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Abstract
This work presents the model for the development of a computer aided tool for heavy oil thermal cracking process simulation.
It is proposed a dual plug flow reactor representation for the light pyrolysis of petroleum distillation residues in coil-type reactors.
The resulting reactor model consists of two parallel plug flows, one vapor and the other liquid, traveling at different speeds in a
coil. Reaction is assumed to be the rate controlling process with equilibrium between the phases. Because of the pyrolysis reactions
and pressure drop, vaporization takes place continuously along the coil so there is a decrease in the liquid hold-up. The model
derived uses a heuristic lumping approach based on pilot plant data and the resulting pseudokinetic scheme presents a certain feed
independence within the range of stocks available for the study. An industrial case study (delayed coking) is explored to provide
insight into the problem of reconciling the kinetics of pyrolysis and carbonization for the upgrade of distillation residues. © 2001
Elsevier Science Ltd. All rights reserved.
Keywords: Delayed coking; Plug flow reactor; Pyrolysis; Thermal cracking; Coking
0098-1354/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 9 8 - 1 3 5 4 ( 0 1 ) 0 0 6 6 9 - X
684 R.M. Filho, M.F. Sugaya / Computers and Chemical Engineering 25 (2001) 683–692
2.3. Kinetics
Table 1
Consolidated yields for eight pilot plant runsa
Run nb. 1 2 3 4 1 2 3 4
a
Compositions in wt.%, gases in mol %.
Table 2
Specific gravities for eight pilot plant runs
Run 1 2 3 4 1 2 3 4
looked at the thermal cracking of vacuum distillation product tank arranged as in Fig. 3. Various crudes have
residues in a pilot. The overall flowsheet comprised a been processed and for each of them an average of four
feed tank, pump, pre-heater, coil reactor, cooler and runs at different temperatures have been reported.
686 R.M. Filho, M.F. Sugaya / Computers and Chemical Engineering 25 (2001) 683–692
dP
= (LzL + VzV)sin q (3)
dx el
Fig. 3. Pilot plant CR-0 where most of the experimental work has been performed.
R.M. Filho, M.F. Sugaya / Computers and Chemical Engineering 25 (2001) 683–692 687
Molar composition
3. Results and discussion
H2 4.85
H2S 2.622 SF–0.1541 SF
C1 30.03 The composition of the light gases (H2 –C4) and
C2 5.68 naphthas (C5 –204) produced by the pyrolysis reactions
C2 16.22 in five different vacuum residues is nearly independent
C3 10.48 of the feed and extent of conversion (Fig. 4 below is
C3 12.36
C4 6.21 typical). Because of this the average values indicated in
iC4 0.73 Table 4 can be used.
nC4 5.76 For the light gas oils composition and quality are
a
also independent of conversion (Figs. 5 and 6 are
Note, SF is the sulfur wt.% in feed.
typical) but a slight variation exists between the specific
gravities obtained from different feedstocks (Fig. 7).
The differences need to be explored if the quality of
products is an important issue.
Here, the focus is on processes where conversion and
quality are mainly defined in soaking reactors down-
stream, the coil reactor being important as a prepara-
tory step. The coil model should deliver appropriate
design parameters such as duties, vaporization, pressure
drop and overall conversion. Therefore, small varia-
tions such as those in Fig. 7 can be neglected and the
averages in Table 5 are assumed.
Fig. 5. Light gasoil obtained from one of the feedstock. Reaction constants (kG, kN, kL, etc.) are obtained by
curve fitting the data using a Newton –Raphson proce-
dure to minimize an objective function based on the
Table 5 the coil outlet. If the kinetic constants are small, re-
Internal composition and quality of the light gasoil lump
duced conversions result. As the temperature is in-
Component NBP (°C) SPOR Composition (wt.%) creased, the pyrolysis reactions increase in rate, but the
residence time decreases because of vaporization. The
204–250 227 0.818 24.2 first effect is superior and the calculated kinetic con-
250–300 275 0.845 33.5 stants display a monotonic tendency to increase with
300–350 325 0.872 42.4
the operating temperature. However, as the tempera-
ture is raised, the conversion gradually increases to a
smaller extent. High coil conversions are ultimately
limited by the available reactor length at constant
pressure.
Robust methods of calculating equilibrium are essen-
tial. Convergence problems often occur near the inlet,
where the pyrolysis reactions produce small quantities
of supercritical gases. Small changes in the amount of
gases can cause large variations in the bubble pressure.
