERMAL REACTOR
$ = 1 FOR ISOTHERMAL REACTOR
$ IPARM( 3) = KINETICS TYPE REQ
$ = 6 FOR HOMOGENEOUS ZN HOMOPOLYMERIZATION
$ = 7 FOR HOMOGENEOUS ZN COPOLYMERIZATION
$ IPARM( 4) = SITES ( 4 MAX ) ON 1ST CATALYST (=N) REQ
$ IPARM( 5) = SITES (4-N MAX) ON 2ND CATALYST (=M OR 0)
$ IPARM( 6) = N/A
$ IPARM( 7) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$
$ IPARM(11) = POLYMER COMPONENT REQ
$ IPARM(12) = MONOMER A COMPONENT REQ
$ IPARM(13) = MONOMER B COMPONENT (OR 0)
$ IPARM(14) = SOLVENT COMPONENT (OR 0)
$ IPARM(15) = MODIFIER COMPONENT (OR 0)
$ IPARM(16) = 1ST CATALYST COMPONENT REQ
$ IPARM(17) = 1ST COCATALYST COMPONENT (OR 0)
$ IPARM(18) = 2ND CATALYST COMPONENT (OR 0)
$ IPARM(19) = 2ND COCATALYST COMPONENT (OR 0)
$------------------------------------------------------------
IPARM 1,0,7,2,2, 0,0,0,0,0, 1,2,3,4,5, 6,7,8,9
$------------------------------------------------------------
$
$ RPARM( 1) = HEAT OF POLYMERIZATION (Haa) , J/GMOL
$ RPARM( 2) = CSTR VOLUME, LITER
$ RPARM( 3) = NONISOTHERMAL REACTOR JACKET TEMPERATURE, K
$ RPARM( 4) = NONISOTHERMAL CSTR JACKET AREA, M2
$ RPARM( 5) = NONISOTHERMAL REACTOR OVERALL HTC, J/SEC/M2/K
$ RPARM( 6) = REACTOR TEMPERATURE, K,
$ = OPERATING TEMPERATURE OF ISOTHERMAL CSTR/PFR
$ = TEMPERATURE ESTIMATE FOR NONISOTHERMAL CSTR
$ RPARM( 7) = CSTR PRESSURE DROP (kPa), (DEFAULT=0.0)
$ RPARM( 8) = N/A
POLYMERS
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(11) = PFR LENGTH, M
$ RPARM(12) = PFR DIAMETER, CM
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ RPARM(15) = HEAT OF POLYMERIZATION (Hba) , J/GMOL
$ RPARM(16) = HEAT OF POLYMERIZATION (Hab) , J/GMOL
$ RPARM(17) = HEAT OF POLYMERIZATION (Hbb) , J/GMOL
$ RPARM(18) = PFR FANNING FRICTION FACTOR
$ RPARM(19) = N/A
POLYMERS
DIME SI
$
$ DIMENSION METRIC, STDTEMP=0, STDPRES=1.03323
$ DIMENSION ENGLISH, STDTEMP=60.0008, STDPRES=14.6959
$
OUTDIME REPLACE, SI, TIME=MIN
$
PRINT RATE=WT
$ PRINT RATE=WT, PWRATE
$
SEGMENT DATA
SEGMENT A, PE1 /B, BUT1, FILL=VANKREVELEN
STRUCTURE A, 4(2)/B, 60(1),4(1)
$
$ (1)Polymer
$ (2)Monomer A (3)Monomer B (4)Solvent
$ (5)Modifier (6)1st Catalyst (7)1st CoCatalyst
$ (8)2nd Catalyst (9)2nd CoCatalyst
$
COMPONENT DATA
LIBID 2,ETHYLENE/ 3,BUT1, BANK=SIMSCI
NONLIB 4,MSZ/ 5,MAO
$
POLYMER 1,PE-BUT
PCOMPOSITION 1, 0.9(A),0.1(B)
MWAVG 1, 100000/ 4, 292.2/ 5, 580.0
PHASE VLS=1
$
SPGR 4, 1.6 / 5, 1.4
NBP(K) 4, 450.0 / 5, 450.0
SOLUPARA 4, 10.0 / 5, 10.0
$
ENTHALPY (L,K,J/G,WT) CORRELATION= 1, DATA= *
1, 400, 200,-457.7994, 1.76/*
2, 400, 200,-457.7994, 1.76/*
3, 400, 200,-457.7994, 1.76/*
4, 400, 200,-457.7994, 1.76/*
5, 400, 200,-457.7994, 1.76
$
DENSITY (L,K,G/LIT,WT) CORRELATION= 1, *
DATA=1, 400, 200, 900/*
2, 400, 200, 905/*
3, 400, 200, 910/*
4, 400, 200, 915/*
POLYMERS
$
$ RPARM( 1) = HEAT OF POLYMERIZATION (Haa) , J/GMOL
$ RPARM( 2) = CSTR VOLUME, LITER
$ RPARM( 3) = NONISOTHERMAL REACTOR JACKET TEMPERATURE, K
$ RPARM( 4) = NONISOTHERMAL CSTR JACKET AREA, M2
$ RPARM( 5) = NONISOTHERMAL REACTOR OVERALL HTC, J/SEC/M2/K
$ RPARM( 6) = REACTOR TEMPERATURE, K,
$ = OPERATING TEMPERATURE OF ISOTHERMAL CSTR/PFR
$ = TEMPERATURE ESTIMATE FOR NONISOTHERMAL CSTR
$ RPARM( 7) = CSTR PRESSURE DROP (kPa), (DEFAULT=0.0)
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ RPARM(15) = HEAT OF POLYMERIZATION (Hba) , J/GMOL
$ RPARM(16) = HEAT OF POLYMERIZATION (Hab) , J/GMOL
$ RPARM(17) = HEAT OF POLYMERIZATION (Hbb) , J/GMOL
$ RPARM(18) = PFR FANNING FRICTION FACTOR
$ RPARM(19) = N/A
$ RPARM(20) = INTERACTION ORDER FOR TRANSFER AGENT TO P*
$ RPARM(21) = INTERACTION ORDER FOR TRANSFER AGENT TO Q*
