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Mercosur Congress on Chemical Engineering
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Mercosur Congress on Process Systems Engineering


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PVC STRIPPING COLUMN MODELING AND SIMULATION
J. H. P. Brooman
1
*
, R. P. Brito
2

1
Braskem
2
Departamento de Engenharia Qumica, Universidade Federal de Campina Grande


Abstract. A simplified steady state model for monomer desorption from poly vinyl chloride (PVC)
suspension resin in a stripping column was developed. Suspension resin is produced as aqueous
slurry with 10% to 20% unconverted monomer. Removal by depressurising can reduce that amount
to 1-3% but stripping is required to take the vinyl chloride amount below the 1 ppm level. Based
on Berens (1974b), the model considers the diffusion process as Fickean. The solubility of vinyl
chloride monomer (VCM) in PVC is considered following the Flory-Hugins model as the monomer
initial concentration can be as high as a few percent. An Arrhenius-like equation was developed
relating the desorption constant to temperature. Some simplifying assumptions were made: the
resin slurry water phase is always saturated and has a negligible amount of VCM; monomer has no
impact on mass and enthalpy balances; if feed temperature is higher than feed tray, the feed flashes
instantly; for desorption effect the trays are considered as perfectly mixed tanks; no effect of
residence time distribution is taken in account. A material and enthalpy balance is developed, on
the same lines as for a common distillation column. A method for quantifying the resin thermal
damage due to the stripping process is proposed based on Arlman (1954). Using this model,
simulations were run to establish the sensitivities to feed rate and column pressure, in an open loop
system. Closed loop cases, where column pressure and steam rate were manipulated to control
monomer concentration in stripped resin, were run for steam usage minimization. The
implementation was made in MS Excel spreadsheet as this software is commonplace, has a friendly
interface and the model intended use is as a training tool for operators and plant engineers.

Keywords: Vinyl Chloride, Stripping, Modeling.



1. Introduction
The reasons for recovering unconverted monomer from PVC resin slurry, usually 10% to 15% wt, evolved
from purely economical to health hazard aspects due to the discovery that VCM is a carcinogenic substance.
The batch stripping technique initially adopted and the low residual VCM levels required generated an
aggressive thermal history causing excessive degradation of the resin in many cases. The basic cause of the
degradation was the long heating time for the batch technique. The discovery that a short time stripping at higher
temperatures would produce less damage resulted in a large number of patents describing continuous stripping
columns.
Presently, continuous stripping is the standard technique for getting low residual VCM suspension resin with
acceptable damage at low cost.
As Braskem, the largest suspension PVC producer in Brazil moved to use this technique in its plants the need
for a simulation tool for training use appeared.

To whom all correspondence should be addressed. Address: Braskem, av. Assis Chateaubriand, 5260, Pontal, 57190-000
Maceio/AL - Brazil. E-mail: john.brooman@braskem.com.br

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Mercosur Congress on Chemical Engineering
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Mercosur Congress on Process Systems Engineering


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2. Model Development

2.1. VCM Dessorption

The theoretical and practical basis established by Berens (1974b) for describing the VCM diffusion through a
PVC matrix in suspension and emulsion resins successfully treats desorption phenomena at low VCM
concentrations as a Fickean diffusive process associated to the resin grain primary particles diameter.
Desorption kinectics follow a Fickean model so:

) (
eq
C C k
dt
dC
= (1)

Where
k is the desorption constant, h
-1
.
C is the average VCM concentration in the resin, weight fraction.
C
eq
is C for resin at equilibrium with VCM existing in gas phase outside the resin particles.

Berens (1974b) found that the diffusivity of VCM in PVC is a function of temperature following an
Arrhenius-like relationship and is independent of molecular weight at least in the commercial resin range. The
desorption constant can be calculated from Berens (1974b) data and primary particle diameter measurements,
and follows the same kind of relationship to temperature.

=
RT
E
a
e k k
0

(2)

Where
E
a
is the activation energy, cal/mol
R is ideal gas constant, cal/mol K
T is the temperature, K

The column trays are considered as perfectly mixed tanks and no effect of residence time distribution is taken
in account so the tray-to-tray VCM in resin concentration changes are given by

( )
r
kt
eqi i
eqi i
e
C C
C C
+
=

1

(3)
Q
h F D
t
L A
R
4
2

= (4)


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Mercosur Congress on Chemical Engineering
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Where
t
R
is the residence time, h
D is column diameter, m
F
A
is fraction of column section not occupied by downcomer
h
L
is liquid height on tray, m
Q is the tray volumetric liquid/solid feed, m
3
/h

