Compurers

Pergamon

0098-1354(95)ooo73-9

THE VISBREAKING

them. Engng

Vol. 19, Suppl., pp. S205-8210.1995

Coavrieht 0 1995 Elsevier Science Ltd
Printed in &eat Britain. All rights reserved
0098-1354/95
$9.50 + 0.00

PROCESS SIMULATION: PRODUCTS AMOUNT AND THEIR

PROPERTIES PREDICTION
M. DENTE, G. BOZZANO, G. BUSSANI*

Politecnico di Milan0 - Chem. Eng. Dept. G. Natta - P.zza L. Da Vinci, 32 - Milan0 -Italy
* K.T.I. S.p.A. - Via Ripamonti, 133 - Milan0 - Italy

ABSTRACT
The visbreaking process is adopted by many refineries. It consists of a liquid phase pyrolysis of
atmospheric or vacuum residues with the aim of increasing the production of light fractions and
simultaneously reducing the viscosity of the visbroken residues. In spite of the economical
importance of this operation, the literature is lacking of scientific informations; only empirical
models have been presented. Major difficulties are constituted by the huge number of components
and reactions that is characterising the system and by the relatively poor level of the available data
for the feedstock characterisation. Due to the complexity of the feed to the reactor also the
characterisation of the products properties, besides their amount, presents considerable problems.
The results coming from a mechanistic approach are here presented. They are compared with
experimental data from literature, research lab tests and commercial units. Moreover they are
covering different aspects like fouling in the coils, effluents amounts and properties (residues
stability, sulphur and asphaltenes content, viscosity, specific gravity, Conradson carbon residue
and so on). The developed model constitutes a valid support for the understanding and prediction
of the complex phenomena that are occurring during the HC liquid phase pyrolysis and can find a
practical and important application both for improving the visbreaking furnaces design and for
monitoring and control of the V.B. operations.

KEYWORDS
Visbreaking; pyrolysis; fouling; residues stability

KINETICS

ASPECTS

Some of the rules and criteria followed facing on this problem are similar to those ones
successfully adopted in an extended gas-phase pyrolysis kinetic scheme. The complexity of the
molecular characterisation of these systems has been resolved (Dente et al., 1993) by lumping the
huge number of real components into a relatively limited number of pseudo-components.
For
every pseudocomponent it has been proposed a specific reaction fate taking also into account the
probability of scission of the different kind of bonds. The global kinetic mechanism is
characterised by initiation, P-scission, H-abstraction, substitution and recombination reactions.
Due to the liquid phase state, molecular rotational movements of the C-C segments are limited so
that isomerization reactions of the radicals can be practically neglected.
S205

s206

European Symposium on Computer Aided Process Engineering-5

The kinetic constants (frequency factors and activation energies) of the reactions involving
paraffines, aromatics, olefines and diolefines, have been derived from the equivalent ones of an
hypothetical equivalent gas phase (where consolidated rules are already available, Dente et al.,
1992). The equivalent constants in the liquid phase have been obtained through correction factors
of the activation entropies and activation energies for the transposition into the condensed state
(Benson, 1960).

REACTOR MODELLING: THE PROBLEM OF FOULING

The typical visbreaking reactor is constituted by long coils (generally two) horizontally placed in a
furnace; where a radiant and a convective section can be distinguished. Often two cells, with
independent heating, are present. Water is sometimes injected at the coil inlet to increase the fluid
velocity, thus controlling the residence time. In the latest years in many plants an adiabatic extravolume , the so called soaker, has been added after the coils. It allows longer residence times and
therefore lower coil outlet temperatures. As a consequence, the reduced fouling into the coils
allows an extended on stream factor for the visbreaking unit.
The fouling phenomena are an important aspect since, as said before, their are dictating the
reactor on stream time. Their mechanisms of fouling formation are essentially two: a catalytic one
and a radicalic one. When the tubes of the coil are relatively clean, as at start-of-run condition, the
reactor metallic walls play the role of an heterogeneous polyaddition catalyst. Starting from vinylaromatic molecules, polymeric material is formed (like in conventional heterogeneous catalysis for
poly-olefines, poly-diolefines, poly-styrenes and so on). The radicalic mechanism becomes more
and more important as the wall surface is covered, increasing with temperature along the coil. The
radicals that are involved in this phase are coming from the surroundings or are provided directly
from the formed polymers (in fact the bonds of these complex molecular structures are weak at
the beginning of the growth before crosslinking and dehydrogenation have taken place). The last
radicalic mechanism, in combination with degradation, dehydrogenation and crosslinking of the
formed polymers, gives place to the formation of more and more amorphous structures; the pure
radicalic mechanism cannot be easily stopped with antifoulants agents.
The theoretical experience gained in the modeling of fouling phenomena in Transfer Line
Exchangers (TLE) in the ethylene production plants and the experimental data, confirm this
phenomenological interpretation of the fouling mechanism. In fact, it is possible to observe a fast
initial growth, due to the action of walls as catalyst, that subsequently slow down toward a quasiasymptotic behaviour. Coke only partially removed during decoking operation may hide the effect
of the catalytic mechanism.
The evolution of the coke layer thickness, of the pressure drop and of the maximum skin coil
temperature resulting from simulations with the proposed model are shown in the following
figures. The developed model seems to be satisfactory for the prevision of the named variables.
However better comparisons and improvements of these features of the model can be obtained
through the knowledge of the complete history of the furnace (in terms of variations of feedstocks
and operating conditions). In fact the last variables influence the different growth rate of the coke
layer. Qualitative and quantitative agreements with some commercial units data have been
encouraging.