$------------------------------------------------------------
POLYMERS
DIME SI
$
$ DIMENSION METRIC, STDTEMP=0, STDPRES=1.03323
$ DIMENSION ENGLISH, STDTEMP=60.0008, STDPRES=14.6959
$
OUTDIME REPLACE, SI, TIME=MIN
$
PRINT RATE=WT
$ PRINT RATE=WT, PWRATE
$
SEGMENT DATA
SEGMENT A, PE1, FILL=VANKREVELEN
STRUCTURE A, 4(2)
$
$ (1)Polymer
$ (2)Monomer A (3)Monomer B (4)Solvent
$ (5)Modifier (6)1st Catalyst (7)1st CoCatalyst
$ (8)2nd Catalyst (9)2nd CoCatalyst
$
COMPONENT DATA
LIBID 2,ETHYLENE/ 3,HEXANE , BANK=SIMSCI
NONLIB 4,MSZ/ 5,MAO
$
POLYMER 1,PETH
PCOMPOSITION 1, 1.0(A)
MWAVG 1, 100000/ 4, 292.2/ 5, 580.0
PHASE VLS=1
$
SPGR 4, 1.6 / 5, 1.4
NBP(K) 4, 450.0 / 5, 450.0
SOLUPARA 4, 10.0 / 5, 10.0
$
ENTHALPY (L,K,J/G,WT) CORRELATION= 1, *
DATA=1, 400, 200,-457.7994, 1.76/*
2, 400, 200,-457.7994, 1.76/*
3, 400, 200,-457.7994, 1.76/*
4, 400, 200,-457.7994, 1.76/*
5, 400, 200,-457.7994, 1.76
$
DENSITY (L,K,G/LIT,WT) CORRELATION= 1, *
DATA=1, 400, 200, 900/*
2, 400, 200, 905/*
3, 400, 200, 910/*
POLYMERS
$
$ RPARM( 1) = HEAT OF POLYMERIZATION (Haa) , J/GMOL
$ RPARM( 2) = CSTR VOLUME, LITER
$ RPARM( 3) = NONISOTHERMAL REACTOR JACKET TEMPERATURE, K
$ RPARM( 4) = NONISOTHERMAL CSTR JACKET AREA, M2
$ RPARM( 5) = NONISOTHERMAL REACTOR OVERALL HTC, J/SEC/M2/K
$ RPARM( 6) = REACTOR TEMPERATURE, K,
$ = OPERATING TEMPERATURE OF ISOTHERMAL CSTR/PFR
$ = TEMPERATURE ESTIMATE FOR NONISOTHERMAL CSTR
$ RPARM( 7) = CSTR PRESSURE DROP (kPa), (DEFAULT=0.0)
POLYMERS
linear copolymer
Type I, Type II and Type III stepwise polymerization
Ideal CSTR (steady-state, well mixed, constant volume reactor)
Ideal PFR (steady-state, plug flow, constant diameter reactor)
The second monomer group describes the reaction between two dif-
ferent bifunctional or polyfunctional monomers in which each of
the reacting monomers contains only one unique functional group.
The monomers of this group are labeled as ARA and BRB. A general
stepwise ARA and BRB polymerization can be represented as:
POLYMERS
ARB polymerization:
*
( n )AR 1 B<>A ( R ) n + ( 2n 1 )X:Y
The step growth polymerization reactions are usually slow and take
on the order of 10 - 20 hours to complete. The polymerization reac-
tions may be reversible, and, if so, they are dominated by equilib-
rium considerations. Consequently, it is important to accurately
simulate a flash in which any condensate or residual monomer is
driven off. The reaction kinetics are then shifted such that increased
yield is obtained. The monomers used in the step growth polymer-
izations include esters, ethers, amines, and amides. Polymer exam-
ples are polyesters, polyethers, nylons (Nylon 6, Nylon 6,6), and
polyimides (Kevlar).
The kinetic data for this reaction require the definition of a single
monomer along with the rate constants for the reaction between X1
and Y1.
If two monomers are involved in the reaction, and the monomers are
of the monofunctional form A-A and B-B (actually A-R-B and B-R-B),
AR 1 A + BR 2 B<> AR 1 R 2 B + C
X 1 A 1 R 1 A 1 X 1 + Y 1 B 1 R 2 B 1 Y 1 <> X 1 A 1 R 1 A 1 B 1 R 2 B 1 Y 1 + X 1 Y 1
The kinetic data for this reaction require the definition of two
monomers along with the rate constants for a reaction between X1
and Y1.
If a single monomer is involved in the reaction and the monomer is
of the monofunctional form A-A (actually A-R-A), the polymer
formed has the structure given by A-R-R-A. This is a Type III step-
wise polymerization.
Type III:
The kinetic data for this reaction requires the definition of a single
monomer along with the rate constants for a reaction between X1
and Y1.
