You are on page 1of 6

2236 Ind. Eng. Chem. Res.

1987, 26, 2236-2241


Chen, S.; Lin, K. Chem. Eng. Sci. 1980, 35, 2325. Ponnuswamv, S. R.; Shah, S.L.; Kiparissides, C. Proceedings of the
Cutter, L. A.; Drexler, T. D. Am. Chem. SOC.Symp. Ser. 1982,197, 1985 ACC, Boston, 1985.
13.
1986a, 3$'3239.'
1 - __
Ponnuswamv. S. R.: Shah. S. L.: Kioarissides. C. J. A D D Polvm.
~. Sci.
Farber, J. N. Ph.D. Thesis, University of Massachusetts, Amherst,
1983. Ponnuswamy, S.R.; Shah, S.L.; Kiparissides, C. J. Lig. Chromatogr.
Franklin, G. F.; Powell, J. D. Digital Control of Dynamic Systems; 1986b, 9, 2411.
Addison-Wesley: Menlo Park, CA, 1981. Ray, W. H. Can J . Chem. Eng. 1967, 45, 356.
Hamer, J. W. Ph.D. Thesis, University of Wisconsin, Madison, 1983. Sacks, M. E.; Lee, S.; Biesenberger, J. A. Chem. Eng. Sci. 1972,27,
Harris, T. J.; Rushing, E. V. Paper presented at the AIChE National 2281.
Meeting in Orlando, FL, 1982. Sacks, M. E.; Lee, S.; Biesenberger, J. A. Chem. Eng. Sci. 1973,28,
Hicks, J.; Mohan, A.; Ray, W. H. Can. J . Chem. Eng. 1969,47,590. 241.
Hoffman, R. F.; Schreiber, S.; Rosen, G. Ind. Eng. Chem. Fundam. Sage, A. P. Optimum Systems Control; Prentice Hall: Englewood
1964, 56, 51. Cliffs, NJ, 1968.
Hoogendoorn, K.; Shaw, R. Proceedings of the 4th IFAC-PRP Au- Schork, F. J.; Ray, W. H. Am. Chem. SOC. Symp. Ser. 1981,165,505.
tomation Conference; Van Cauwenberghe, A., Ed.; Pergamon: Thomas, I.; Kiparissides, C. Can. J . Chem. Eng. 1984, 62, 284.
Belgium, 1980; p 623. Timm, D. C.; Gilbert, R. E.; KO,T. T.; Simmons, M. R. Am. Chem.
Jo, J. H.; Bankoff, S. G. AIChE J . 1976, 22, 361. SOC.Symp. Ser. 1982, 197, 3.
Kenat, T. A.; Kermode, R. I.; Rosen, S.L. Ind. Eng. Chem. Proc. Tirrell, M.; Gromley, K. Chem. Eng. Sci. 1981, 36, 367.
Des. Deo. 1967, 6, 363. Tsoukas, A.; Tirrell, M.; Stephanopoulos, G. Chem. Eng. Sci. 1982,
Keyes, M. A.; Kennedy, J. P. Proceedings of the 2nd Purdue Con- 37, 1785.
ference on Process Control, New York, 1974, p 89. Tzouanas, V.; Shah, S. L. Proceedings of the 1985 IFAC Conference
Kiparissides, C.; MacGregor, J. F.; Hamielec, A. E. AZChE J . 1981, on Adaptive Control of Chemical Processes, Frankfurt, Germany,
27, 13. 1985, p 114.
Kiparissides, C.; Ponnuswamy, S.R. Can. J . Chem. Eng. 1981, 59, . oresented
Wu. G. Z. A.: Denton. L. A.: Laurence. R. L. Paoer - at the
752. Annual AIChE Meeting'in Chicago, 1980.
Kirk, D. E. Optimal Control Theory; Prentice Hall: Englewood Yoshimoto, Y.; Yanagawa, H.; Suzuki, T.; Araki, T.; Inaba, Y. Int.
Cliffs, NJ, 1970. Chem. Eng. 1971, 11, 147.
MacGregor, F. J.; Hamielec, A. E.; Penlidis, A. Proceedings of the
5th IFAC-PRP Conference, Antwerp, Belgium, 1983, p 291. Received for review March 27, 1986
Ponnuswamy, S. R. Ph.D. Thesis, University of Alberta, Edmonton, Revised manuscript received July 13, 1987
Canada, 1984. Accepted July 27, 1987