2.2. VCM Solubility in PVC

Berens (1974a) found that solubility of VCM in PVC at concentrations below 4,000 ppm and at temperatures
above glass transition (ca. 85C) follows the Flory-Huggins model, showing a Henry Law behavior at low
concentrations. In this work the Flory-Huggins model was considered valid from zero to 20,000 ppm. The Flory-
Huggins model equation is given by:

) (
0
2
) 1 (

+
= e
P
P
m
m

(5)

Where
P
m
is VCM partial pressure, atm
P
m0
is VCM vapor pressure, atm
is PVC volumetric fraction in the swollen resin
is the solvent interaction parameter

VCM weight fraction at equilibrium (solubility) is given by:

p
m
eq
C

) 1 (
=
(6)

Where

m
is liquid saturated VCM density, g/cc

p
is PVC density, assumed as constant (1.35 g/cc)

Xie et al. (1991) present the following relation of to temperature:

02 . 3
15 . 273
4 . 1286

+
=
T
(7)


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Where
T is temperature in C.

Considering all relationships presented, it can be stated that:

) , (
m eq eq
P T C C =
(8)

There is no analytical solution for this equation system so an approximate quadratic expression was
developed based on data generated for the range 90C-130C x 1 ppm-15,000 ppm. MS Excel regression
routines were used and lower significance terms were eliminated. The obtained relation is:

Ceq = 35621 P
m
+ 146.77 P
m
2
- 78.84 P
m
T -2.84 (9)

Where: C
eq
in wt ppm, P
m
in atm and T in K.
A R-square correlation coefficient of 99.9% was obtained, indicating low errors inside the work region.


2.3. Mass and Energy Balances

Mass and energy balances are the same used for distillation columns with some simplifying assumptions.
The VCM stream was not included in the general mass and energy balances as it is very small (ca. 0.5%
of feed). A separate VCM balance will be developed based on Eq. 3.
VCM solubility in water was not taken in account as it is small (ca. 10% the VCM solubility in PVC).
Water phase in trays is always saturated.

In Figure 1 a stream diagram for a generic tray is presented.


Fig. 1 Tray Stream Diagram



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Where
L = liquid stream (contains only water), kg/h
V = vapor stream (contains only water), kg/h
P = PVC stream (contains only PVC), kg/h

Mass and energy balance
i i i i i i
V P L V P L + + = + +
+ 1 1 1
(10)

i V i P L i V i P i L
V h P h L h V h P h L h
i i i 1 1 1 1 1 1
1 1 1 1
+ + = + +
+
+

(11)

As PVC does not vaporize or dissolve,
F o i
P P P = =


Fig. 2 Top Section of the Column

It was considered that the feed when hot would immediately flash to tray 1 temperature before reaching this
tray. This approach is conservative as the flashed steam does not contribute much to lower the VCM partial
pressure above tray 1.

Feed flash mass and energy balance

0 0 0
V P L P L
F F
+ + = + (12)

0 0 0 0 0 0 V L PF F LF F
h V h P h L h P h L + + = + (13)

Combining the previous two equations the top liquid and vapor streams are given by

) (
) ( ) ( ) (
0 0
0 0 0 0 0
0
L V
V F PF V F LF V
h h
P h h P h h L h h
L

+
=
(14)


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) ( ) (
0 0 0
P L P L V
F F
+ = (15)

Stream flowrates

i i i i i i
V P V P L L + + =
+ + 1 1 1
(16)

) (
) ( ) ( ) ( ) (
1
1 1 1 1
1
+

+

+
=
Vi Li
i Pi Li i Li Li i Vi Li i Pi Li
i
h h
P h h L h h V h h P h h
V
(17)

As the temperature increase along the column is small h
Vi+1
can be approximated as h
Vi
.

) (
) ( ) ( ) ( ) (
1 1 1 1
1
Vi Li
i Pi Li i Li Li i Vi Li i Pi Li
i
h h
P h h L h h V h h P h h
V

+
=

+

(18)

2.4. VCM Mass Balance

As VCM flows down the column absorbed in the PVC stream, VCM vapor will be desorbed following Eq. 3.
For each tray i the same amount of VCM that comes in stream P
i-1
go up as vapor. This presumes the
stripping column will be operating perfectly, with no VCM in its bottom stream, what is a conservative
assumption as it causes a higher VCM partial pressure to be used in the desorption calculations.
One operation parameter is the water vapor/VCM vapor mass ratio over tray 1. Eq. 19 shows the required
water vapor flowrate over tray 1.

