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Ind. Eng. Chem. Res., Vol. 44, No.

25, 2005 9411


600
.0. Distillates
500 -
,c„...) 400 • VGO
____________________________________________________ • Gases k7
g 300 - Figure 5. k2 Proposed
kinetic model for the
200 - hydrocracking of heavy oils. I('
k,
100 -
___ • Naphtha kip,
0
ka
0 10 20 30 40 50 60 70 80

wt°A
It is also seen from Figures 3 and 4 that the effect of
Fig ure 2. Effect of th e LHSV on th e d isti llat i on cu rve of LHSV on the conversion and product yields at values
hydrotreated products at 380 °C: ( —) Maya; (•) Isthmus; (0) kg the
LHSV = 1.25 h - I; (•) LHSV = 1.0 h -1 ; (❑) LHSV = 0.75 h - t. lower than 1.0 is minimal, which implies that

1
equilibrium conversion is almost reached. This also
means that, under moderate hydrocracking, the a
50 • reaction severity must not be higher than that employed
in our experiments. If the severity is increased, the
45 - •
40 - • conversion will achieve values higher than 50% and
consequently sediment formation will also be high at
35 -

• levels where commercial plant operation has to be
Conversion, %

0
30 - stopped.
0
25 - Another observation from these figures is that the
0

20 - 0
reaction selectivity is mainly oriented toward the pro-
duction of VGO and distillates. Naphtha production is
15- only slightly higher than that of the original feed. This
10-
0
behavior has two explanations: (1) the naphtha forma-
5- 0.5 1.5 2 2.5 35tion rate is almost equal to the naphtha hydrocracking
0
1/LHSV, h rate, or (2) naphtha formation from heavy fractions is
Figure 3. Effect of the LHSV and temperature on the insignificant. By this means, i.e., only observing the
conversion: (0) 380 °C; (•) 400 °C. experimenUil results, it is not possible to establish which
1/LHSV, h of the two mechanisms is prevailing. However, calcula-
Figure 4. Product composition as a function of the LHSV at 400 15 tion of the kinetic parameters for each reaction path
could help in this task, which is explained in the
following section.
35 - 0 - • 3.2. Kinetic Modeling. Figure 5 shows the proposed
0❑ 0
0 kinetic model, which includes 5 lumps (unconverted
00 resid, VGO, distillates, naphtha, and gases) and 10
4--0
30 - kinetic parameters (k 1 , k10). For each reaction, a
0
-4.-.
kinetic expression (n) was formulated as a function of

• • the product composition (yi) and kinetic constants (Ilei).


P 25 - • ■►—
Product compositions were determined with pilot-plant
 mass balances and distillation curves. All reactions were
4- •  0
assumed to be first order. On the basis of these
I■
considerations, the reaction rates of the proposed model
20 are:
0 0.5 1.5 2 2.5 3 35
Resid: rR = —(k1 + k 2 + k 3 + kdyR (2)
°C: (0) VGO; (•) distillates; ( ❑) naphtha; (•) gases.

consequently sediment formation in all of the products VGO: rvG0 = letyR — (h5 + k6 + h7vvoo (3)
was lower than 0.05 wt %.
The variation of the conversion as a function of the
temperature and LHSV is presented in Figure 3. This Distillates: rD = k2yR k5Yvoo (ks k0).YD (4)
conversion is defined as follows:
conversion = Naphtha: rN = kaYR kaYvoo kaYn kioYN (5)
538 °C+ in feed — 538 °C+ in product x 100 (1) 538
°C+ in feed Gases: rG = k4yR + how() k9YD kioYN (6)

The product composition, determined as the grams The kinetic model was incorporated into an isother-
of each product divided by the total grams of the reactor mal plug-flow reactor model. On the basis of previous
effluent except hydrogen, is shown in Figure 4. experiences, axial dispersion and external and internal
The expected behavior is observed; that is, the higher gradients are neglected.17 The following mass balance,
the temperature and the lower the space velocity, the solved with a Runge—Kutta method, was used to eval-
higher the conversion and product yields.
Residue

ks