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PYROLYSIS AND CHLORINATION OF SMALL
HYDROCARBONS
E. RANZI
a
, M. DENTE
a
, M. ROVAGLIO
a
, T. FARAVELLI
b
& S.B. KARRA
c
a
Dipartimento di Chimica Industriale ed Ingegneria Chimica , Politecnico di Milano , Italy
b
K.T.I S.p.A , Roma, Italy
c
Pyrotec NA , Monrovia, CA
Published online: 06 Nov 2007.
To cite this article: E. RANZI , M. DENTE , M. ROVAGLIO , T. FARAVELLI & S.B. KARRA (1992) PYROLYSIS AND CHLORINATION OF
SMALL HYDROCARBONS, Chemical Engineering Communications, 117:1, 17-39, DOI: 10.1080/00986449208936055
To link to this article: http://dx.doi.org/10.1080/00986449208936055
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Chem. Eng. Comm. 1992, Vol. 117, pp. 17-39
Reprints available directly from the publisher.
Photocopying permitted by license only.
1992Gordon and Breach Science Publishers S.A.
Printed in the United States of America
PYROLYSIS AND CHLORINATION OF SMALL
HYDROCARBONS
E. RANZI,t M. DENTE, M. ROYAGLIO
Dipartimento di Chimica Industriale ed lngegneria Chimica
Politecnico di Milano, Italy
T. FARAYELLI
K. T.I S.p.A., Roma, Italy
and
S.B. KARRA
Pyrotec NA, Monrovia, CA
(Received April 18, 1991; in final form March 17, 1992)
The bases of the kinetic modeling of Chlorine containing systems are addressed in this article,
A kinetic scheme, involving more than 300 elementary reactions and 46 molecular and radicalic
species, has been developed based on general thermochemical kinetic theories as well as the
consolidated know-how in the field of hydrocarbon pyrolysis.
Several comparisons with commercial and laboratory experimental data indicate a fair agreement in
a wide area of lower and higher pressures (up to 30 atm) also covering the high temperature range of
methylchloride pyrolysis (1000"C). Mathematical model of EDC pyrolysis furnaces already allows to
evaluate process performances and alternatives accounting for fouling rates and on-stream times.
The kinetic scheme can be applied to study the methane chlorination reaction system and the
dichloroethane (EDC) pyrolysis system. The kinetic scheme is coupled with a furnace model and
appropriate mathematical techniques to solve the resulting system of material, energy and momentum
conservation equations. A coking model has also been incorporated as fouling of coils determines the
run length of the furnaces. Simulation of the pyrolysis of EDC to produce vinyl chloride shows that
the results are in reasonable agreement with observed values and trends. Application of the model for
the design of coils and evaluation of process alternatives is discussed.
INTRODUCTION
In the last years a renewed attention has been put to the chloride hydrocarbons.
Two reasons can be seen at the origin of this interest:
(a) the possibility of converting methane into more valuable products. A new
approach is the direct chlorination to CH
3CI,
whose pyrolysis gives rise to
acetylene and ethylene via ethylchloride and dichloroethane and HCI
(eventually converted back to chlorine and recycled).
t Author to whom correspondence should be addressed.
17
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18 E. RANZI et al.
(b) the need of revamping or new design for the dichloroethane de-
hydrochlorination furnaces that can respond to the requirements for op-
timized processes, not only to increase the profits, but also to reduce the
potential environmental damages related to the chlorinated emission.
A direct consequence of what above observed is the effort in developing
computer models that can take into account a proper characterization of the
elementary kinetic steps and increase the general knowledge of the process itself.
In this paper, on the basis of previous experiences in the field, a detailed
mechanism is presented and fair comparisons with literature experimental data
confirm the possibility to describe a wide range of condition with a limited
number of elementary reaction steps.
These comparisons refer to:
-Chlorination of methylchloride (methylene chloride, chloroform and carbon
tetrachloride) together with their by-products (chloroethanes and
chloroethylenes).
-Dehydrochlorination of dichloroethane
-Pyrolysis of methylchloride at high temperature
The model presented is based on the development of "a priori" reaction scheme,
identifying the reasonable set of chemical species and their overall reaction
network, using the numerous and reliable thermochemical and kinetic data
provided by the progress made in the experimental techniques.
Once a reasonable model is developed a necessary step is always related to the
validation of the model and the tuning of kinetic parameters on the basis of the
available experimental data (commercial, pilot or bench).
KINETIC SCHEME AND MECHANISM CONSIDERATIONS
A very simplified kinetic scheme of pyrolysis and chlorination of methane is
presented in Figure 1, where the subset of reaction network mainly pertaining to
the pyrolysis of 1,2-dichloroethane (EDC) is also outlined.
From this figure it is clear that always the same elementary reactions with the
same kinetic parameters must be considered when analyzing the pyrolysis of
methane and methylchloride, chlorination of methane as well as de-
hydrochlorination of EDC. Therefore experimental knowledge and data related
to specific systems can be extended and applied in wider conditions. For instance,
primary products of methylchloride pyrolysis, recently investigated by many
authors (Holbrook, 1961; Kondo et al., 1980; Weissman and Benson, 1984;
Granada et al., 1987; Senkan, 1987), are mainly the results of recombination
reactions of CH
J
and CH
2CI
radicals:
2CH
2CI
-+ CH
2CI-CH2Cl
CH
2CI
+ CH
J-+CHJ-CH2CI
2CH
J
-+ CzH
6
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CHLORINATED HYDROCARBONS PYROLYSIS 19
Pyrolysis
/
_ VC4
CZHb -----.. C
2H4
BUTAD
,
,
,
MCE "

!EDC ------.. VC ... -----.. CzHz - - -..- components l
:...._._._._._._._._._._._._--, "'...: .!