Such problems can be avoided if the state of the
mixture (subcooled or not) is checked before the proper
flash calculation routine. Non-polar hydrocarbons at
low pressures show ideal behavior but the use of cubic
Fig. 8. Kinetic constants for feed VR-4. methods (SRK) is justified to establish a reliable phase
equilibrium routine since tiny amounts of light hydro-
Table 6 carbons can be expected to cause large variations in the
Conditions employed during processing of VR-4 residence time because of the large vapor specific vol-
umes at low pressures.
Run number Temperature Pressure (MPa) Conversion
(°C) (wt.%)
To ensure no grid resolution problems thousands of
flash calculations are necessary. This requires knowl-
1 490 0.2 13.2 edge of the composition of the previous calculation as a
2 495 0.2 15.0 starting point for the next step. Typical calculated
3 500 0.2 18.7
kinetic constants are presented in Fig. 8 as an example.
4 475 2.0 16.6
As can be seen, the activation energies are similar.
Moreover, linear relationships are obtained in spite of
the large differences in pressure between some runs. For
VR-4, for example, run number 4 has been performed
at a much lower temperature. Because the pressure
employed during this run is much higher than in others,
the residence time increases and compensates for the
lower temperature. The overall result is an intermediate
conversion (Table 6).
Fig. 9 below presents an equivalent set of kinetic
constants for another feed. The results are very similar
and show the same dependency when compared with
Fig. 8. This suggests feed independence in spite of the
significant although not strong differences in feedstock
Fig. 9. Kinetic constants for feed VR-3.
quality (Table 7).
Table 7
Properties of feeds VR-3 and VR-4 3.1. Case study: delayed coking
walls and are fired from the center. Each furnace feeds Because the conversion is nearly the same (Fig. 10d)
a pair of drums. The flow is from top to bottom in the as is the temperature distribution (Fig. 10f), the vapor
furnace and the first tube row in the convection section fraction remains unchanged (Fig. 10e). Overall, there is
is 17.5 m high. Because vaporization takes place, this to be no significant change in terms of duty (as can be
static head is not totally recovered as flow proceeds concluded from the similarity between the outlet tem-
downwards through the furnace. peratures and vaporized fractions in the two cases) and
Furnace B contains more coke than A, since the conversion due to the uncertainty in the estimate of the
measured pressure drop is 30% higher. The campaign pressure loss. This result also helps to explain why no
time for furnace B has not been reported but furnace A significant changes in product quality and yield are
had recently been decoked. To reconcile these, the observed during a furnace campaign, as would have
pressure drop for B is corrected using a multiplier been expected if a change in the vapor fraction at the
(1.23). For furnace A the multiplier of 0.69 has to be inlet to the soaking reactors had occurred. Moreover, it
used to match the plant pressure drop. helps to explain why the design can be successful in
terms of duty and conversion in spite of the large
3.2. Duty uncertainty in the estimated pressure loss.
The heat duty and fuel gas consumption match the 3.4. Soaking reactors
industrial data very well, as can be seen in Table 8.
Changes in temperature in the tubes predicted by the The feed to the soaking drums predicted by the
model also compare with plant data. In making the model is given in Table 9 below. A comparison with the
comparison it is necessary to take account of uncertain- feed (577 a.m.u.) reveals that a substantial molecular
ties arising from instrument error or coke deposition. weight reduction takes place in the furnaces, i.e. the
Generally, the outlet temperatures can be regarded as reaction delay is reasonable. In practical terms, delayed
being important operating parameters. The reaction is coking does not mean delayed pyrolysis.
significant only in the last third of reactor, where the The effluent of the soaking reactors can be estimated
temperature is above 400°C. No significant reaction using standard procedures (Barros et al., 1997) and is
occurs in the convection zone. presented in Table 10. Although the boiling ranges for
the gasoils are not exactly the same in Table 9, it can be
3.3. Error in pressure drop correlation seen that a significant reduction of molecular weight
takes place in the case of the heavy gasoil, mainly
Fig. 10a –f compare the furnace conditions for differ- because the value in Table 9 includes non-distillable
ent pressure losses. The inlet and outlet temperatures fractions while the value in Table 10 is free from such
are kept constant and a multiplier is added to the fractions.
calculated local pressure drop to verify the sensitivity of
the results. Although the average pressure in the ‘coked’
furnace is much higher because of the increased pres- 4. Conclusions
sure drop (Fig. 10a), the conversion has not increased
(Fig. 10d), as would be expected from the increase in The linear relation observed between the kinetic con-
residence time (Fig. 10c) at constant temperature (Fig. stants derived from the proposed heuristic lumping
10c), caused by the increased liquid hold-up (Fig. 10b). methodology and DPFR representation indicates a
This is because the differences in hold-up are most pressure, temperature and even feedstock independence
significant at the inlet, where the reaction rate is low. of the corresponding Arrhenius parameters. Therefore,
the results presented here indicate that coil reactor
Table 8
Results used to compare model predictions with industrial dataa
modeling at low con6ersions can be performed with a
single set of Arrhenius parameters within a limited
52-F-1 A Model 52-F-1 B Model feedstock range.