Ultimately, it is required that a value for the number of monomer
units be incorporated into the average stepwise polymer and that
the number of active functional groups (X and Y) on the average
polymer chain be available. This characterization begins with the
population balance. The term Pm,a,b is introduced to indicate a linear
polymer molecule containing m repeat units terminated on one end
by an a functional group and the other end by a b functional group.
The vectors m, a, and b are defined by:
m1 X1 Y1
m m2 a X2 b Y2
POLYMERS
M M M
2 k2 Polymer addition
P n, a, b + P m, x, y >P n + m, a + x ( i ), b + y d ( j )
3 k3 Polycondensation II
P n, a, b + P m, x, y >P n + m, a + x ( i ), b + y d ( j ) + P ( k ), 2 ( i ) ( j ), 0
6 k6 Monomer salting
S ( i ) + S ( j ) >P ( i ) + ( j ), a, b + C i:j
7 k7 Two-chain reformation
P n, a, b + P m, x, y >P n ( r1 ), a ( i ), b + ( b1 ) +
P m ( r2 ) + ( r3 ), x ( j ) ( a1 ), y
8 k8 Deactivation of A group
P n, a, b + Z k >P n, a ( i ), b + ( C i:k )
9 k9 Deactivation of B group
P n, a, b + Z k >P n, a, b ( j ) + ( C i:k )
User-Added Subroutines
An outline of the keyword input syntax for user-added unit opera-
tions such as the polymer reactor unit US21 is given below. IPARM
and RPARM arrays are used to pass information on the component
and reactor configuration from the keyword file to the user-added
subroutine. The SUPPLE array is used to supply kinetics data.
$
$ NON RING REVERSIBLE KINETIC DATA
$
$ REACTION 1 POLYCONDENSATION I
$ SUPPLE( 1) = PREEXPONENTIAL FACTOR FOR INTRINSIC REACTION
$ SUPPLE( 2) = ACTIVATION ENERGY
$ SUPPLE( 3) = PREEXPONENTIAL FACTOR FOR CATALYZED RXN
$ SUPPLE( 4) = ACTIVATION ENERGY
$ SUPPLE( 5) = DEL(H) FOR EQUILIBRIUM RXN
$ SUPPLE( 6) = DEL(S)
$ REACTION 8 DEACTIVATION
$ SUPPLE(39) = PREEXPONENTIAL FACTOR FOR INTRINSIC RXN
$ SUPPLE(40) = ACTIVATION ENERGY
$ SUPPLE(41) = PREEXPONENTIAL FACTOR FOR CATALYZED RXN
$ SUPPLE(42) = ACTIVATION ENERGY
$
$ REACTION 9 DEACTIVATION
$ SUPPLE(43) = PREEXPONENTIAL FACTOR FOR INTRINSIC RXN
$ SUPPLE(44) = ACTIVATION ENERGY
$ SUPPLE(45) = PREEXPONENTIAL FACTOR FOR CATALYZED RXN
$ SUPPLE(46) = ACTIVATION ENERGY
$
$ REACTION 12c POLYADDITION OF TRIMER
$ SUPPLE(81) = PREEXPONENTIAL FACTOR FOR INTRINSIC RXN
$ SUPPLE(82) = ACTIVATION ENERGY
$ SUPPLE(83) = PREEXPONENTIAL FACTOR FOR CATALYZED RXN
$ SUPPLE(84) = ACTIVATION ENERGY
$ SUPPLE(85) = DEL(H) FOR EQUILIBRIUM RXN
$ SUPPLE(86) = DEL(S)
$
Type I Nylon 6
Type II Ethylene Glycol and Adipic Acid, Nylon 6,6
Type III BHET homopolymerization
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ RPARM(15) = HEAT OF POLYMERIZATION (Hba) , J/GMOL
$ RPARM(16) = HEAT OF POLYMERIZATION (Hab) , J/GMOL
$ RPARM(17) = HEAT OF POLYMERIZATION (Hbb) , J/GMOL
$ RPARM(18) = PFR FANNING FRICTION FACTOR
$---------------------------------------------------------------
RPARM 16900., 6400.0, 350., 2.5, 60., 494.15, 0.0, &
0.0, 0.0, 0.0, 0.0, 0.0, 0.0, 0.0, &
0.0, 0.0, 0.0, 0.0
$---------------------------------------------------------------
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, NYLON1, FILL=VANKREVELEN
STRUCTURE A, 4(5), 231(1), 403(1)
COMPONENT DATA
LIBID 2,CPLC/3,NPHT/4,H20
POLYMER 1, NYLON6
PCOMPOSITION 1, 1(A)
MWAVG 1, 8400
PHASE VLS = 1
ENTHALPY (L,K,J/G,WT) CORRELATION=1, DATA= *
1,400,200,-457.7994,1.676/*
2,400,200,-457.7994,1.676/*
3,400,200,-457.7994,1.676/*
4,400,200,-457.7994,1.676
DENSITY (L,K,G/LIT,WT) CORRELATION = 1, DATA= *
1, 400, 200, 897/*
2, 400, 200, 897/*
3, 400, 200, 897/*
4, 400, 200, 897
ATTRIBUTE COMP=1, KINE= SG, *
MWD = 1000,2000,3000,5000,6000,7000, *
8000,9000,10000,15000,20000, *
30000,40000,50000,*
MMWD = PSI0, PSI1, PSI2
THERMO DATA
METHODS SYSTEM=ALM
KVALUE
ALME A,2, 0.00681127
ALMC A, 0.475503
STREAM DATA
PROP STRM=FEED_0, TEMP(K)=518.15, PRES(ATM)=5, *
COMP(WT, KG/MIN)=0.0/9.650/0.000/0.0830
UNIT OPERATION
US21 UID=REACTOR_1, NAME=NYLON6 PFReactor
FEED FEED_0
PROD PROD_1
$---------------------------------------------------------------
$ IPARM( 1) = REACTOR TYPE REQ