!, I 1
C}lP, - VC2 !....., ;
! heavy chlorinated components !
i AI" !
C,H,Ci, - VO; II ! :"0., .1
,
,
-
-,
J,"'P"
'I L
'''''
CHCI,
J'CO,.,
CCI,
CH,
I'0',"
c::
.9
-
..
.9
Lo
.2
.c::
u
SIMPLIFIED KINETIC SCHEME
FIGURE 1 Simplified kinetic scheme.
In the successive steps, ethylene and vinylchloride (VC) are formed through the
following dehydrochlorination reactions of ethylchloride (MCE) and EDC:
CH
3CHzCI-+
CzH
4
+HCI
CHzCICHzCI-+ CHCI=CH
z
+ HC]
Acetylene is mainly obtained via dehydrochlorination of VC as well as via
dehydrogenation of CzH
4
.
The previous recombination reactions, and also the interactions with CHCl
z
and CCI
3
radicals, are the main sources for Cz species even in the case of
chlorination of methane (Kurtz, 1972).
Moreover, for both these situations, the main path towards heavier species
always goes through successive (molecular and radicalic) condensation reactions
with the formation of chloroprene, butadiene, vinylacetylene, benzene and
heavier chlorinated components.
A detailed list of the main species involved and considered in the overall
reaction scheme is reported in Table I, where thermochemical quantities, such as
fj.HJ, SO and C, are also reported.
Heat capacities are reported in terms of the following general regression:
C
p
=a +b(T/10(0) +c(T/l00W+d(T/1(00)3 +e(T/lOOW [cal/mol/K]
with temperatures in the range of 300-1500 K.
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20 E. RANZI et at.
TABLE 1
Thermodynamic properties of molecular and radicalic species
Name Mf'}
6.SJ
a b c d e
CCI. -22.886 74.108 8.474 58.493 -81.070 50.805 -11.669
CHCI, -24.610 70.710 7.411 31.694 -8.597 -22.259 14.599
CH
2CI2
-22.793 64.621 4.647 27.826 -4.402 -17.490 10.189
CH,CI -19.971 56.012 4.605 14.448 16.291 -27.382 10.871
CH. -17.874 44.495 1.547 34.709 -55.279 60.567 -24.307
C,CI. -3.600 81.300 6.150 58.130 -50.900 17.520 0.000
C,CI. -35.300 94.800 17.378 68.843 -64.868 20.629 0.000
C,HCI, 0.950 75.000 4.150 58.130 -50.900 17.520 0.000
C,HCl
s
-35.300 ,90.000 13.580 68.370 -60.820 19.190 0.000
C,H
2
54.186 48.057 3.999 30.168 -32.100 18.031 -3.799
C,H
2C12
8.000 68.800 2.150 57.130 -47.880 14.820 0.000
C,H
2C1.
-34.400 84.000 9.630 . 67.960 -57.030 17.520 0.000
C,H,CI 5.000 63.100 1.419 48.080 -35.960 10.780 0.000
C,H,CI, -34.400 78.090 5.720 67.580 -53.950 16.620 0.000
C,H. 12.551 52.415 -1.711 55.532 -67.299 55.313 -19.339
C,H.CI
2
-30.185 73.433 4.363 46.856 -5.491 -22.624 10.362
C,H.CI
2
-31.700 73.800 1.263 71.380 -60.380 21.150 0.000
C,HsCI -26.287 66.097 2.015 47.286 -7.624 -23.976 13.664
C,H. -20.008 54.772 2.905 30.772 11.480 -24.981 9.108
C,H.Cl
2
-5.220 78.890 4.660 84.540 -75.130 25.940 0.000
C,HsCi -50.190 72.180 7.850 42.420 -13.960 -0.970 0.000
c,H"
4.914 61.579 2.966 41.557 8.911 -33.145 14.216
C,H.CI
2
39.600 84.800 2.160 89.180 -65.250 19.990 0.000
C.H.CI
2
14.590 83.020 0.505 108.980 -101.060 35.790 0.000
C.HsCI 17.450 76.720 5.180 71.940 -49.530 13.260 0.000
C.H"
26.750 66.620 -0.403 81.650 -55.890 15.130 0.000
C.H.CI.
-58.220 107.570 12.560 96.250 -67.240 20.300 0.000
C.H.