Kinetic Investigation and Reactor Simulation for the


Catalytic Gas-Phase Oxidation of n -Butane to Maleic
Anhydride
P. Schneider
Enka AG, 0-8573 Obernburg, West Germany

G. Emig* and H. Hofmann*


Institute of Technical Chemistry I , University o f Erlangen-Niirnberg, 0-8520 Erlangen, West Germany

Kinetic investigations on n-butane oxidation on a V-P-0 catalyst prepared in an aqueous solution


are presented. The complex reaction could be described accurately enough by three parallel reactions
leading to maleic anhydride, CO, and COz. The rates of the different reactions have been modeled
by an Eley-Rideal mechanism more suitable than by a Mars-Van Krevelen mechanism. Simulation
and optimization of technical tube bundle and fluidized bed reactors have been performed on the
basis of these kinetic results.

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-
,o pared in an aqueous medium. We shall further demon-
strate by simulation of possible reactor configurationshow
this catalyst can be attractive for industrial application.
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
0888-5885/87/2626-2236$01.50/0 0 1987 American Chemical Society
Ind. Eng. Chem. Res., Vol. 26, No. 11, 1987 2237

0
,------- \ A
I

Figure 1. Experimental setup (gradientless reactor with external


recycle): a, reactor; b, metal bellows pump; c, sample valve; d, gas
chromatograph; e, vent; f, absorber; g, switch unit; h, data analysis
with process computer; i, printer; k, gas mixing pump; 1, gas cylin-
ders.

1 T I
8
Figure 3. Typical chromatogram. He carrier gas flow: TCD = 36

i mL/min; FID = 29 mL/min.

UV spectrometry (Schneider, 1985).