S207

European Symposium on Computer Aided Process Engineering-5

COIL+SOAKER
?
r
$j
5

0.006

0.005

COIL

COIL+SOAKER
lD-

40

60

120

160

20

6O

200

40

60

DAYS

80

100

120

140

160

TIME (DAYS)

COIL+SOAKER

COIL
DAY: 5
630 610.
590 -

0.0

0.1

0.2

o.,

0.4

0.5

0.6

0.7

0.6

6.9

i! TOTAL COIL LENGTH

1.0

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.6

0.9

1.D

Z TOTAL COIL LENGTH

PRODUCTS PROPERTIES
A rigorous visbreaking simulation model cannot neglect the prediction of products properties like
viscosity, specific gravity, sulphur and asphaltenes content, Conradson Carbon Residue and
residue stability. The last one is the most important so that it is necessary to spend some words on
it.

The asphaltenes and their stabilitv

The asphaltenes are defined like those components that are precipitated by adding a certain
amount of n-heptane to a residue (IP 143). This type of determination, being not founded on
molecular basis, obviously gives place to determination errors.

S208

European Symposium on Computer Aided Process Engineering-S

Asphaltenes can be figured like polycatacondensed aromatic rings (the experimental H/C ratio
confirm their aromatic nature) with short pa&ink side chain, whereas still can be defined as
aromatics the same type of components with a longer side chain. During the pyrolysis the last
ones are decomposed so that the content of asphahenes in the residue increases. The final
mixture, constituted by aromatics, asphaltenes, olefines, diolefines and paraffines, is a typical
colloidal solution. Asphaltenes can join and flocculate giving place to muds; this phenomenon
limits the visbreaking severity so that the prediction of residue stability can be of real help in
determining the best operating conditions.
By now the most commonly accepted stability index is the peptisation value (PV): it is
determined by adding to a certain amount of residue increasing quantities of cetane (Cl,) till the
beginning of asphaltenes flocculation. Cetane is used in order to simulate the addition of the worst
possible fluxant cutter stock to the residue. The preferred operating values to be maintained in
v&breaking operations are in the range of 1.l-l .2.
The problem of PV modelling can be approached by representing the system with three
macroclasses of pseudo-components: aromatics, asphaltenes and paraffines, (the last
grouping paraffines, olefines and diolefines). The Hildebrand method for the study of mixtures
stability against separation, based on the determination of the mixing free energy minima in order
to find the unmixing area, is very sensitive if applied to the considered system. The mixture can be
considered as formed by two phases that are compatible only under certain conditions. The first
one is constituted by aromatics and paraf&es, the latter by aromatics and asphaltenes.
Aromatics are adsorbed on asphahenes so that the last ones are kept hidden to the
paraffines with whom they are incompatibles. The coverage degree can be inferred (through the
molecular structure of aromatics and that of asphaltenes) together with the critical
concentration of aromatics, parafIines and asphahenes after their precipitation starts taking
place. The coverage degree is also directly related to the sulphur content in the asphaltenes. In
fact S atoms are larger than C atoms so that a major amount of aromatics is needed in order to
assure asphaltenes coverage. The repartition constant of aromatics is given by the ratio
between the activity coefficient of adsorbed aromatics and that present in the maltenic phase.
The last one is correlated to the Hildebrand solubility parameters that has been obtained through
the analysis of some experimental data available from literature (typically a group contribution
method has been specifically developed for this problem).
The results obtained by adopting this phenomenological approach, when compared with
experimental data, are in a very good agreement, both in the prediction of the PV of the
feedstocks and of the visbroken residues at different severity. Next figure presents the comparison
between experimental and simulation data: the lines are showing the experimental average error in
PV determination. Experimental data are referred to industrial plants, to research lab tests (priv.
comm.) and to pilot plant (Di Carlo, 1992).

EXP. PV

European Symposium on Computer Aided Process Engineering-5

S2O!J

OTHER RESULTS AND COMPARISON

The next figures shows the comparison between experimental and calculated effluent yields. The
experimental data have been obtained by lab tests at different residence times and f&stocks
(particularly the latter were characterised by different kinematic viscosity, specific gravity and
sulphur content) at the same operating temperature. The comparison is very satisfactory.