121.740 69.622 -2.583 76.788 -7.237 -52.998 28.816
C.H"
19.839 64.454 -6.232 93.801 -5.883 -64.800 34.133
Cl
2
0.016 53.307 6.220 9.731 -13.785 8.894 -2.110
HCI -22.036 44.660 7.000 0.060 -1.712 4.167 -1.959
H
2
0.013 31.237 6.550 1.638 -1.617 -0.188 0.821
N
2
0.000 45.800 7.550 -3.440 5.903 -2.184 0.000
Radicals
CCI, 18.500 70.800 8.659 27.540 -24.380 7.225 0.000
CHCI
2
23.200 65.300 5.185 29.530 -23.260 6.389 0.000
CH
2CI
31.100 59.600 4.760 17.340 -7.843 1.267 0.000
CH, 34.819 46.408 4.827 22.092 -33.369 32.210 -11.648
C,H
2C1
59.500 67.000 1.419 48.080 -35.960 10.780 0.000
C,H, 68.393 55.361 4.884 14.640 4.190 -2.625 -2.353
nC,H,Cl
2
14.700 78.000 2.654 52.970 -37.050 10.210 0.000
iC,H,Cl
2
17.100 75.340 4.800 40.110 -17.550 1.430 0.000
C,H.CI 21.000 68.000 1.978 43.970 -28.260 9.003 0.000
C,H
s
28.022 60.177 5.344 17.316 8.778 1.855 -7.801
C,HsCI 7.960 82.890 3.950 72.370 -51.560 16.640 0.000
CI 28.982 39.464 4.126 5.856 -8.722 4.866 -0.814
H 52.076 27.405 4.965 0.000 0.000 0.000 0.000
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CHLORINATED HYDROCARBONS PYROLYSIS
THERMODYNAMIC
THERMOOIEMICAL
CONSISTENCY WITH
KINETIC THEORIES
LITERATIJRE DATA
REVERSE REACTIONS

ANALOGIES AMONG KINETIC
COMPLFrENESS AND
SIMILAR REACTIONS SQiEME
SIMPUFICATION
LEVEL
REACTOR NUMERICAL
MODEL METHODS
TUNING OF KINETIC
SIMULATIONS OF
PARAMETERS
EXPERIMENTAL
DATA
FIGURE 2 Block diagram of kinetic model development.
21
These data have been taken from CHEMKIN data bank (Kee et al., 1980) or
directly estimated on the basis of groups contributions (Benson, 1976).
A schematic representation of the different phases of model development is
presented in Figure 2.
On the basis of literature information and experimental data a preliminary
kinetic network can be drafted by first guessing some simplification rules in order
to avoid the inclusion of an excessive number of species and reactions.
Thermodynamic consistency, as well as the individuation of reaction classes on
the basis of mechanistic analogies, allows a reduction of the overall dimension of
this problem. In fact, structural analogies inside the classes are essential to extend
the knowledge from a relatively small amount of specific elementary reactions to
the similar ones. In this way analogous reactions can be predicted (in terms of
stoichiometry as well as in terms of kinetic parameters) without direct experimen-
tal information (Ranzi et al., 1991).
The main free radical reactions can be classified in the following four classes of
direct and reverse reactions:
(a) Initiation and termination reactions
(b) Atoms-abstraction reactions (metathesis reactions)
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22 E. RANZI et al.
(c) Radical decomposition reactions and radical additions to unsaturated bonds
(d) Radical isomerization reactions
In a parallel way some purely molecular reactions can playa significant role, for
instance the molecular dehydrochlorination of 1,2-dichloroethane has been
extensively investigated and is a relevant path for vinylchloride production in the
usual operating conditions. (Yano and Tschulkow-Roux 1980).
Once the "a priori" kinetic scheme has been defined still simulations based on
experimental results are necessary in order to validate and confirm the model
itself. At this stage it becomes important to define the simplification level for the
reactor model as well as the selection of the numerical methods to be adopted to
solve the system of balance equations. Mainly based on the comparison between
experimental and predicted results it is viable to tune in a better way the kinetic
parameters and it is also possible to modify the simplification rules and/or the
completeness of the description level.
The complete reaction scheme, constituted by more than 300 elementary
reactions involving 46 molecular and radical species, is reported elsewhere
(Maccabiani 1989; Ranzi et al., 1990a).
Table II reports only a small subset of reactions that are of a relative
importance in the chlorination of methyl chloride at 700 K and atmospheric
pressure with the relative kinetic parameters in the Arrhenius form. Due to their
relevant importance only H abstraction reactions of CI radicals are explicitly
referred.
Despite the theoretical limitation of the simple Arrhenius behavior adopted for
the kinetic constants, the deviations between predicted and experimental results
seem to suggest that, for the range of pressure and temperatures considered here,
these limitations are of scarce practical importance. Therefore, the kinetic scheme
remains a simple unifying element among the different experimental sources and
conditions. Further developments of the kinetic scheme through implementation
of 3-parameter Arrhenius rate expressions or accounting for the pressure
dependency of complex reaction rates seem unnecessary for the purpose of
present illustration. Within a reasonable temperature range however, Arrhenius
rate expression for atom transfer reactions is sufficient. Also within a reasonable
pressure range, pressure dependency of unimolecular decompositions can be
taken into account by using Arrhenius rate parameters alone and third body
density in the rate expression.
To study the response of large kinetic schemes to parameter variations, there is
a growing research interest in the area of sensitivity analysis (Hwang, 1983;
Frenklach, 1984). Such information can contribute to parameter estimation, can
be useful in determining kinetically important or unimportant elementary steps,
however the partial derivatives of the model variables with respect to kinetic
parameters (sensitivity coefficients) are strongly varying for different chemical
systems and for different conditions (pressure, temperature and conversion).