0 0 1
C P V = (19)

Where
is the water vapor/VCM vapor mass ratio in the top of the column
P
0
is the feed PVC stream , kg/h
C
0
is the VCM weight fraction in feed PVC stream

2.5. Pressure Profile

Water vapor pressure can be calculated:

m A
P P P + =
0
(20)

( ) [ ]
MVC A m A
MW MW V V P P / ( / 1
0
+ = (21)


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Where
P
A0
is the water partial pressure, atm
P is pressure over tray, atm
V
m
is VCM vapor mass flowrate, kg/h
V is water vapor mass flowrate, kg/h
MW
A
is the water molecular weight
MW
MVC
is the VCM molecular weight

Column top pressure is known and controlled and as the water is saturated, tray 1 temperature and all
temperature dependent properties can be calculated.
Assuming a pressure drop for each tray, each tray pressure can be calculated and Eq. 21 applied to each tray.

P P P
i i
+ =
+1
(22)

2.6. Resin Damage

It is known that exposure to high temperatures, especially above 100C, causes colouring of the resin due to
polymer degradation with HCl evolution. This is a major difficulty in removing VCM from PVC as high colour is
a quality non-conformity. Arlman (1954) presented a correlation for HCl evolution from PVC in absence of
oxygen.

E
HCl
b
M
n
=
.

(23)

Where
E
HCl
is HCl evolution rate, mol HCl / gPVC-h
b = 7 x 10
5
mol HCl / gPVC-h (at 182C)
M
n
= PVC molecular weight

Arlman (1954) found for this process an activation energy of 138 KJ/mol, so E
HCl
can be put as a function of
temperature and polymer molecular weight:

E
HCl
k
0
M
n
exp
E
a

R T

=
.

(24)



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Where:
k
0
= 1x 10
10
mol HCl / gPVC-h
E
a
= 33 000 cal/mol

Associating the HCl evolution to resin damage, a convenient multiple of the amount of HCl evolved during
stripping can be used as damage index for comparison between different operations modes.

3. Simulations and Results
A base case was run for a 22 tray column. Figure 3 depicts that an operation with steam to VCM ratio equal
to 4 is enough to reduce the VCM concentration in resin at bottom of the column close to 10 ppm. Figure 4
shows that the product damage is proportional to temperature in the column.

Table 1 Base Case Input
Feed Temperature, C 107
Column Pressure, kgf/cm
2
abs 1.25
P/tray, mmHg 8
Average t
R
/tray, s 12
, Steam/VC ratio 4
h
L
, mm 120

VCM Concentration in Resin
1
10
100
1 000
10 000
100 000
0 5 10 15 20 25
Tray
C
m
v
c
,

p
p
m

Fig. 3 Base Case - VCM Removal Performance


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Product Damage
0
20
40
60
80
100
120
140
0 5 10 15 20 25
Tray
D
a
m
a
g
e

I
n
d
e
x

Fig. 4 Base Case - Resin Damage

Figure 5 presents the sensitivity for column top pressure with open loop control.

Product VCM Concentration
0.01
0.10
1
10
100
0.00 0.50 1.00 1.50 2.00 2.50
Column Pressure, kgf/cm2 a
C
,

p
p
m

M
V
C

Fig. 5 Sensitivity to Column Top Pressure

According to Figure 5 and Table 2 it can be seen that performance is very sensitive to column pressure.

Table 2 Steam Cost Optimized Closed Loop Response to Residual VCM Target
VCM in Product, ppm wt 1 5 10 15 20 30
Column Pressure, kgf/cm
2
abs 1,710 1,447 1,337 1,271 1,224 1,156
Steam/VCM ratio, 1,029 1,562 1,525 1,499 1,480 1,450
Minimized Steam Usage, kg/kg PVC 0,074 0,070 0,070 0,069 0,069 0,069


4. Conclusions

The stripper simulator presented a robust performance, accurate enough results with an adequate and friendly
interface. It has already been put to use by plant operators and engineers as a training and "what-if" tool,

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fulfilling its intend use. Use of MS Excel Solver routine can make the spreadsheet represent the process on a
closed loop control basis that can be used to optimize the column performance in cost or quality.

References
Arlman, E. J. (1954). J.Polym.Sci., 12, 543. (in Kirk-Othmer, Encyclopedia of Chemical Technology, vol 23, pp 897. John
Wiley & Sons. 1969)
Berens, A. (1974a). The Solubility of Vinyl Chloride in Polyvinylchloride. Polym. Prep. 15(2), 197.
Berens, A. (1974b). The Diffusion of Vinyl Chloride in Polyvinylchloride. Polym. Prep. 15(2), 203.
Xie T. Y., Hamielec A. E., Wood P. E., Woods D. R. (1991). Experimental Investigation of Vinyl Chloride Polymerization at
High Conversion: Mechanism, Kinetics and Modelling. Polymer, vol. 32, n 3, pp. 537-557.

Acknowledgments
The authors are grateful to Braskem for permission to publish this work.