0-

9412 Ind. Eng. Chem. Res., Vol. 44, No. 25, 2005
-I -
Table 1. Kinetic Parameters of the Proposed Model
kinetic temperature activation energy
constant (h - - ') 380 C 40 0 C 42 0 C EA (kCa1/11101)
Resid
k 0.042 0.147 0.362 48.5
k2 0,008 0.022 0.057 44.2
0.008 0.020 0.043 38.0
k4 0.041 0.098 0.137 27.3 -6 -
VGO -7 ______________________________________________________________
k5 0.018 0.057 0.104 39.5
0.00142 0.00144 0.00146 0.00148 0.0015 0.00152 0.00154
0 0.007 0.016 37.1
/e7 0 0 0 VT, is
Distillate Figure 6. Arrhenius plot for the different kinetic parameters:
ks 0 0.003 0.010 53.7 (0) ki; (S) k2; (D) k3; () k4; (A) k5; (A) ks; (0) ks.
kg 0 0 0
Naphtha
kin 0 0 0

uate the product composition from a set of kinetic

constants for each temperature: 19

Calculated product composition, wt %

dyi
(7)
d(1/LHSV) =r.

The minimization of the objective function, based on

the sum of square errors between the experimental and
calculated product compositions, was applied to find the
best set of kinetic parameters. This objective function
was solved using the least-squares criterion with a
nonlinear regression procedure based on Marquardt's
algorithm.19
Table 1 summarizes the values of the kinetic param-
eters together with the activation energies for each
reaction. The first finding from the results presented
in Table 1 is the confirmation of what we were discuss-
ing in the last paragraph of the previous section:
naphtha hydrocracking is insignificant at the conditions
of this work because the values found for k10 are null.
This means that naphtha formation comes from the
hydrocracking of heavy fractions, especially from the
resid fraction, but at a very small rate.
Given that ka = 0 and k7 = k9 = kin = 0, it is then.
concluded that gas production is exclusively from the
resid at the temperature range of this study, 380 -420
C.
- Hydrocracking selectivity slightly changes at the
different temperatures. For instance, at 380 C no
formation of naphtha from VGO and distillates is
observed because the values of k6 and k8 are zero. On
the contrary, at 400 and 420 C the values of these
parameters are different from zero.
Because some values of the kinetic parameters were
found to be zero, not all of the activation energies could
be estiinated. Figure 6 shows the Arrhenius plot for all
kinetic constants. The correlation coefficients for all
cases were virtually unity. The values of the activation
energies for some reactions are also presented in Table
1 and are within the range of those reported in the
liter'ature.9,19
A comparison of the experimental product composition
and those determined by solving eqs 2-7 with the ki
values given in Table 1 is shown in Figure 7. It is
observed that the product composition is quite well
predicted with an average absolute error of less than
5%, which indicates that the proposed kinetic model is
adequate for the moderate hydrocracking of heavy oils.
From the results presented in this investigation, it
should be highlighted that hydrocracking can be carried
Experimental product composition, wt %
Figure 7. Comparison between the experimental and
calculated product compositions: (0) resid; CS) VGO; ()
distillates; (IN) naphtha; (a) gases.
out at moderate operating conditions in order to avoid
sludge and sediment Ibrmation by keeping the conver-
sion below than 50%. At these conditions, the hydro-
cracking reaction is not deep enough to increase the
yields of light products (naphtha and gases) and only
the production of distillates and VGO is affected. The
decision of operating or designing the commercial hy-
drocracking units at the proposed reaction conditions
will be dictated by further detailed technical and
economical studies.
4. Conclusion
A five-lump kinetic model for the moderate hydro -
cracking of heavy oils was developed. The proposed
model is capable of predicting the production of uncon-
verted resid, VGO, distillates, naphtha, and gases, with
an average absolute error of less than 5%.
Acknowledgment
The authors thank IMP for financial support. M.A.R.
also thanks CONACyT for financial support.
Nomenclature
rR = reaction rate of resid (wt %/h)
rN = reaction rate of naphtha (wt %/h)
ro = reaction rate of distillates (wt %/h)
rvoo = reaction rate of VGO (wt %/h)
rG= reaction rate of gases (wt %/h)
k i = first-order rate constant for the hydrocracking of resid
to VGO