Kinetic Modeling
The reaction scheme was derived by knowing that under
more severe conditions as compared to the butene oxida-
Figure 2. GC configuration for simultaneous product analysis: a,
sample loop; b, sample; c, gas chromatograph; d, data analysis with tion (Hofmann et al., 1984),only MAN,COz,CO, and H20
process computer; e, printer. are formed. The result is the following hypothetical re-
action scheme:
Table I. Characteristic Data of t h e Catalyst Used 1
(Schneider, 1985) n-C4HlO C4H203
specific surface area, m2/g 18.3
micropore radius, m 8.5
macropore radius, lo-'' m 720
specific pore vol (Hg), 10" m3/kg
specific pore vol (He), 10" m3/kg
292
374 co e - co2
true density, lo3 kg/m3 3.11
particle porosity 0.54 As regression calculations showed, the redundant reaction
P/V ratio 1.25 paths 4,5, and 6 can be neglected compared with reactions
1,2, and 3. Therefore, the following reactions were chosen
to a minimum temperatue of 170 OC. The reactant mixture
of n-butane (95.3% n-butane, the remainder was other
hydrocarbons), oxygen, and nitrogen was supplied from
C4H10 4- 3.502 -
as a basis for the investigations in this work:
C4H2O3+ 4Hz0
- A H R = 1.2606 X lo6 kJ/kmol (1)
a gas mixing pump (Wosthoff, Type M 300/a-F). The
analysis of the feed and product gases was accomplished
with a gas chromatograph (Varian Moduline 1520, with
CdH10 + 4.502 - +
4CO 5Hz0
- A H R = 1.5262 X lo6 kJ/kmol (2)
thermal conductivity detector (TCD) and flame ionization
detector (FID)). The simultaneous analysis of all reactants
was possible with the column arrangement as illustrated
CdH10 + 6.502 - 4C02 + 5H2O
- A H R = 2.6586 X lo6 kJ/kmol (3)
in Figure 2. A typical chromatogram is shown in Figure
3. The redox mechanism with the influence of lattice oxygen
from the catalyst for reaction 1is well established (Haber,
Catalyst Preparation and Characterization 1973). Such redox reactions can be formally described by
A systematically optimized V-P-O compound was used the kinetic equations of Mars and Van Krevelen (1954) or
as the catalyst. For its preparation, V205was dissolved Eley and Rideal (Rideal, 1943). The essential difference
in an aqueous solution of hydrochloric/phosphoric/oxalic between the two models is the mechanism of the formation
acids and subsequentially reduced; by adding 5% TiOz, of MAN. In the Mars-Van Krevelen model, after an ad-
the final catalyst was prepared (compare Schneider et al. sorption step of butane, the adsorbed butane and lattice
(1985)). The characteristic data of the granulated catalyst oxygen react to form MAN,whereas with the Eley-Rideal
are summarized in Table I. The amount of available model, butane out of the gas phase without a preceding
lattice oxygen of the catalyst was determined through adsorption step reacts directly with the oxygen from the
reduction-oxidation cycles with n-butane or oxygen, re- metal oxide lattice, forming a surface compound. Since
spectively, on a thermobalance (Schneider, 1985). The TPD measurements (Schneider, 1985) revealed that n-
average oxidation state of vanadium was found to lie be- butane is not adsorbed noticeably on the investigated
tween 4.1 and 3.7. As a reference, the oxidation state of catalyst, the formal kinetics were derived following the
the fresh catalyst was 4.0, determined by wet analysis and model of Eley-Rideal.
2238 Ind. Eng. Chem. Res., Vol. 26,No. 11, 1987

Kazansky and Shvets (1972) used ESR spectroscopy to


prove that the adsorbed oxygen in V206on a SiO, carrier
tends toward the dissociated form as 0- anions with in-
creasing temperature. The necessary electrons for the
dissociation are provided by the transition element
+
o2 2v(n-1)+ Ft 20-vn+ (4)
which has the rate equation c:

rdiSs = kdisso2POn- kbsso20- (with = e20-/(82Po,))


(5)
where 0 represents a reduced metal site and Bo- stands for
an oxidized metal site. A t the same time, oxygen is also
adsorbed at other sites in molecular form, following
0 2 + 1 * 021 (6) I
with the appropriate sorption rate:
rsorpt= ksBgo, - k'soo, (with Ksorpt= 00,/(61~oJ) (7)
28 I ,
U. ' Iu. k
-(67.

Figure 4. Catalyst aging in the recycle reactor.


' 2bs. A,
tine on stream Ihl

Now, butane in the gas phase can react with the lattice
oxygen Bo- and also with the molecularly adsorbed oxygen
Oo2. According to the general understanding (Haber, 1973)
of the reaction, Bo- will yield the desired product in a
selective reaction, while the oxygen adsorbed as 00 leads
to the unseledive oxidation of the hydrocarbon to C6, C02,
and water. As a consequence, one obtains the reaction B,
n- butane
steps IO h 1
C4H10 + 70-Vn+ - + +
(C4H20JV2(n-1)+ 4H2O 5V(n-1)+
+