0.5

0.7

0.0

1.1

1 3 1.5

1.7

1.0

2.1 2,

EXP. GASOLINE

EXP.CAS

14

.4
.:

13

EXP. LGO

EXP. HGO

94.

.,:
80

80

s
82

84

86

EXP. 350f

88

90
RESIDUE

,
92

.
94
EXP. 500+

RESIDUE

Table 1 shows the comparison between experimental data and calculated effluent yields and
products properties for some commercial cases. The first two cases are related to a coil plus
soaker configuration of the reactor whereas the third one is typical of the same reactor without
soaker.

s210

European Symposium on Computer Aided Process Engineering-5

Table 1
I

Inlet temp.
C
Outlet temp.
OC
Outlet pressure
bar
Total residence time min

326
455
12
24 (with soak.)

330
450
12
26 (with soak.)

326
468
183
9

Kin. vise. at 100 C cSt

Kin. vise. at 120 C cSt
Asphaltenes wt%
CCR
W%
Sulphur wt%
Yield wt%
HrS wt%
TBP (0
Specific gravity 15/4gkm3
Sulphur
Wt%
Yield
Wt%
Bromine Number
TBP (C)
Specific gravity 15/4gkm3
Kin. vise. at 50C cSt
Kin. vise. at 70C cSt
Sulphur ti%
Bromine number
Yield
wt%
TBP (C)
Specific gravity 15/4&m3
Kin. vise. at 50C cSt
Kin. vise. at 70 C cSt
Sulphur wt%
Bromine number
Yield
wt%
TBP (C)
Specific gravity 15/4gkm3
Kin. visc.at IOOCcSt
P. value
Sulphur wt%
Asphaltenes wt%
CCR wt%
Yield wt%
Yield
Wt%
Sulphur wt%
Specific gravity 15/4g/cm3

2070
620
10.5
18.0
3.8
1.8
0.5
QOO
0.730
0.70
6.9
65
<315
0.85
2.0
1.4
1.9
33
7.1
c390

11.9
18.9
2.0
0.4
0.730
0.75
7.0
66

17.2
25.3
1.9
0.4
0.729
0.66
6.6
56

0.86
1.9
1.4
2.0
31
7.1
-

13400
2800
17
23
3.4
1.9
0.4
Cl95
0.738
0.65
6.8
51.
Q90
0.85
1.9
1.3
2.1
29
5.0
<385

0.95

0.96

0.89

6.6
4.2
2.2
22
6.6
>305
1.04
530
1.15
3.7
20
24
84.9

7.2
4.6
3.1
23
6.9
500
1.11
3.7
19
22
83.9

5.8
3.9
2.5
21
7
>285
1.05
1414
1.27
3.2
25
27
87.0

1.07
1900
1.14
3.3
22
25
86.4

Vacuum Residues
Operating
Conditions

FEEDSTOCK

GAS

GASOLINE

E
F
F
L
U
E
N
T

LGO

HGG

TAR+HGO

(39*!5:
C)

1.06

<340
0.86

8.0
15.4
1.8
0.3
0.74
0.93
4.0
66
0.88

2.0

2.4

9.1
<395

9.2
-

0.90

0.91

0.92

6.3
4.1
2.7
20
7.7

2.1
6.1
>510
1.06
1.2
3.8
17.5
61.6
17.2
2.4
0.94

0.86
1.8
1.3
1.8
32
5.1
-

1680
5.7
17.7
3.47
2.0
0.3
<175
0.73
0.78
3.9

2.6
6.2
1.06
1.3
3.6
17.8
61.5
17.2
2.6
0.94

REFERENCES
Al So&I, Savaya, Z.F., Mohammed, H.K. and Al-Azawi, 1.A. (1988). Thermal conversion (visbreaking) of heavy
Iraqi residue. Fuel, 67, 1714-1715.
Benson, S.W. (1960).The Foundations of Chemical Kinetics, McGraw Hill, N.Y.
Dente, M., Pierucci, S., Ranzi, E. and Bussani, G. (1992). New improvements in modeling kinetic schemes for
hydrocarbons pyrolysis reactors. Chem.Eng.Sc.. 47, No.9-11, 2629-2634.
Dente, M., Bozzano, G. and Rossi M. (1993). Reactor and kinetic modelling of the visbreaking process.
Proceedings of First Conf. on Chem. and Proc. Eng.,l63-172
Di Carlo, S. and Janis,B. (1992). Composition and visbreakability of petroleum residues. Chem.Eng.Sc., 47, No.91l,June-Aug.1992, 2695-2700
Zimmerman, G., Dente, M. and Van Leeuwen, C. (1990). On the mechanism of the fouling, AIChE meeting,
Orlando, FL, March 18-22.