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 2) = REACTOR THERMAL CONDITION FLAG REQ
$ = 0 FOR NONISOTHERMAL REACTOR
$ = 1 FOR ISOTHERMAL REACTOR
POLYMERS
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0
$ FIRST STAGE - FLASH DEVOLATILIZER
FLASH UID=PRODUCT
FEED PROD_1
POLYMERS
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, EG1/B, ADIPIC1 , FILL=VANKREVELEN
STRUCTURE A, 4(2)/B, 4(4), 237(2)
COMPONENT DATA
LIBID 2,EG/3,ADIPIC/4,H20
POLYMER 1, FPOLYMER
PCOMPOSITION 1, 0.5(A),0.5(B)
MWAVG 1, 160
PHASE VLS=1
ENTHALPY (L,K,J/G,WT) CORRELATION= 1,DATA= *
1,400,200,-457.7994,1.676/*
2,400,200,-457.7994,1.676/*
3,400,200,-457.7994,1.676/*
4,400,200,-457.7994,1.676
DENSITY (L,K,G/LIT,WT) CORRELATION = 1, DATA= *
1, 400, 200, 945/*
2, 400, 200, 945/*
3, 400, 200, 945/*
4, 400, 200, 945
ATTRIBUTE COMP=1, KINE = SG, MWD = *
10,20,30,40,50,60,80,100,120,150,*
170,200,500,700,800,900,1000,2000,*
3000,4000,5000,*
MMWD = PSI0, PSI1, PSI2
THERMO DATA
METHODS SYSTEM=FLORY
STREAM DATA
PROP STRM=FEED_0, TEMP(K)=439.15, PRES(ATM)=10, *
COMP(WT, KG/MIN)=0.0/4.850/11.450/0.00
UNIT OPERATION
US21 UID=REACTOR_1, NAME=FLORY-P PFReactor
FEED FEED_0
PROD PROD_1
$---------------------------------------------------------------
$ IPARM( 1) = REACTOR TYPE
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 2) = REACTOR THERMAL CONDITION FLAG REQ
$ = 0 FOR NONISOTHERMAL REACTOR
$ = 1 FOR ISOTHERMAL REACTOR
$ IPARM( 3) = KINETICS TYPE
$ = 3 FOR STEP GROWTH POLYMERIZATION ( TYPE I )
$ = 4 FOR STEP GROWTH POLYMERIZATION ( TYPE II )
POLYMERS
0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &
1 K3 -2.4883e4 3.9496e0
$ IPARM(10) = N/A
$---------------------------------------------------------------
IPARM 1,1,5,0,0, 0,2,0,0,0, 1,2,0,0,0, 0,3,0,0,0, 0,0,0,0
$---------------------------------------------------------------
$ IPARM(11) = POLYMER COMPONENT
$ IPARM(12) = MONOMER 1 ( A1-R1-B1 ) COMPONENT
$ IPARM(13) = MONOMER 2 ( A2-R2-B2 ) COMPONENT (OR 0)
$ IPARM(14) = MONOMER 1 - RING 1 ( A-R[1]-B ) COMPONENT
$ IPARM(15) = MONOMER 1 - RING 2 ( A-R[2]-B ) COMPONENT (OR 0)
$ IPARM(16) = MONOMER 1 - RING 3 ( A-R[3]-B ) COMPONENT (OR 0)
MWAVG 1, 400
ATTRIBUTE COMP=1, KINE = SG, MWD= *
10,20,30,50,70,100,150,200,250,*
300,350,400,500,700,800,1000,2000,*
3000,5000,7000,10000,*
MMWD= PSI0, PSI1, PSI2
THERMO DATA
METHODS SYSTEM=FLORY
STREAM DATA
PROP STRM=FEED_0, TEMP(K)=453.15, PRES(ATM)=10, *
PROD PROD_1
$---------------------------------------------------------------
$ IPARM( 1) = REACTOR TYPE REQ
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 2) = REACTOR THERMAL CONDITION FLAG REQ
$ = 0 FOR NONISOTHERMAL REACTOR
$ = 1 FOR ISOTHERMAL REACTOR
$ IPARM( 3) = KINETICS TYPE REQ
$ = 3 FOR STEP GROWTH POLYMERIZATION ( TYPE I )
$ = 4 FOR STEP GROWTH POLYMERIZATION ( TYPE II )
$ = 5 FOR STEP GROWTH POLYMERIZATION ( TYPE III )
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = N/A
$ IPARM( 7) = BASIS FOR KINETIC RATE CONSTANTS REQ
$ = 1 FOR VOLUME BASIS
$ = 2 FOR WEIGHT BASIS
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$---------------------------------------------------------------
IPARM 2,1,5,0,0, 0,2,0,0,0, 1,2,0,0,0, 0,3,0,0,0, 0,0,0,0
$---------------------------------------------------------------
$ IPARM(11) = POLYMER COMPONENT
$ IPARM(12) = MONOMER 1 ( A1-R1-B1 ) COMPONENT
$ IPARM(13) = MONOMER 2 ( A2-R2-B2 ) COMPONENT (OR 0)
$ IPARM(14) = MONOMER 1 - RING 1 ( A-R[1]-B ) COMPONENT
$ IPARM(15) = MONOMER 1 - RING 2 ( A-R[2]-B ) COMPONENT (OR 0)
$ IPARM(16) = MONOMER 1 - RING 3 ( A-R[3]-B ) COMPONENT (OR 0)
$ IPARM(17) = P1 COMPONENT (OR 0)
$ IPARM(18) = P2 COMPONENT (OR 0)
$ IPARM(19) = P3 COMPONENT (OR 0)
$ IPARM(20) = CONDENSATE COMPONENT (OR 0)
$ IPARM(21) = CATALYST COMPONENT (OR 0)
$ IPARM(22) = DEACTIVATION AGENT COMPONENT (OR 0)
$ IPARM(23) = SALTING AGENT COMPONENT (OR 0)
$ IPARM(24) = INERT COMPONENT, N2 (OR 0)
$---------------------------------------------------------------
$ RPARM( 1) = HEAT OF POLYMERIZATION (Haa) , J/GMOL
$ RPARM( 2) = CSTR VOLUME, LITER