(8)
or
-+ +
C4H10 + 4.502(1) 4CO 5H2O + 4.51 (9) Figure 5. Experimental design (factorial) as a basis for the esti-
mation of kinetic parameters.
and
C4H10 + 6.502(1) 4co2 + 5H20 + 6.51 (10)
-+
of the Mars-Van Krevelen mechanism solely PBut. would
with the rate expressions appear in the denominator.
rl = kl(OO-)PBut. (11) Experimental Results
r2 = k2(002)PBut. (12) By assessing the influence of mass and heat transport
with the appropriate criteria, it was ensured that no hidden
r3 = k3(eOz)PBut. (13) factors due to transport limitations were influencing the
With Bo- and Ooz in parentheses, it should be indicated that kinetic parameters under the present experimental con-
more than one site is necessary in reaction steps 8-10 in 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(n-1)+ e C4H203 + 2V(n-1)+ (14) during the experiments for the kinetic analysis. All ex-
with rate periments adopted in the evaluation were conducted after
the decline to a stationary level (as shown by Figure 4).
rdes = ltdesoMAN - beso2PMAN
It needs to be mentioned, however, that changing operation
(with Kdes = 0 2 p ~ . m / (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).
Temperature and the concentrations of oxygen and butane
were chosen as the adjbtable variables. The range of these
variables was determined by the operation conditions of
the catalyst as well as by the limitations of the equipment,
e.g., the accuracy of analysis.
The parameters are obtained in a three-step strategy by
nonlinear regression. The starting values for the parameter
estimation were assessed from plots of the experimental
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 poz,while in the corresponding derivation parameters was achieved with a robust search procedure
Ind. Eng. Chem. Res., Vol. 26, No. 11, 1987 2239

I
P -
I

rLu lkmor/kg.rld
Figure 6. Parity diagrams for (a, left) an Eley-Rideal model and (b, right) a Mars-Van Krevelen model.

Table 11. Parameter Estimation for Model Equations 16-18


temperature IKI 0
I
true individual
confidence intervals,
% of estimate
param- lower upper
eter optimal estimate limit limit
kl 9.66 X kmol/(kg cat..s.Pa) +11.6
k2 1.72 X kmol/(kg cat..s.Pa) -1.5 +2.7
k3 2.21 X kmol/(kg cat..s.Pa) -8.3 +5.6
Ei/R 8677 K -27.7 +9.5
E,/R 8663 K -1.3 +2.5
EB/R 8940 K -6.6 +4.8
Kdias 0.11 x Pa-' -0.8 +0.9
Ksorpt 0.42 X lo4 Pa-' -1.1 +1.2
600
0 0517 1033 1550 2 087 2583 3100
(Nelder and Mead, 1965);the final optimization and sta- reactor lengh In1

tistical evaluation was then followed with a Newton me- Figure 7. Experimental and simulated temperature profile for a
thod (Marquardt, 1963). The rate and equilibrium pa- pilot reactor.
rameters were reparametrized (Emig et al., 1975) in order
to improve the conditioning of the objective function. The nomically favorable performance can be achieved with the
obtained results are summarized in Table 11. catalyst under technical conditions. Therefore, in the
The involvation of the temperature dependence of the present case, we simulated possible reactors for this re-
adsorption constants did not result in a better fit of the action with the aid of suitable computer programs (Hof-
model (see also Berty (1979)). The quality of the param- mann, 1979; Sitzmann et al., 1985). In particular, for the
eters for the Eley-Rideal mechanism is demonstrated in synthesis of MAN, a multitubular reactor with a fixed
the parity chart of Figure 6a and compared with the results catalyst bed or a fluidized bed was considered. The
obtained by application of the Mars-Van Krevelen model fluidized bed is of significant importance here, since it can
(Figure 6b). While the data points in Figure 6a are evenly be operated under isothermal conditions (Arnold et al.,
scattered over the whole range, inspection of the data in 1985).
Figure 6b reveals a significant trend particularly in the Figure 8 shows the results using a pseudohomogeneous
technically interesting range of high MAN formation rates. two-dimensional reactor model (Hofmann, 1979) in the
This trend expresses the lack of suitability of the Mars- form of simulated temperature and concentration profiles
Van Krevelen model, and this result was further confirmed within the multitubular reactor. Of course, the goal is to
by a model discrimination using nonintrinsic diagnosis find a reactor configuration that represents an economical
parameters (Williams, 1959). This model discrimination and technical optimum. Therefore, under different ob-
was particularly suitable in the case where already all jectives, such as selectivity (S),maximum conversion ( X ) ,
experimental results were available (simultaneous exper- or hourly space yield, the dimensions of the reactor and
imental design). The measurements in a pilot reactor catalyst, as well as operation conditions, were optimized
(Schneider, 1985),finally, could be correlated better with with the aid of a search method (Nelder and Mead, 1965).
the Eley-Rideal model than with the Mars-Van Krevelen In this search, the range of the variables was predeter-
model. As a typical result, the comparison between a mined by technically reasonable values. With respect to
measured and a simulated temperature profile for the pilot a minimum yield or conversion, additional objectives were
reactor is given in Figure 7. introduced. Table I11 contains some typical reactor con-
figurations resulting from such optimization calculations.
Simulation of Possible Technical Reactors Column 3 in this table refers to the case of Figure 8. If
It is recommended that the applicability of every newly only optimal selectivity is asked for (column l), the yield
developed catalyst be tested as to whether or not eco- is at a maximal value but the low hourly space yield (HSY)
2240 Ind. Eng. Chem. Res., Vol. 26, No. 11, 1987
70C
mole fraction
1x'GOi
693
temperature
lKl 1 xB Xc"esp