Despite the possibility to use alternative approach, like the Green's function
method (Demiralp and Rabitz, 1981a and b), the Fourier amplitude sensitivity
test (Cukier et al., 1978), the stochastic sensitivity analysis (Constanza and
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TABLE II
Main elementary reactions for chlorination of methyl chloride
Kinetic parameters
,
Lit. Source
# A E
CHAIN INmATION REACTIONS
I O.looE + 14 47000. CI, + T1iIRD = 2CI + T1iIRD a
2 0.200E + 16 75000. CH,CI + T1iIRD = CH, + CI + T1iIRD b
3 O.600E+ 16 77000. CHCI, = CHCI, + CI c
4 O.tooE + 17 roeoo. CCI. = CCI, + CI c
H ABSTRACTION REACTIONS
5 R + CH,CI = RH + CH,CI
5A) O.600E+ 11 3400.0 CI + CH,CI = HCI + CH,CI b
6 R + CH,CI, = RH + CHCI,
6A) 0.200E + 11 2000.0 CI + CH,CI, = HCI + CHCI, d
7 R + CHCI, = RH + CCI,
7A) 0.7ooE + 10 2000.0 CI + CHCI, = HCI + CCI, d
8 R + (;,H,CI, = RH + (;,H,CI, + CI
8A) 0.200E + 11 3100.0 CI + (;,H,CI, = HCI + (;,H,CI, + CI
9 R + (;,H,CI. = RH + (;,HCI, + CI
9A) 0.150E + 11 3100.0 CI + (;,H,CI. = HCI + (;,HCI, + CI b
10 R + (;,HCI, = RH + (;,CI. + CI
lOA) 0.750E + 10 3100.0 CI + (;,HCI, = HCI + (;,CI. + CI b
METATliETICAL REACTIONS OF CI
II O.400E+ 10 3000.0 CH,CI + CI, ~ CH,CI, + CI d
12 e.ioos 10 5000.0 CHCI, + CI, = CHCI, + CI d
13 0.5OOE+09 6000.0 CCI, + CI, = CCI. + CI d
MOLECULAR REACTIONS
14 0.200E + 14 58000. (;,H,CI, = (;,H,CI, + HCI b
15 0.3OOE+09 44000. (;,H,CI, + HCI = (;,H,CI, c
16 O.I30E+ 14 58000. (;,H,CI. = HCI + (;,HCl, b
17 0.3OOE+09 44000. (;,HCI, + HCI = (;,H,CI. c
18 O.looE+ 14 58000. (;,HCI, = HCI + (;,CI. e
19 0.3OOE+09 44000. (;,CI. = HCI = (;,HCI, c
RADICAL RECOMBINATION REACTIONS
20 O.looE + 10 -11000. 2CI + T1iIRD = CI, + T1iIRD c
21 0.250E + 10 -12000. CH, + CI + T1iIRD = CH,CI + T1iIRD c
22 0.200E + 11 o o 2CH, = (;,I!" g
23 0.7ooE+ 10 o o 2CH,CI = (;,H.CI, b
24 o.iooa- 11 o o 2CHCI, = (;,H,CI. h
25 O.looE + 11 o o 2CCI,=(;,CI" h
26 O.5ooE+ 11 o o CH, + CH,CI = (;,H,CI c
27 0.200E + 11 o o CHCI, + CH,CI = (;,H,CI, c
28 0.200E + 11 o o CCI, + CH, = (;,H,CI, c
29 0.200E + 11 o o CCI, + CH,CI = (;,H,CI. c
30 0.200E + 11 o o CCI, + CHCI, = (;,HCI, c
31 O.looE + 11 o o CI + CHCI, = CHCI, h
32 o.roos + 11 o o CI + CH,CI = CH,CI, h
33 O.IOOE + 11 o o CI + CCI, = CCI. h
, A FREQUENCY FACTORS
E ACTIVATION ENERGIES
[I/S] FOR UNIMOLECULAR REACTIONS
[M3/KMOL/SI FOR BIMOLECULAR REACTIONS
[KCAL/KMOL]
a) Baulch et al. 1981, b) Weissman and Benson 1984, c) Benson 1976,
d) Kurtz 1972, e) Benson and O'Neal 1972, f) Karra and Senkan 1988,
g) Dente et al. 1979, h) Ranzi et al. 1990.
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24 E. RANZI et al.
Seinfield, 1981), the direct method (the so called "brutal force" method), even if
not computationally efficient, is at least the easier to be implemented (Dickinson
and Gelinas, 1976).
Sensitivity coefficients that take into account the response of the system, are
usually defined with the following non-dimensional expression:
Sac; K
J
aln C;
J.i= aK
J
C; = aK
J
K
J
where C; is the concentration of the i'h species and K
J
is the kinetic parameter of
the J'h reaction.
It is worthwhile observing that these sensitivity coefficients, obviously strongly
dependent on the reaction system, are also influenced by operating conditions
and mainly by decomposition extent.
To clarify this concept the reaction scheme of Table II for the chlorination of
methylchloride can constitute a simple and interesting example.
It is well established that propagation reactions to form CCl. proceed through
the intermediate formation of CH
2CI2
and CHCl
3
via the following reaction path:
A sample of the behavior of sensitivity coefficients versus the contact time is
presented in Figures 3 and they are related to the chlorination of CHCI
3
at 450C,
1 atm and a molar ratio of chloride and methylchloride of 4.
From these figures it is evident, not only the strong influence of the conversion
level on the sensitivity coefficients, but also the difficulty in understanding, even
in this simple case, the complete meaning of these information. For instance the
strong rising of S6A, CH
3Cl
can be justified mainly on the basis of the low residual
concentration of methylchloride, more than on the basis of a complete analysis of
the whole kinetic scheme. Therefore, as the number of elementary reaction steps
becomes larger, this general approach becomes impractical and a more effective
way to tune and modify kinetic parameters is to judiciously select the experimen-
tal information.