$ RPARM( 3) = NONISOTHERMAL REACTOR JACKET TEMPERATURE, K
$ RPARM( 4) = NONISOTHERMAL CSTR JACKET AREA, M2
POLYMERS
POLYMERS
Live Chains The live or growing chains contain an active center and
as such can be considered macroradicals. The activity
of the live chains has not been curtailed by a transfer or
termination reaction, and the live chains continue to
incorporate monomer. In the case of the free radical
copolymer, the live chain may be terminated with an
active radical formed from either the A monomer or B
monomer. These radicals are labeled as Live A and
Live B Chains, respectively. In step growth kinetics all
chains are considered live.
Dead Chains The dead or polymer chains are chains that have
undergone a transfer or termination reaction and are no
longer growing. These chains are labeled as Dead
Chains.
Bulk Chains The bulk chain is defined as the average chain in the
product. The properties of the bulk chain are derived
from the arithmetic average of the equivalent proper-
ties of all types of chains found in the product. For free
radical kinetics, the dead chain properties dominate the
POLYMERS
The number and weight average molecular weights for the dead
chains can be obtained as
M n = -----1
0
and
M w = -----2
1
POLYMERS
FEED STREAM S1
PRODUCT STREAM S2
OPERATING CONDITIONS
TEMPERATURE, K 333.15
VOLUME, M3 1.0000
DUTY, M*KJ/HR -8.678E-03
TOTAL HEAT OF REACTION, M*KJ/HR 8.678E-03
SPACE-TIME, HR, AT OUTLET CONDITIONS 6.9357
SPACE-VELOCITY, /HR, AT OUTLET CONDITIONS .1442
PERCENT
COMPONENT FEED CHANGE PRODUCT CONVERTED
1 PMMAC-VA POLYMER .000 13.525 13.525
2 MMAC MONOMER A 18.000 -10.341 7.659 57.452
3 VACT MONOMER B 90.000 -3.143 86.857 3.492
4 BNZN SOLVENT 36.000 -1.042E-03 35.999 2.738E-03
5 BOBZ INITIATOR A .180 -3.966E-02 .140 22.032
FEED PRODUCT
AT OPERATING CONDITIONS
TEMPERATURE, K 333.1300 333.1500
PRESSURE, KPA 506.6265 101.3253
ENTHALPY, M*KJ/HR .0145 .0145
COPOLYMER COMPOSITION
POLYDISPERSITY DATA
LIVE B CHAINS:
WEIGHT FRACTION IN POLYMER .1758E-07
NUMBER AVERAGE MOLECULAR WT .2839E+05
WEIGHT AVERAGE MOLECULAR WT .5709E+05
POLYDISPERSITY INDEX 2.0107
DEAD CHAINS:
WEIGHT FRACTION IN POLYMER .1000E+01
NUMBER AVERAGE MOLECULAR WT .5430E+05
WEIGHT AVERAGE MOLECULAR WT .8417E+05
POLYDISPERSITY INDEX 1.5500
BULK CHAINS:
NUMBER AVERAGE MOLECULAR WT .5430E+05
WEIGHT AVERAGE MOLECULAR WT .8417E+05
POLYDISPERSITY INDEX 1.5500
==================================================================
STREAM ID POLYMER_MELT S1 S2
NAME
PHASE LIQUID LIQUID LIQUID
STREAM ID POLYMER_MELT S2
NAME
PHASE LIQUID LIQUID
POLYMERS
POLYMERS
polymer melt that is pushed along on the leading edge of the wiper
blades. For polymer melts of high viscosity, it is usually beneficial
to tilt the wiper blades so that they propel the melt downward rather
than allowing pure gravity-induced flow. The melt in the bow wave
is under shear. This assists in the vertical transport of Bingham and
pseudoplastic fluids by decreasing their viscosity in this region.
The melt devolatilizes as it advances through the WFE. The thin
film of melt on the wall provides a large surface-area-to-volume
ratio that is critical in rate-limited mass transfer. The wiper blades
serve both to transport the melt axially, as well as to remix it, thus
maintaining the maximum concentration of volatiles near the liq-
uid-vapor interface. Mass transfer is increased by the periodic
remixing of the melt as it enters a bow wave and is subsequently
smeared back onto the wall.
Operating Modes
There are two WFE operating modes: rating and design. In the rat-
ing mode, you specify an existing piece of equipment. The model
can then be used to evaluate the performance of that equipment
under various process conditions. In the design mode, you must
specify the desired outlet weight fraction of consecutive volatile
components. A relative tolerance around this specification may also
be given (default 10-5). The design mode calculations will predict
the required WFE diameter and height to meet the specification.