4
I
;687 t - bubble phase
disperse
_._ __ phase

3 25-

-.-+ r e c t o r !ength I m 1

mol

Figure 8. Simulated profiles for a tubular reactor of technical di-


o r
I
1
1
2
1
3
I
L
1
5
- I
6
I
7
1

tee height I m l

Figure 9. Simulated concentrationprofiles in bubble and emulsion


8

mensions: (a, top) temperature and main products; (b, bottom) phase in a fluidized bed reactor.
oxidation products (conditions given in Table 111, column 3).
Table IV. Reactor Conditions of a Fluidized Bed Reactor
Table 111. ODtimal Reactor Conficfurations bed depth, m 7.53 (no cooling)
objective bed diameter, m 6.00
"5' i- HSY I SMAN =
bed porosity 0.57
optimization parameters Max Max Max" catalyst mass, kg 1.5 x 105
inlet pressure, Pa 3.9 x 105
To, K 573 633.8 666.0 temp, K 780
dt, m 1.15 1.59 2.0 YO2 0.08
pM, kg cat./m3 562 680 790 XBut. 0.02
G, k g / ( m 2 4 0.49 2.69 5.84 XBUt. 83.8
Po, io5 Pa 20 8.48 20 YMAN 42.5
L, m 6.5 0.5 1.76 %AN 50.7
d,, m 4 3.85 4 fluid densitv,
- . kn/m3
_, 1.538
dh, m 4 3.13 4 app density of cat. particle, lo3 kg/m3 1.89
%But., feed 0.2 X 2.56 X 0.359 X superfic. veloc., m/s 0.45
xol, feed 0.5 0.24 0.5 min fluidization veloc., m/s 0.03
YmN, mol '70 61.74 36.23 58.24 HSY,kg MAN/(m3.h) 10
SmN,mol 70 61.74 50.14 60.84
XB,,~., mol % 100.00 72.26 95.74 phases), concentration profiles of the reactants in the two
HSY, kg MAN/(m3 RVeh) 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 O00 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. C h e m . R e s . 1987,26, 2241-2245 2241

