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Kinetic Study On The Hydrotreating of Heavy Oil. 1. Effect of Catalyst Pellet Size in Relation To Pore Size
Kinetic Study On The Hydrotreating of Heavy Oil. 1. Effect of Catalyst Pellet Size in Relation To Pore Size
Kinetic Study On The Hydrotreating of Heavy Oil. 1. Effect of Catalyst Pellet Size in Relation To Pore Size
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While numerous publications deal with the mechanism into two groups: catalysts prepared in an aqueous solution
of the n-butane oxidation reaction to maleic anhydride or alternatively in an alcoholic solution. In this work, we
according to intended to report about the kinetics with a catalyst pre-
pared in an aqueous medium. We shall further demon-
,ch3 strate by simulation of possible reactor configurations how
h2c" HC' this catalyst can be attractive for industrial application.
+ 3.50o II O + 4H20
H2Cx HC.
'CHa Experimental Equipment
The experimental investigations (Schneider, 1985) were
and the role of oxidic catalysts (Moser and Schrader, 1985; conducted in a gradientless recycle reactor with an external
Hodnett, 1985; Volta and Portefaix 1985), one hardly finds recycle loop (Figure 1). Approximately 3 g of catalyst
published works about the quantitative investigations of having a particle size between 0.8 and 1.2 mm was intro-
the kinetics and reaction engineering considerations for duced into the reactor; a metal bellow pump (Metal Bel-
the optimal design of this reaction (Centi et al., 1985; lows, type MB-158 HT) recycled the gas and was mounted
Escardino et al., 1973). The large number of recipes for in a hot air thermostat (operating temperature, 170 °C)
the production of industrially relevant vanadium-phos- together with the gas sampling valve, in order to avoid
phorus oxide catalysts for this reaction can be divided up condensation. All other external tubing was also heated
k
I- LL
C4H10 + 4.502(1)
—
4CO + 5H20 + 4.51 (9) Figure 5. Experimental design (factorial) as a basis for the esti-
mation of kinetic parameters.
and
C4H10 + 6.502(1)
—
4C02 + 5H20 + 6.51 (10) of the Mars-Van Krevelen mechanism solely pBut would
with the rate expressions appear in the denominator.
=
fci(0O-)PBut. (11) Experimental Results
(12) By assessing the influence of mass and heat transport
=
r2 k2(e02)pBut
with the appropriate criteria, it was ensured that no hidden
r3
=
k3(e0i)pBm (13)
factors due to transport limitations were influencing the
With and 2 in parentheses, it should be indicated that
0O-
kinetic parameters under the present experimental con-
more one site is necessary in reaction steps 8-10 in
than ditions. In addition, preliminary experiments showed that
order to get from reactants to products (for example, as no reaction occurred in the absence of the catalyst
clusters or in the context of the rake mechanism). (Schneider, 1985).
The product, MAN, finally desorbs according to It was further tested in repeated experiments that both
the activity and selectivity of the catalyst were not altered
(C4H203)V2<"-1)+ C4H203 + 2V(n~1)+ (14)
during the experiments for the kinetic analysis. All ex-
with rate periments adopted in the evaluation were conducted after
^ de8^ the decline to a stationary level (as shown by Figure 4).
^des ^ries^MAN PMAN
It needs to be mentioned, however, that changing operation
(with Kdes
=
02Pman/^man) (15) conditions with respect to reactant concentrations and
If, as is usually the case at ordinary pressure, the surface temperature can damage the V-P-0 catalyst irreversibly.
reactions 8-10 are the rate-limiting steps, all other process This fact is of great importance in the technical application
steps should be in equilibrium. Then, the unknown surface of the catalyst.
coverages can be eliminated via the equilibrium constants The actual experiments for the determination of the
defined above, leading to the final rate equations kinetic parameters in rate eq 16-18 were performed ac-
cording to a modified factorial design (compare Figure 5).
(Kdi88Po2)1/2
ri =
(16) Temperature and the concentrations of oxygen and butane
1 + (Kdi88Po2)1/2PBut were chosen as the adjustable variables. The range of these
variables was determined by the operation conditions of
^sorptP()2 the catalyst as well as by the limitations of the equipment,
r2
=
S + Ks orptPo2PBUt·
(17)
e.g., the accuracy of analysis.
The parameters are obtained in a three-step strategy by
^8orptP02 nonlinear regression. The starting values for the parameter
r3
=
(18) estimation were assessed from plots of the experimental
1 " ^sorptP02 PBut.
values in linear form according to some suitable trans-
The “adsorption term” in the preceding rate expressions formations of eq 16-18. A preliminary optimization of the
only contains p02, while in the corresponding derivation parameters was achieved with a robust search procedure
Ind. Eng. Chem. Res., Vol. 26, No. 11, 1987 2239
Figure 6. Parity diagrams for (a, left) an Eley-Rideal model and (b, right) a Mars-Van Krevelen model.
temperature
IK ]
Figure 8. Simulated profiles for a tubular reactor of technical di- Figure 9. Simulated concentration profiles in bubble and emulsion
mensions: (a, top) temperature and main products; (b, bottom) phase in a fluidized bed reactor.
oxidation products (conditions given in Table III, column 3).