Some pyrolysis processes for the upgrade of distilla-
Tin convection 238 238 238 238 tion residues are performed in two sequential units in
Tout convection 396 396 372 372
Dutyconvection n.a. 7.2 n.a. 6.0
order to optimize the delicate balance between selectiv-
Tout, radiation 502 502 502 503 ity and campaign time caused by the parallelism be-
Dutyradiation n.a. 6.6 n.a. 7.6 tween radical decomposition and condensation
Dutyfurnace 12.9 13.8 13.4 13.6 reactions (e.g. delayed coking). Since differences in
Fuel gas 1380 1470 1420 1450 product quality at high conversions are known to be
Tswitch valve n.a. 490 n.a. 490
feed and conversion dependent, the results presented
a
Pressures in bar, temperatures in °C, duties in GW and fuel gas here suggest that the changes responsible for the differ-
consumption in Nm3 per day. ences take place mainly in the downstream unit, in spite
690 R.M. Filho, M.F. Sugaya / Computers and Chemical Engineering 25 (2001) 683–692
Fig. 10. Sensitivity of results for an error in the estimated pressure loss.
of the fact that substantial conversion can occur in the this energy will have to be supplied as sensible heat, to
upstream unit, as revealed by the case study. keep the distillate yields in the process at the same level.
While coke formation can be successfully delayed to This implies higher furnace process temperatures,
the soaking reactors downstream, the pyrolysis reac- higher tube wall temperatures and lower velocities,
tions cannot. This is because the energy required for the which will effectively increase the plugging tendency in
cracking reactions and vaporization of products in the the furnace. Moreover, this may lead to the formation
soaking reactors is supplied by the furnace. If conver- of shot coke in the soaking stage (Ellis and Bacha,
sion is delayed too much the vaporization is low and 1996).
R.M. Filho, M.F. Sugaya / Computers and Chemical Engineering 25 (2001) 683–692 691
High temperatures in the soaking reactors result in by using multiple passes and by reducing pressure losses
increased vaporization and a net reduction in coke in critical areas as indicated above.
production. Hence, to minimize the production of coke The case study has also revealed that in spite of the
in both the furnace (to maximize the time of campaign) large uncertainty in the estimate of the pressure loss in
and soaking drums (to maximize the production of the furnace and transfer line, mild changes in duty and
distillates), it is important to achieve a significant con- conversion result. As already mentioned, this helps to
version and vaporization of products in the furnace at explain why no significant changes in product quality
the lowest possible temperature (limited perhaps by the and yield are observed during a furnace campaign.
coke VMC). At the same time, the soaking reactors Moreover, it helps to explain why the design can be
should be at the highest possible temperature (limited successful in terms of duty and conversion in spite of
perhaps by the coke hardness or the heavy gasoil the large uncertainty in the estimated pressure loss.
quality). These two conflicting objectives synthesize the The choice of appropriate operating conditions is
nature of the delayed coking process. crucial in seeking to increase the production of liquids
Reducing the total pressure, the pressure drop in the and needs to be anticipated at the design stage because
system or the hydrocarbons partial pressure (increasing more options are then available. The model derived
steam) will improve the vaporization of products, here can be a useful tool to study the effect of some
thereby increasing the transfer of latent heat to the design parameters.
soaking reactors at the expense of sensible heat, thus
avoiding the conflict stated above. Unfortunately, any
of these options represents a substantial increase in References
costs, which severely limits choices. Nevertheless, the
case study results (Fig. 10) indicate that most of the Agrawal, S. S., Gregory, G. A., & Govier, G. W. (1973). An analysis
conversion and pressure loss in the system takes place of horizontal stratified two phase flow in pipes. Canadian Journal
of Chemical Engineering, 51, 280.
at the few last tubes in the furnace and at the transfer Altgelt, K. H., & Boduszynski, M. M. (1994). Composition and
line to the soaking reactors. Clearly, design efforts to analysis of hea6y petroleum fractions. New York: Marcel Dekker.