Model discrimination criteria confirmed the better fit Subscript


of the Eley-Rideal model compared to the Mars-Van But. = n-butane
Krevelen type. Registry No. CO, 630-08-0; COz, 124-38-9; C4HI0,106-97-8;
Design calculations for technical reactors showed quite maleic anhydride, 108-31-6; vanadium oxide, 11099-11-9; phos-
reasonable yields for the fiied bed as well as fluidized bed phorus oxide, 12640-86-7.
type with the developed catalyst.
Literature Cited
Nomenclature Arnold, S. C.; Suciu, G. D.; Verde, L.; Neri, A. Hydrocarbon Process.
1985, Sept, 123-126.
dh = particle height, m Berty, J. M. Cat. Rev.-Sci. Eng. 1979, 20(1), 75.
d, = particle diameter, m Centi, G.: Fornasari, G.: Trifiro, F. Ind. Eng. Chem. Prod. Res. Deu.
d, = tube diameter, m 1985, 24, 32-37.
E . = activation energy, kJ/kmol Emig, G.; Hoffmann, U.; Hofmann, H. Manual Dechema-course,
FiD = flame ionization detector 1975: Erlanaen, West Germany.
G = mass velocity, kg/(m2-s) Escardino, A.;Sola, C.; Ruiz, F. An. Quim. 1973, 69, 385, 1157.
AHR = reaction enthalpy, kJ/kmol Haber, J. Z . Chem. 1973, 13, 241.
HSY = hourly space yield Hodnett, B. K. Cat. Rev.-Sci. Eng. 1985,27(3), 373-424.
koj = preexponential factor, kmol/ (kg of catalyst-s-Pa) Hofmann, H. Chem.-1ng.-Tech. 1979, 51, 257.
k . = reaction rate constant, kmol/(kg of catalyst.s.Pa) Hofmann, H.; Emig, G.; Roder, W. EFCE Public. Ser. No. 37; Per-
Ifi = sorption constant, Pa-' gamon: (ISCRE8) Edinburgh, 1984; pp 419-426.
Kazansky, V. B.; Shvets, V. A. J. Catal. 1972,25, 123.
1 = unoccupied site
L = length of reactor, m Marquardt, D. W. SOC. Znd. Appl. Math. J. 1963,11, 431-441.
MAN = maleic anhydride Mars, P.; Van Krevelen, D. W. Chem. Eng. Sci. 1954,3,(spec. suppl.),
p i = partial pressure, Pa 41.
Po = total pressure at reactor inlet, Pa Moser, T. P.; Schrader, G. L. J . Catal. 1985, 92, 216-231.
Nelder, J. A.; Mead, R. Comput. J . 1965, 7, 308-313.
r = rate of reaction, kmol/(kg of cata1yst.s) Rideal, E. K. Chem. Ind. 1943,62, 355.
AV = reactor volume Schneider, P. Ph.D. Thesis, University of Erlangen-Nurnberg, 1985.
S = selectivity Schneider, P.; Emig, G.; Hofmann, H. Chem.-1ng.-Tech. 1985, 57,
T = temperature, K 728-736.
TCD = thermal conductivity detector Sitzmann, W.; Werther, J.; Bock, W.; Emig, G. Ger. Chem. Eng.
x i = mole fraction 1985,8, 107-301.
X = conversion Volta, J. C.; Portefaix, J. L. Appl. Catal. 1985, 18, 1-32.
Y = yield Williams, E. J. Regression Analysis; Wiley: New York, 1959.
Greek Symbols Received for review June 9, 1986
6 = surface coverage Revised manuscript received June 29, 1987
pbed = bed density, kg of catalyst/m3 RV Accepted July 29, 1987

Kinetic Study on the Hydrotreating of Heavy Oil. 1.


Effect of Catalyst Pellet Size in Relation to Pore Size
Satoru Kobayashi,* Satoshi Kushiyama, Reiji Aizawa, Yutaka Koinuma, Keiichi Inoue,
Yoshikazu Shimizu, and Kozo Egi
National Research Institute for Pollution and Resources, 16-3, Onogawa, Yatabe-mtlchi, Tsukuba, Ibaraki 305,
Japan

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 cm2/s for the metal compounds in Khafji residual oil a t
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-
0888-5885/87/2626-2241$01.50/0 0 1987 American Chemical Society