The design mode can be used with any of the combinations of feed-
back ratio, temperature profile, and blade configuration described in
this section.
One important parameter in the design mode calculations is the bow
wave to film area ratio. The bow wave area is determined by the
POLYMERS
WFE feed volumetric flow rate. The bow wave to film area ratio is
used to determine the design diameter of the WFE directly. You can
specify this parameter or accept the default of 0.05. As this ratio
gets larger, the design diameter decreases. The implications are that
too large a diameter will result in extreme power consumption,
while too small a diameter will require a very long WFE to meet the
specification. Adjustment of this parameter is important in obtain-
4500 100
90
4000 Final Concentration
80
3500 Power (%)
Concentration (ppm)
70
3000
60
2500
50
2000
40
1500
30
1000 20
500 10
0 0
0 0.5 1 1.5 2 2.5 3
Rotation Rate
Feedback Ratio
PRO/II models a Wiped Film Evaporator unit operation as a series
of levels. A level consists of a number of identical stages equal to
the number of blades in its cross section. Each stage consists of a
POLYMERS
this mixed melt is then wiped behind the blade, and the rest is
passed to the next lower stage. If the feedback ratio is 0.0, the model
is called Surface Renewal. The picked up melt is passed to the next
stage and the bow wave from above is wiped behind the blade. The
PRO/II model allows continuous intermediate values of the feed-
back ratio to simulate imperfect mixing.
Evaporation element
Q Q
Mixing element
From level n-1
To level n
Stage n in level n
16
Surface Renewal
Concentration (1000 ppm)
14
Feedback
12
POLYMERS
10
0
0 5 10 15 20 25 30 35 40 45 50
Number of Stages
300
Surface Renewal
280
Feedback
Concentration (ppm)
260
Equilibrium Concentration
240
220
200
180
160
140
120
30 32 34 36 38 40 42
Number of Stages
Blade Configurations
A WFE unit operation can have either vertical, pitched, or alternat-
ing blade configuration. The selection of blade configuration
depends on the properties of the polymer melt. Pitched or alternat-
ing blades are preferred for high-viscosity solutions. Note that
pitched blades with an angle of zero degrees are not the same as
vertical blades, because with vertical blades axial velocity is deter-
mined by gravity flow, while with pitched blades axial velocity is
determined by the pitch angle and rotation rate of the wiper blades.
With pitched or alternating blades, you must specify their pitch
angle or a default of 22.5 degrees will be assumed. Additionally,
you must specify the number of blades in a horizontal cross section
of the WFE or accept the default of eight. If alternating blades are
specified, there must be an even number.
You should also specify blade length, blade width, and wall clear-
ance.
Straight
Wall Pitched
Alternating
Blades
Liquid Viscosity
You can specify liquid viscosity for the polymer as shown in Chap-
ter 5. Take note, however, that this release of PRO/II applies a molar
mixing rule to polymer mixtures. This will cause the system to gen-
erate inaccurate viscosity estimates for a polymer melt containing
volatiles. For this reason, the WFE model allows you to input a zero
shear melt viscosity to be used in the model. This viscosity is inter-
nal to the WFE model and will not be shown in any section of the
output other than the WFE report. If you do not input the zero shear
melt viscosity, the WFE will use the viscosity predicted by PRO/II
as its default.
POLYMERS
Note: If you specify the melt viscosity for the WFE, the WFE will
not consider the variance of viscosity with temperature. This is
especially important when specifying temperature profiles and
may wish to enter the zero shear melt viscosity as the average
between the inlet and outlet temperatures.
Liquid Diffusivity
The WFE model is very sensitive to the diffusivities of the volatiles
in the polymer melt. The predictive diffusivity method within
PRO/II may give inaccurate results; therefore, you will probably
want to input diffusivity data for the specific system. Refer to the
PRO/II Keyword Manual or the PRO/II Users Guide for informa-
tion on entering diffusivity data. Enter data for the binary pairs of
volatiles (i) diffusing through every other component (j). If the
polymer component is number 1 and the solutes are numbers 2 and
3, you must enter data for D21, D23, D31, and D32. In most cases, you
will enter the same coefficients for all ij pairs of the same ith index.
Example 13-1 shows the proper syntax for the DIFDATA statement.
POLYMERS
These diffusivity values are not expected to be the exact values for
mass diffusivity. Since the film is never entirely stagnant, it is safer
to think of these values for diffusivity as effective diffusivities.
The diffusivity data are probably the best choices for attempting to
tune a WFE model. For design estimates, true diffusivity data will
provide a conservative estimate. Values of Dij on the order of 10-6 to
Output
Both modes will output the height, diameter, operating pressure,
mass flow of evaporate, heat duty, and shaft power requirements of
the WFE. In addition, the WFE output report will contain a zone
report that will show conditions at periodic levels within the WFE.
The diffusivities for volatile components at the entering and exiting
conditions will also be shown.
General Information
The wiped film evaporator unit operation provides the capability to
separate solvents and/or monomers from a polymer melt. A wiped
film evaporator should be used when the removal of volatiles from a
viscous polymer melt is diffusion limited. The blades inside the
3. Required entry for design mode.
the evaporator. The volatiles are pulled out of the evaporator under
vacuum.
A mixture of up to ten feed streams is allowed and the unit requires
both an overhead and a bottoms product.