reduce the pressure loss should be directed to these Barros, F. C. C., Bernardo, F. C. A., Chan, A., and Bria, M. (1997).
sections, in particular by minimizing the length of the ‘Maximum distillates yields in a delayed coking unit’, 30b, Amer-
transfer lines and the number of pipe fittings, which are ican Institute of Chemical Engineers Spring Meeting, New
Orleans.
determined by plant layout. Beggs, H. D., and Brill, J. P. (1973). A study of two phase flow in
Therefore, furnace tube plugging should be mini- inclined pipes. Journal of Petroleum Technology, 17, 607.
mized by using high velocities while not reducing resi- Bozzano, G., Dente, M., Sugaya, M., McGreavy, C. (1998). The
dence times, e.g. by using small diameters, long lengths characterization of residual hydrocarbon fractions with model
compunds — retaining the essential information, 216th ACS
and low heat fluxes. Unfortunately, these give rise to an
National Meeting. Di6ision of Fuel Chemistry Preprints 43 (3), 653
undesirable pressure increase which has to be handled Bria, M., and Filgueiras, R. (1982). Relatório Diter 18, Petrobras
R&D Center.
Table 9 Dean, D. E., & Stiel, L. I. (1965). The viscosity of nonpolar gas
Feed composition at the switch valve of a delayed coking drum mixtures at moderate and high pressures. American Institute of
Chemical Engineering Journal, 11, 526.
Component Molecular weight wt.% Dente, M., Bozzano, G., & Bussani, G. A. (1997). Comprehensive
program for visbreaking simulation: products amount and their
Light gases 33 2.5 properties prediction. Computers and Chemical Engineering, 21,
Naphtha (C5–204°C) 119 8.4 1125.
Light gasoil (204–350°C) 222 6.9 Dukler, A. E., Wicks, M., III, & Cleveland, R. G. (1964). Frictional
Medium gasoil (350–500°C) 369 16.5 pressure drop in two-phase flow: B. An approach through similar-
Heavy gasoil (500+) 704 65.7 ity analysis. American Institute of Chemical Engineering Journal,
Total 317 100.0 10, 44.
Ellis, P. J., and Bacha J. D. (1996). Shot coke, Light Metals, 43, 477.
Griffith, P., & Wallis, G. B. (1961). Two-phase slug flow. Journal of
Table 10 Heat Transfer, 83, 307.
Soaking reactor top effluent Gunn, R. D., & Yamada, T. (1971). A corresponding states correla-
tion of saturated liquid volumes. American Institute of Chemical
Component Molecular weight wt.% Engineering Journal, 17, 1341.
Hughmark, G. A. (1962). Holdup in gas– liquid flow. Chemical
Light gases (H2–C4) 25 10.6 Engineering Progress, 58 (4), 62.
Naphtha (C5–204°C) 115 19.4 Le Page, J. F., Chatila, S. G., & Davidson, M. (1990). Raffinage et
Light gasoil (204–343°C) 242 30.9 Con6ersion des Produits Lourds du Pétrole. Paris: Éditions
Medium gasoil (343–510°C) 288 27.9 Technip.
Heavy gasoil (510°C+) 318 11.2 Lee, B. I., & Kesler, M. G. (1975). A generalized thermodynamic
Total 117 100.0 correlation based on three-parameter corresponding states. Amer-
ican Institute of Chemical Engineering Journal, 21, 510.
692 R.M. Filho, M.F. Sugaya / Computers and Chemical Engineering 25 (2001) 683–692
Mallan, G. M., Michaelian, M. S., & Lockhart, F. J. (1972). Journal Kwong equation of state. Chemical Engineering Science, 27, 1197.
of Chemical Engineering Data, 17, 412. Stiel, L. I., & Thodos, G. (1964). The thermal conductivity of
McGreavy, C., Sugaya, M. (1998). ‘The two phase, two plug reactor nonpolar substances in the dense gaseous and liquid regions.
— the separate phase residence times effect’, 216th ACS National American Institute of Chemical Engineering Journal, 10, 26.
Meeting Di6ision of Fuel Chemistry Preprints 43 (3) 684. Twu, C. H. (1985). Internally consistent correlation for predicting
Rachford, H. H., Rice, J. D., (1952). Journal of Petroleum Technol- liquid viscosities of petroleum fractions. Industrial Engineering and
ogy, 4, s.1, 19, s.2, 3. Chemical Processing Design and De6elopment, 24, 1287.
Soave, G. (1972). Equilibrium constants from a modified Redlich– Wright, W. A. (1969). Journal of Materials, 4 (1), 19.