Table IV. Reactor Conditions of a Fluidized Bed Reactor
Table III. Optimal Reactor Configurations bed depth, m 7.53 (no cooling)
objective bed diameter, m 6.00
bed porosity 0.57
Sman -- HSY ~
Sman =
catalyst mass, kg 1.5 X 105
optimization parameters Max Max Max-
inlet pressure, Pa 3.9 x 10s
T0, K 573 633.8 666.0 temp, K 780
'"Q o s 1.15 1.59 2.0 0.08
*o2
Pbed,kg cat./m3 562 680 790 *But. 0.02
G, kg/(m2-s) 0.49 2.69 5.84 VBut 83.8
P0, 105 Pa 20 8.48 20 Tman 42.5
L, m 6.5 0.5 1.76 Sman 50.7
dp, 10"3 m 4 3.85 4 fluid density, kg/m3 1.538
dh, 10""3 m 4 3.13 4 app density of cat. particle, 103 kg/m3 1.89
*But.> feed 0.2 X 10"3 2.56 X 10"2 0.359 X 10' superfic. veloc., m/s 0.45
*o2> feed 0.5 0.24 0.5 min fluidization veloc., m/s 0.03
Yman, mol % 61.74 36.23 58.24 HSY, kg MAN/(m3-h) 10
Sman» m°l % 61.74 50.14 60.84
XBuv mol % 100.00 72.26 95.74 phases), concentration profiles of the reactants in the two
HSY, kg MAN/(m3 RV-h) 0.11 591.9 81.6
phases are given for a particular reactor configuration that
-Where XBut. > 0.8, HSY > 80 kg MAN/(m3 RV-h), bulk cata- does not necessarily represent optimal conditions. The
lyst. pertinent conditions for the reactor are summarized in
Table IV.
makes this configuration economically unfavorable. On The comparison demonstrates that the improved tem-
the other hand, for a maximal hourly space yield (column perature control in the fluidized bed reactor makes it
2), the selectivity drops markedly. possible to raise the butane concentration and temperature
An economically viable compromise would be to max- but allows only low oxygen concentrations.
imize the selectivity under the condition of a minimum
conversion and hourly space yield as given in column 3. Conclusion
For the resulting reactor configuration in column 3 and The important results of the kinetic investigation of the
with an annual production of 17 000 ton of MAN, the result catalytic gas-phase oxidation of n-butane to maleic anhy-
is a total number of 46000 tubes which are divided up into dride can be summarized as follows.
a number of subunits. It is yet to be shown, however, if Kinetic experiments have been performed in an external
the kinetics described here is still valid for an oxygen mole recycle reactor.
fraction of 0.5, as was found to be the optimal value in this On the basis of reaction engineering and physicochemical
case. analyzing techniques as well as mechanistic considerations,
As the fluidized bed technique is an interesting alter- an Eley-Rideal model was found to be most suitable for
native to the fixed bed, calculations were also done for this the description of the kinetics.
type. In Figure 9, for a one-dimensional two-phase model In a three-step procedure, the corresponding kinetic
(Sitzmann et al., 1985) (plug flow in bubble and emulsion parameter estimates had been evaluated.
Ind. Eng. Chem. Res. 1987, 26, 2241-2245 2241
In order to investigate the relation between hydrodemetalation of heavy oil and the catalyst pellet
size, reactions were carried out by a batch reactor using four kinds of commercial HDS catalysts
with different pore size distributions. In the vicinity of 1-mm catalyst pellet size, demetalation activity
was significantly affected by pellet size. However, as the pellet size decreased, the activity reached
a constant level. These results were analyzed by a simple equation including the Thiele modulus,
and it was revealed that the equation can be applied even to such complicated reactions as residue
hydrodemetalation. By use of the Thiele modulus, it was estimated that the order of the magnitude
of the diffusion coefficient (De) was 10"7 cm2/s for the metal compounds in Khafji residual oil at
400 °C.
Residual oils usually contain a high proportion of sulfur residues (Beuther and Schmid, 1963; Ohtsuka et al., 1967;
and metal contaminants. These not only contribute to the Shimizu et al., 1970; Kosugi and Yoshizawa, 1978). On the
problems of air pollution but also cause major problems other hand, first (Chang and Silvestri, 1974; Riley, 1978)
in hydrorefining and catalytic cracking operation. and second (Beuther and Schmid, 1963; Oleck and Sherry,
Therefore, many processes to remove sulfur and metals 1977) kinetic orders have been reported for HDM. Many
from crude residues have been developed. researchers have explained these results by simultaneous
Various investigators have studied the kinetics of the first-order kinetic model (Beuther and Schmid, 1963;
hydrodesulfurization (HDS) and hydrodemetalation Kosugi and Yoshizawa, 1978) or reactor performance
(HDM) of residues. As for HDS, it has been established (Mears, 1974; Paraskos et al., 1975).
that the rate of sulfur removal can be expressed as second It is well-known that residue hydrorefining is more or
order with respect to the total sulfur concentration in less influenced by intraparticle diffusion limitations, es-