The mechanistic model for chlorinated reaction systems can be tuned following
some fundamental indications. Due to their lower importance in this condition,
the reactions deeply studied in the field of hydrocarbon pyrolysis remained
unchanged (Dente and Ranzi, 1983). The more typical chlorine interactions with
CH
3Cl,
MCE and DCE have been tuned on the basis of low temperature
experimental data (Ranzi et al., 1990a), while chloromethane and VC decom-
position reactions have been validated on the basis of experimental data obtained
at higher temperatures.
A further example of this procedure is practically contained in the experimental
work of Weissman and Benson (1984) where chloromethane decomposition has
been investigated with the addition of intermediate products like methane,
ethylene, acetylene and benzene. In this way the sensitivity coefficients of the
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CHLORINATED HYDROCARBONS PYROLYSIS
25
5A,CH2Cl:
1.2 1.0 0 .s 0.6 0.4 0.2
o
(a) Conlec1 TIme (I)
,.
0
..
e
eX
0.0
(b)
0.2 0.4
Contact Time (s)
0.6 0 .a 1.0
FIGURE 3 (a) Sensitivity coefficients for reaction SA vs. contact time (s). (b) Sensitivity
coefficientsfor reaction 6A vs, contact time (s). (c) Sensitivity coefficients for reaction 12 vs. contact
time (s). (d) Sensitivity coefficients for reaction 13 vs. contact time (s).
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26
E. RANZI et al.
0.4
C<mlact TIIM (a)
(c)
0.6 0.8 1.0
o
0.2 0.4
Contact Time (s)
0.6 0.8 1.0
(d)
FIGURE 3--{Conlinued)
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CHLORINATED HYDROCARBONS PYROLYSIS 27
system are modified and it becomes possible to stress the relative importance of
successive reactions of these intermediate products.
MATHEMATICAL MODEL AND NUMERICAL METHODS
The reaction system can be mathematically described using the fundamental
balance equations; specifically, the material balance for each molecular and
radicalic component as well as momentum and energy balances.
Assuming plug flow conditions, mass balances in steady state are:
dFj NR
dV = ~ v i r = RJ
where Fj and R
J
are the flowrate and the net reaction rate for species J, V is the
reactor volume and ViJ is the stoichiometric coefficient of species J in reaction rio
The solution of this set of ordinary differential equations is complicated by the
stiffness arising from the wide range of kinetic parameters values.
As noted solving these systems usually requires stiff integrators (White and
Seider, 1984). LSODE package (Hindmarsh 1980) is known to be reliable and
efficient for a wide range of operating conditions. Nevertheless the numerical
integration remains costly due to the large number of steps and related Jacobian
evaluations.
It is well established that, for the usual conditions of hydrocarbon pyrolysis,
Continuous Varying Steady State Assumption (CVSSA) for radical species allows
to overcome the stiffness of the problem without practical losses of accuracy.
However, with the rise in temperature and therefore with the reduction of
effective contact times, CVSSA becomes no longer valid. (Dente et al., 1979,
Ranzi eta/., 1988a and b).
We observed the necessity for a more complete stiff integration for the
simulation of high temperature pyrolysis of chloromethane. For the de-
hydrochlorination of dichloroethane however, CVSSA can be judiciously applied
accounting for a normalization factor in order to respect the overall H, C and Cl
balances along the coil.
VALIDATION OF THE KINETIC MODEL AND COMPARISON WITH
EXPERIMENTAL RESULTS
The major part of experimental information used in the tuning and validation
phase is coming from the literature and can be grouped into three main classes.
(a) Data on CH
4
chlorination at 350-500C and atmospheric pressure
(b) Data on CH
3Cl
pyrolysis at high temperatures (800-1200C) and atmospheric
pressure.
(c) Data on EDC pyrolysis in a wide range of pressure (1-40 atm) and moderate
temperature (300-600C).
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28 E. RANZI et al.
One of the basic advantages of mechanistic kinetic schemes is the possibility to
apply the same kinetic model in very different operating conditions. Therefore all
the experimental data have been simultaneously used in order to elucidate the
whole scheme of Figure l.
In addition to direct experimental data a large number of qualitative and/or
semiquantitative information related to the real performances of commercial units
have been also collected. These data can be used in order to match the overall
conversion of EDC but are mainly useful in order to characterize the fouling or
the polymerization process taking place inside the pyrolysis coils. Literature data
on EDC pyrolysis (Barton and Howlett 1949; Holbrook et al., 1971; Huybrechts
et al., 1972; Yano et al., 1980; Ashmore et al., 1982) usually report some
mechanistic considerations and the overall rate expressions, but are very poor if
the attention is towards the minor or trace components. Thermal de-
hydrochlorination of EDC is a very selective process and VC yields are usually
higher than 95% with conversions in the range of 50-60%. Mainly for this reason
quantitative information on by-products are practically absent in the literature.
Nevertheless, purity of vinylchloride for polymerization processes is tightly
demanded.
From, these considerations it is evident that the possibility to tune the kinetic
scheme for EDC pyrolysis on the basis of different experimental data can enhance
the reliability of the resulting kinetic model.