The wiped film evaporator can be modeled under several heating
conditions. It can be modeled isothermally (using the combined
feed temperature or user-specified temperature), adiabatically
(allowing heat input only through friction with the wiper blades), at
steady state (allowing heat input from a heating/cooling jacket), or
with a user-specified temperature profile.
The wiped film evaporator will operate at the lowest of the feed
stream pressures unless an inlet pressure and/or inlet pressure drop
are specified.
Keyword Description
POLYMERS
temperature is used.
Default values are underlined.
In columns 2 and 3, In indicates the variable may be input, Out indicates it may be output.
* Required input.
Required input in design mode only.
In user input units.
Example 13-1
This example problem describes a polystyrene polymerization and
separation process, comprised of a polymer CSTR, a flash, a con-
troller, and a WFE. The CSTR produces a continuous polymer
molecular weight distribution that it uses to calculate the polymer
pseudocomponent concentrations in its product stream. The flash
and controller work to reduce the volatile concentration in the prod-
uct stream to the point where the process becomes rate-limited. The
WFE then takes the equilibrium liquid from the flash as its feed.
POLYMERS
Notice that the operating temperature of the WFE is higher than that
of the flash. This puts the feed stream in a non-equilibrium condi-
tion in the WFE. If an equilibrated liquid stream is fed to a WFE,
and the WFE temperature and pressure are not different (higher
and/or lower, respectively) from the feed conditions, the feed will
not devolatilize.
0/277,0/0/0/0/285,0/0/0/0/293,0/0/0/0/301,0/0/0/0
FLASH UID=F1
FEED PROD_1
PRODUCT V=VAP1, W=PROD_2
ISO TEMPERATURE=400, PRESSURE=0.666
CONTROLLER UID=CN1
SPEC STREAM=PROD_2,FRACTION(WT), COMP=2,4, VALUE=0.02
VARY FLASH=F1, TEMP, PCT2=10
CPARAMETER IPRINT, NOSTOP
WFEV UID=WFE1
FEED PROD_2
PRODUCT PROD_3,VAP4
IPARM =1,,,1
RPARM =3,0.50,0.2,,,,,,,,500,,,,,,,,,0.0001,1E-5,460
END
POLYMERS
=====================================================================
UNIT 4, 'WFE1'
WIPED FILM EVAPORATOR - RATING MODE
TEMPERATURE PROFILE: ISOTHERMAL
FEEDS PROD_2
PRODUCTS VAPOR VAP4
LIQUID PROD_3
OPERATING CONDITIONS
INLET TEMPERATURE, DEG K 460.0000
OUTLET TEMPERATURE, DEG K 460.0000
EVPORATOR PRESSURE, KPA .6660
REQUIRED SHAFT POWER, KW 2.0861
REQUIRED HEAT DUTY, KW 4.4966
VOLUMETRIC VAPOR FLOW RATE, M3/HR 107.7954
PHYSICAL CONFIGURATION
DIAMETER, M .5000
HEIGHT, M 3.0000
NUMBER OF VERTICAL BLADES 8
BLADE LENGTH, M .2000
BLADE WIDTH, M 5.000E-03
BLADE TO WALL CLEARANCE, M 5.000E-03
FEEDBACK RATIO 1.0000
POWER PARAMETER (GAMMA) 1.0000
VISCOSITY PARAMETER (OMEGA) 1.0000
VISCOSITY RELAXATION TIME, SEC .3000
POWER LAW INDEX .3000
BOW WAVE TO FILM AREA RATIO .0500
SHAFT ROTATION RATE, REV/SEC 1.5000
VELOCITY PROFILE, 1/SEC 471.2389
STREAM PROPERTIES
LIQUID LIQUID VAPOR
POLYMERS
INLET OUTLET OUTLET
STREAM ID PROD_2 PROD_3 VAP4
MASS FLOW RATE, KG/HR 143.2308 140.9980 2.2328
DENSITY, KG/M3 972.6086 976.6445
VISCOSITY, PAS 500.0000 500.0000
for esters
210 -OH(pri) OH Primary hydroxyl group -
211 -OH(sec) OH Secondary hydroxyl -
group
212 -OH(tert) OH Tertiary hydroxyl group -
213 -OH(phen) OH Phenolic hydroxyl -
group
214 -OH(hydr.bond) OH Hydrogen bonded Special contribution for -
hydroxyl group hydrogen bonded hydroxyl
group
215 -OH(twin or Correction for twinned Correction for each hydroxyl -
alpha) or alpha positioned group on adjacent or
hydroxyl group hydroxyl- bisubstituted
carbon atoms
220 -CH(OH)- CH(OH) Hydroxymethylene Substituted main chain unit +
or general contribution
221 -CH(OH)(wet)- CH(OH) Hydroxymethylene - Substituted main chain unit +
wet or general contribution
222 -CH(OCH3)- CH(OCH3) Methoxymethylene Substituted main chain unit +
or general contribution
230 -CO- O Carbonyl group General contribution -
||
C
231 -CO-(nc) O Non-conjugated Main chain unit or general +
|| carbonyl group as main contribution
C chain fragment
232 -CO-(c) O One-side conjugated Main chain unit or general +
|| carbonyl group as main contribution
C chain fragment
233 -CO-(cc) O Two-side conjugated Main chain unit or general +
|| carbonyl group as main contribution
C chain fragment
234 -CHO O Aldehyde group General contribution -
POLYMERS
||
CH
235 -COO- O Ester group General contribution (not -
|| O conjugated)
C
+ Indicates main chain group - Indicates side group
a sequence of an odd
number of CH2 units in
a main chain with
thioether groups
706 Odd(-OCOO-) Special contribution of Main chain contribution +
a sequence of an odd
number of CH2 units in
a main chain with
carbonate or equivalent
group
707 Odd(-OCONH-) Special contribution of Main chain contribution +
a sequence of an odd
number of CH2 unit in a
main chain with
carbonamide or
equivalent groups
708 Backbone atom Special contribution of -
each backbone atom (in
a main chain)
709 Cross link Special contribution of -
a side-chain bivalent
group
710 Side group Special contribution of -
side-chain group
711 Small molecule Special contribution for -
a small molecule - (not
polymeric)
712 Symmetry(1p) One plane of symmetry -
- special contribution
713 Symmetry(2p) Two planes of -
symmetry - special
contribution
714 Symmetry(mp) More than two planes -
of symmetry - special
contribution
POLYMERS
D
F
Dead chains , 12-1
Devolatilization , 13-1
Feedback model , 13-4
Diffusivity , 13-6
Feedback ratio , 13-3
Flory-Huggins model
attibutes , 7-10
E example , 7-15
POLYMERS
K-values , 7-11
Emulsion polymerization , 1-4, 5-3 METHOD statement , 7-10
Energy operating equations overview , 7-9
CSTR , 8-2 typical usage , 7-10
PFR , 8-4 Flowsheet, building the , 2-6
Energy parameter , 7-17 Free radical initiation , 9-7
Equations of state Free radical kinetics
attributes , 7-16 mechanisms , 9-2
example , 7-22 polymerization via , 9-2
Input description
invariant properties , 4-5 L
polymer attributes , 4-3
polymer definition , 4-2
temperature-dependent properties , 4-5 Live chains , 12-1, 12-3
POLYMERS
Invariant properties
input description , 4-5
keyword summary , 4-2 M
types , 4-1
Ionic polymerization , 1-1 Macromolecules , 1-2
IPARM variables , 9-13, 10-9, 11-8 Mass operating equations
definitions , 13-11 CSTR , 8-2
entering , 2-7 PFR , 8-4
I-3 Index
Melt physical properties
liquid diffusity , 13-7
P
liquid viscosity , 13-6
options , 13-6 Pairs
homopolymer segment-colvent , 7-4, 7-13
METHOD statement
advanced lattice model , 7-2 Parameters
equations of state , 7-17 binary interaction , 7-3
Flory-Huggins model , 7-10 equations of state for solvents , 7-17
UNIFAC free volume model , 7-8 Omega , 13-7
operating, wiped film evaporator , 13-9, 13-11
Mole balances , 8-3, 8-4
pure chain length , 7-17
Molecular weight distribution , 12-2
pure energy , 7-17
calculating , 2-3, 4-8
pure size , 7-17
entering data , 2-4, 4-9, 5-10
pure species , 7-26
moments , 4-1, 5-1
PCFRAC attributes
providing , 4-1
free radical , 5-5
Molecular weight fractions , 5-11 step-growth polymerization , 5-6
Molecular weight, average , 2-3, 12-3 Ziegler-Natta , 5-5
Moment expansions , 8-7 Perturbed hard-sphere-chain (PHSC) theory
Moments , 8-3, 8-4, 12-3 See Equations of state
Monomers , 1-1, 1-2, 1-3, 9-2 PFR , 8-1, 9-1, 10-1, 11-1
coordination polymerization , 10-31
MWD or MMWD attibutes
Ziegler-Natta polymerization , 5-4 free radical copolymerization , 9-38
free radical homopolymerization , 9-29
MWD or MMWD attributes
mass and energy balances , 8-4
example , 5-6
type 1 step growth polymerization , 11-15
free radical polymerization , 5-3
type 2 step growth polymerization , 11-21
step growth polymerization , 5-4
type 3 step growth polymerization , 11-27
PFRAC attributes, example , 5-7
N Phase equilibrium calculations , 7-1
Poly(vinylchloride) , 1-2
Non-Newtonian fluids , 13-6 Polyamides , 1-2
Nylon 6 , 11-13 Polydispersity index , 12-2
Polyesters , 1-2
Polyethylene , 1-2
O Polymer blend , 1-3
Polymer chain , 1-3
Omega parameter , 13-7 Polymer characterization conversion , 6-2
Operating data , 2-7 Polymer characterization conversion utility , 5-1
Operating modes, wiped film evaporator , 13-2 Polymer characterization via moments , 12-3
Operating parameters, wiped film evaporator , 13-9, Polymer components
POLYMERS
I-5 Index
Report options SUPPLE variables , 9-13, 10-9, 11-8
output , 6-1 entering , 2-7
PRINT statement , 6-1 Surface renewal model , 13-4
PWRATE and PCONV statements , 6-2
Suspension , 5-3
Rotation rate, wiped film evaporator , 13-3
Suspension polymerization , 1-4
RPARM variables , 8-5, 9-13, 10-9, 11-8
definitions , 13-11
entering , 2-7 T
emulsion/suspension , 5-3
entering PWRATE and PCONV , 6-2 UNIFAC free volume model
limits for wiped film evaporator , 13-10 application ranges , 7-7
MWD or MMWD attributes , 5-3, 5-4 attributes , 7-7
PCFRAC attributes , 5-5, 5-6 example , 7-9
polymer keyword summary , 5-2 K-values , 7-8
polymer solids in , 5-1 METHOD statement , 7-8
supplying data , 5-1 overview , 7-7
wiped film evaporator keywords , 13-9, 13-10 pure component properties , 7-7
I-7 Index
POLYMERS