As already mentioned, there is nowaday a strong research interest towards the
possibility of obtaining olefins directly from methane. Processes exist to convert
methane into acetylene, ethylene and hydrogen by using high temperature
pyrolysis (Miller 1965, Khan and Crynes 1970), however, selectivities are too low
due to the large formations of heavier species. Benson patented a process where
the chlorination of methane, followed by the pyrolysis of the intermediate
chloromethanes, results in an attractive production of ethylene and acetylene
(Benson 1980).
On the same subject Senkan developed the chlorine catalyzed oxidative
pyrolysis (Senkan 1987). Mainly for this renewed interest on chlorination
reactions it is possible to find in the recent literature reliable and complete
experimental results on the thermal decomposition of methyl-chloride (Weissman
and Benson 1983, 1984, Granada et al., 1987, Forst and Laurent 1965). Therefore
the validation and tuning of the kinetic scheme has been performed on the basis
of a significant set of experimental results not only related to different sources,
but also referring to different reacting systems and different operating conditions.
Figures 4 show fair comparisons between experimental and predicted results in
the case of methylchloride pyrolysis. As mentioned before, theoretical results
have been obtained by solving the material balance equations with LSODE
program assuming isothermal conditions inside the reactors.
In Figure 4a, at low conversion, it is possible to see the primary formation of
mono and di-chloroethane. The reactor here utilized (Granada et al., 1987) is a
quartz tube of 2.1 cm ID and 60ern long, with mean gas velocity of 1.5 m/s
indicating that laminar flow conditions occur with the following operating
conditions: T = 980C; P = 0.678 atm; CH
3Cl
= 7.47% mol in Argon.
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CHLORINATED HYDROCARBONS PYROLYSIS
29
0,3
C2R4
0,2
>-
>
';;
.!
..
III
0,1
DCB
0,3 0,1 0,2
CH3CL Conver.lon
(a)
0,0
0,0

+
+
+
CR4 +
1,0
U
'" :z:

0,5
C2R4
0,4 0,3 0,2 0,1
0,0
0,0
Contact Tlma (a>
(b)
FIGURE 4 (a)Mcthylchloride decomposition. Comparison between predicted and experimental
results. (b) Methylchloride decomposition. Comparison between predicted and experimental
results. (c) Melhylchloride decomposition. Comparison between predicted and experimental results.
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30
E. RANZI et al.
1,2
CH4

1,0
c::; 0,8
'" :z:

0.6
:
0,4
0.2

0,0
0.000 0.025 0,050 0,075 0,100
Conlect Time Ie)
(c)
FIGURE 4-{Conlinued)
Due to the high temperature here considered and the fast decomposition of
chloroethanes, experimental information are limited to selectivities (moles of
product/mole of CH
3C1
decomposed) of vinylchloride, ethylene and acetylene.
Methane selectivities are in the range of 15% -;- 20% and are slightly overpre-
dieted in comparison with experimental indications.
A part from HCI and Hz (that were experimentally deduced on the basis of
chlorine and hydrogen mass balances) other minor species identified, but not
quantified, were C
6
H,;, butadiene, CHzCl
z.
Figure 4b and 4c present comparisons between experimental and predicted
results for the decomposition of methylchloride in presence of large amount of
methane in the feedstock even in the presence of ethylene (Figure 4b) and in the
presence of acetylene and ethylene (Figure 4c), Also in these cases (Weissman
and Benson 1984) temperatures are close to 1000C, pressure of methylchloride is
between 0,2 and 0,5 atm and reaction yields are reported in terms of ratios
between the concentration of the products and the initial concentration of
methylchloride , From these figures, it appears evident that the absolute and
relative reactivities of the different species are in a close agreement with
experimental data. Only methane seems slightly underpredicted but the opposite
deviation can be observed if we refer to different sources. Experimental profiles
reported for HCI and Hz were based on chlorine and hydrogen atom balances.
Vinylchloride, as well as mono- and dichloroethane, observed by Weissman and
Benson (1984) are in trace amounts.
The last set of experimental data refers to methyl chloride chlorination at 460C
and atmospheric pressure (Kurtz 1972). As mentioned in the sensivity analysis the
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CHLORINATED HYDROCARBONS PYROLYSIS
1.0..,.-----------------.
31
0.6
o 0.6
...
u..,
0.4
0.2
1 2
Mol CI ReactecttMol CH Cl Fed
2 3
3
FIGURE 5 Chlorination of CH
3CI-Primary
products.
dominant reaction steps, summarized in Table II, are quite clear and main
products CHzCl
z,
CHCI
3
and CCl
4
are very well predicted by the model (Figure
,5).
Tri-, tetra-, penta- and exa-chloroethanes obtained through radicals recom-
binations, despite their very low relative amount are fully in line with experimen-
tal information. Absolute values for the maxima, as well as their relative position,
fairly agrees with experimental data (Figure 6a) indicating the correct relative
weight of the chain termination reactions (reactions 22-30) in comparison with
the propagation ones.
A further indication of the proper kinetic values for the dehydrochlorination
steps can be deduced from Figure 6b where di-, tri- and tetra-chloro ethylenes are
reported.
Similar kinetic modeling approach for pyrolisis of methane showed successful
prediction of the product distribution at both low and high conversion (Ranzi et
al., 1988a).
MATHEMATICAL MODEL OF EDC PYROLYSIS COIL
Commercial processes for the production of vinylchloride from ethylene and
chlorine include direct chlorination of ethylene to produce 1,2-dichloroetane
(ethylene dichloride or EDC) followed by pyrolysis of EDC to produce
vinylchloride. Commercial EDC cracking furnaces operate in the 480-550C
range with pressures up 30-40 atmospheres. Single pass conversion of EDC is in
the 50-60% range. This optimizes the costs between coking or fouling cycle,
utilities and yields. By products from this very selective EDC pyrolysis include
acetylene, ethylene, methylchloride, butadiene, vinylacetylene, benzene, chlo-
roprene and other chlorinated hydrocarbons (Pherson et aI., 1979).
Always maintaining the same overall kinetic scheme, according to the global
procedure of Figure 2, it becomes necessary to properly define the reactor model.
The differential and algebraic conservation equations are described in Table III.
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32 E. RANZI et at.
0.0025.,.-----------------,,-------,
0.0020
0.0015
....
2: 0.0010
0.0005
3 , 2
Mol CI r8actedlMol CH CI Fed
2 ,
0.0000
a
(a)
0.0025.,.-------------------.,.----,
0.0020
0.0015
-0
....
-u
0.0010
0.0005
C H <':1
2 2 2
3 2
Reacted/Mol CH Cl Fed
,
1
Mol Cl
2
0.0000
a
(b)
FIGURE 6 (a) Chlorination of CH,C1-Secondary products. (b) Chlorination of CH,CI-Tertiary
products.
Typically, industrial data are given for the reactor inlet composition and
temperature and the outlet pressure and temperature (or conversion); as a
consequence of these boundary conditions an iterative method is required for the
solution of differential equations.
The pressure profile is established with a good accuracy and an effective first
guess for the temperature and composition profiles is determined by a global
simplified kinetic and an explicit integration method (Barendregt et al., 1981). In
a second phase, the whole kinetic scheme is used, together with the CVSSA to
overcome the stiffness problem. Employing the gas temperature profiles calcu-
lated in the first phase, it is possible to separate partially, within each integration
step, the enthalpy balance from the material ones. If the updated average
temperature inside the step differs from the preestimated one by more than an
accepted deviation (OSC), the computation procedure is repeated. Usually one
or two iterations are sufficient.
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CHLORINATED HYDROCARBONS PYROLYSIS
TABLE III
Model equations
Mass Balance
33
Energy balance
d (NR )
G..3=M - vr
dz } I; '.}'
j= 1, ... , NC
Tube side:
dT NR 4
Gc -= - !>Hr+- U(T. - T)
P dz I; I' D, r
Firebox side:
Momentum balance
where
(p + G
Z
) = _ L G
Z
dz p D,2p
C'}
C
z
c
p
D,
f
G
!>H,
M
j
NC
NR
P
T
v.,
p
constants containing emissivity factors, view factors
and Stefan Boltzmann constants
process gas specific heat
inside tube diameter
friction factor
mass ftux
heat of reaction i
molecular weight of component j
number of total compounds (molecular plus radical)
number of reactions
pressure
reaction rate
process gas bulk temperature
outside tube-wall temperature
ftue gas temperature
refractory wall temperature
overall inside heat transfer coefficient
ftue gas convective heat transfer coefficient
length along the coil
stoichiometric constant of component j in reaction i
process gas density
mass fractions of component j
The run length before decoking is a further complicating aspect in the
operation of EDC furnaces and is determined by the pressure drops, the
reduction in conversion and/or by the maximum allowable tube metal
temperature.
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34
COKING MODEL
E. RANZI et at.
Fouling processes strongly affect the performances of cracking furnaces. As a first
consequence of this deposition of "carbonaceous material" into the pyrolysis
tubes, two major points can be observed:
Increase in pressure drops along the coils
Increase in the tube metal temperature
As a consequence of the continuous growing of coke thickness inside the coil (and
related thermal resistances) firebox efficiency is declining and fuel consumption is
rising. For this reason runtime of the furnace is limited and periodic shutdowns
are required with a penalty for the overall capacity and for the equipment life.
Therefrom a predictive fouling model can be of real importance in analyzing
process and design alternatives.
The analogy between the fouling phenomenon in EDC pyrolysis and olefin
cracking processes (Ranzi et al., 1985) provided the possibility to implement a
preliminary coking model. This model assumes that initial coking is due to a
catalytic polymerization process on the active sites of the metallic surface.
Subsequent dehydrochlorination and dehydrogenation of the polymer structure
cause reticulation and cross-linking within this structure. This increases the
resistance to the diffusion of olefinic monomers and prevents them from reaching
the active sites on the metal surface. Simultaneously the "older" polymer gets
transformed into "coke" by further dehydrogenation.
The apparent activation energy for the deposit growth is in the order of
40-45 kcal/mole and is very close to the activation energy for the reticulation
process. The net result is that the polymeric layer practically maintains a constant
thickness (of few hundred microns) by being constantly renewed at the gas-solid
interface while there is an apparent growing of the inner "coke" layer.
After a few days of operation, radicals addition to the unsaturated bonds on
the polymeric layer becomes the prevailing coking mechanism. Chlorovinyl, vinyl
and vinyl or phenyl-like radicals are the main coking precursors and their
concentration, due to their short life-time, has to be evaluated at the temperature
of gas-polymer interface. Vinyl-chloride, acetylene, chloroprene and similar
components are also coking precursors through direct addition reactions at the
surface.
The coking model accounts for both these mechanisms: radical additions (rrad)
and molecular additions (rmol). Using theoretical values, this preliminary coking
model has been implemented:
rmol = 10
7
.
5
exp( -22500/RT)C
vc
[mm/rnonth]
[mrn/rnonth]
where f3 constant reflects the lower relative polymerization reactivity of vinyl
radicals in respect of vinyl-chloride radicals (RYCl) and the similarity with gas
phase condensation reactions suggests a negligible activation energy.
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CHLORINATED HYDROCARBONS PYROLYSIS
TABLE IV
Geometry and operating conditions of conventional coil
3S
Total length 280 m
Total ftowrate 16000Kg/h
Outlet pressure 10 Kg/em
2
abs.
EDC conversion 55%
Internal diameter 0.12 m
Inlet temperature 200'C
Contact time 12-14 s
Outlet temperature 500'C
Some adjustments of kinetic parameters have been made on the basis of
available experimental data on pressure drop and tube metal temperature rise
and commercial data on actual on-stream time.
For the thermal conductivity of coke deposit, an average value of Kc =3
[kcal/rn hOC] has been assumed. Due to the lower temperatures here considered,
this value is lower than the one assumed for the coke formed in the steam
cracking process (Kc = 4-12 kcal/m hOC).
EFFECT OF ON-STREAM TIME ON FURNACE PERFORMANCE
In this example attention is given to a simulation problem where, assuming
always the same firing in the radiant section, it is possible to follow the aging of
the furnace. It means that, updating continuously the "coke" thickness inside the
pyrolysis coils on the basis of the fouling rates predicted by the model itself,
performances of the furnace are analyzed along the running time.
Geometry as well as operating conditions for this furnace are given in Table
IV.
Figures 7 to 11 report temperature, pressure, conversion, heat fluxes and
700
U
600
'"
..
a:
"c
500
a:
..
..
..


c
400
,;,
'"
..
CJ
0
a:
..
300
200
0 , 0
20 30
FIGURE 7 EDe Pyrolysis-Process and skin temperature vs. coil length.
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36 E. RANZI et al.
lS
16
..
E
14
a.
!!.
"'
a:
5l
on
12
"'
a:
..
10
8
0
10 20 30
TUBE NUMBER
FIGURE 8 EDC Pyrolysis-Pressure vs, coil length.
fouling rates profiles along the coil for the initial clean conditions and for three
different times (or fouling conditions inside the coil). Final conditions, with
practically 20 mm of coke in the last tube, would correspond to about nine
months of operation. Typical on-stream time for these furnaces is around 6
months during which it is possible to verify that the rise in pressure drops and in
tube metal temperature is less important in comparison with the reduction of
EDC conversion. As far as selectivity towards vinylchloride is concerned it is
100
90
80
s
"' c
"'
l:i 70
c
::!
z
:>
60
50
40
0 10 20 30
TUBE HUMBER
FIGURE 9 EDC Pyrolysis-Unreacted EDC (%) vs. coil length.
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CHLORINATED HYDROCARBONS PYROLYSIS 37
40000,---------------------------,

30000

CLEAN COD.S
;;
u

K
:>

c
"'
:r
20000
30 20 10
10000
o
TUBE HUMSR
FIGURE 10 EDC Pyrolysis-Local heat fluxes (based on clean internal surface) vs. coil length.
possible to observe that there is only a very marginal increase due to the lower
conversion and to the rising of pressure level inside the furnace.
This example shows a possible application of the overaIl kinetic scheme,
coupled with a mathematical model of the pyrolysis coils. Anyway the possibility
of a more accurate design and/or optimization of operating conditions of EDC
furnaces would require a more detailed model of the firebox side too.
6-,----------------------,
5
4
2
30 20 10
o+-O.....--.........
o
TUBE NUUBER
FIGURE 11 EDC Pyrolysis-Fouling rates (on relative bases) vs. coil length.
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38
CONCLUSIONS
E. RANZI et al.
The general concepts employed in developing a mechanistic kinetic scheme for
chlorinated hydrocarbons have been presented in this paper and several com-
parisons with experimental results as well as an application to commercial unit
have been illustrated. The model itself can constitute a valid starting point for the
study of different reacting systems both in terms of design of new reactors for
EDC pyrolysis and in terms of the evaluation of the effect of possible additives,
typically chlorinated and brominated hydrocarbons.
Only observing the chain initiation reaction of carbon tetrachloride (CCl.) it is
possible to derive that the formation of radicals following reaction 4:
CCl...... CCl
3
+ CI k = 10
16
.
00
exp( -70000/RT) [s-II
is highly more important than the initiation reaction of EDC:
CH,Cl-eH,CI ..... 2CH,Cl k= lO'6.8 exp(- 90000/ RT) [s-II
CH,Cl-eH,Cl ..... CH,Cl-eH, +Cl k = 10
16
.
30
exp( -83000/RT) [s-II
Therefore it is easy to justify the effect of CCl. in terms of a possible additive in
EDC furnaces. The additions of 1000 ppm of CCl. can increase the radical
formation by a factor of about 2 at 500C.
From this experience, once again, the main advantages of well balanced and
adequately extensive mechanistic models can be singled out:
-Theoretical kinetic and all available experimental data (bench scale, pilot and
commercial) contribute to the kinetic model development and validation.
-There is a capacity for wide extrapolations and considerable flexibility in terms
of components, mixtures and operating conditions.
-Simulations of process alternatives are readily produced and it is no longer
necessary to employ expensive pilot units.
-When an extension and/or development is through, the marginal cost for new
improvements tends to be small.
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