KINETIC AND EQUILIBRIUM STUDIES OF BENZENE HYDROGENATION I N BATCH RECYCLE REACTOR

P A U L F. KORBACH' A N D W A R R E N E. S T E W A R T
Department of Chemical Engineering, University of Tl'zsconsin, .Madison, Wis.

Rate and equilibrium data are reported for vapor-phase hydrogenation of benzene over a pulverized platinum-alumina catalyst. The measurements were made with a fixed-bed differential reactor in a batch recycle system, and illustrate the possibilities of this unusual experimental technique. The reaction conditions studied range from 500" to 600" F., 2- to 14-atm. total pressure, 6 to 12 moles of Hz charged per mole of benzene, and 0 to 99.9% conversion. The results do not indicate a definite reaction order, but the initial rate varies approximately as the cube of the total pressure. No side reactions were observed.

hydrogenation of benzene to cyclohexane is a reaction continuing importance for kinetic investigation. T h e reaction is industrially important, kinetically complicated, and subject to significant heat and mass transport effects. The present paper provides new kinetic and equilibrium data for this reaction. Of greater importance, however, is the experimental technique developed in this research ( 3 ) . The technique is presented here in some detail, as it appears promising for the study of many types of fixed-bed reactions. Kinetic studies of rapid solid-catalyzed reactions are generally difficult. I n the conventional one-pass differential reactor, operation at conversions large enough for accurate measurement may lead to gross uncertainties in the temperature or cornposition at the catalyst particle surfaces ( 6 ) . \Yhile it is possible to reduce these uncertainties by use of lowactivity catalyst. high mass velocities, or a series of catalyst beds with intermediate heat exchange, each of these methods raises neiv difficulties. Another difficulty encountered with one-pass reactors is that large variations in feed rate or catalyst charge are usually necessary to study the change in reaction rate with reaction conditions; this also app1:es to recycle reactors when operated a t steady state. The above difficulties \vere avoided in the present study by using a batch recycle reaction system (Figure 1). The high flow velocity through the reactor, and the small catalyst particle size, minimized heat and mass transfer difficulties. The batchwise operation allo\ved rapid determination of rate and equilibrium data, from measurements of the composition of the reaction mixture as a function of time. A thousandfold range of reaction rates was measured readily on a single catalyst charge. Xo continuous feed system was required. The small feed consumption minimized the danger of cumulative poisoning of the catalyst. Accurate determinations of reaction selectivity \\'ere made, which \vould not have been possible in a onepass differential reactor. Since the composition in a batch reaction system varies with time. the results obtained may depend on the transient response of the catalyst to changes in fluid composition. The present system, however, \vas operated \vith a very small catalyst-reactant ratio, JO give a small rate of composition change and a close approach to steady-state catalyst performance. Results given later indicate that this objective was achieved. The present paper is devoted to the experimental technique
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and results. The questions of mechanism and rate equations are still under study, and are not discussed here.
Reactants

Spectrometer-grade benzene from Distillation Product Industries was used. Chromatographic analysis indicated the composition to be 99.31 mole 76 benzene, 0.69 mole % cyclohexane; this analysis was used in all calculations. Electrolytic hydrogen from Sational Cylinder Gas Co. was used. This gas contained about 0.5 mole 70 oxygen and some \cater vapor. To remove these impurities the gas was passed through a bed of platinum and palladium catalysts, and then through a bed of activated alumina, before entering the reaction system.
Catalyst

A commercial platinum-alumina catalyst, Sinclair-Baker RD-150, was used. Pertinent properties of this catalyst are: BET nitrogen area approximately 500 sq. meters per gram, bulk density 0.79 gram per cc.: pore volume 0.56 cc. per gram, platinum content 0.6 weight yc. T h e catalyst charge (0.250 gram) used for the main part of the study was ground to 45 to 50 mesh in a nitrogen-purged dry box, transported to the reactor in a sealed vessel, and inserted into the reactor in a stream of dry nitrogen.
Apparatus

The flow plan of the reaction system is shown in Figure 1. Details are given by Korbach ( 3 ) . The system consisted essentially of a small fixed-bed reactor and two variable-volume p i s holders, with a pump continuously circulating the reaction mixture through them. T h e reactor was operated at 500' to 600' F., and the balance of the system was maintained at 400' F. or above to keep the reaction mixture fully vaporized. The variable-volume vessels, circulation pump, and pressure controller were mounted in a vapor chest, heated by Tetralin vapor condensing at 402' F: The reactor shell was an 18-inch length of 1; ?-inch Schedule 40 stainless steel 304 pipe. The catalyst was mounted in a screen-bottomed annular basket which fitted closely to the axial thermowell and the tube \\.all. The catalyst bed had a n inside diameter of 0.14 inch, a n outside diameter of 0.54 inch, and a depth of about 0.1 inch. The reactor tube and preheat coil were mounted in a sand bath fluidized with preheated air, Lvhich proved to be a simple and effective thermostat. Two variable-volume vessels ivere provided (see Figure 1) to allow operation at a steady total pressure during the reaction. The volumes were controlled by means of a diaphragm pressure sbvitch, pump, and solenoid valve, which regulated the amount of hydraulic oil in the space around the bellows. In-

Present address, Humble Oil and Refining Co., Baytown, Tex.

l&EC FUNDAMENTALS

24

REACTOR nsond bath heater, with preheal coil

HYDRAULIC BACKUP SYSTEM

Figure 1 .

Flow plan of reaction unit

side each bello\vs a hollclw filler was mounted to allow greater flexibility in operation. \\'ith the filler volume excluded from the system, the operation of the bellows allowed a 337, shrinkage in system volume (from 8.6 liters to 5.75 liters) ; with the filler volume included, a 1970 shrinkage could be obtained (from 14.8 liters to 11.95 liters). Protection of the bellows against unbalanced pressures proved difficult. T h e first method used was to install rupture disks bet\veen the hydraulic oil and the discharge of the gas recycle pump; this method \vas discontinued after several premature disk failures and consequent oil contamination of the reaction system. T h e second method was to limit the travel of the bellows by means of level-sensing switches on the external oil reservoir; this method w.as used in most of the runs reported here. T h e level-sensing method worked well but was not infallible, and the work reported here was terminated by rupture of the bellows. Gas circulation was provided by a diaphragm pump (Pressure Products Model 2705) with a stainless steel diaphragm and Viton-A gaskets and seals. This pump gave a circulation rate of about 0.65 cu. foot per minute a t suction conditions, which was sufficient to e:jtablish a well-stirred system within 1 or 2 minutes from the start of each run. T h e rapid circulation also minimized temperature and composition gradients in the catalyst bed.
Operation

system \vas activated. and the reactor was brought to operating temperature. \\'hen the desired reactor temperature was reachvd. the hydrogen flo\v \vas directed through the charge pot of vaporized benzene (see Figure 1 ) to start the run. 7'he progress of the reaction v a s measured frequently during each run, by chromatographic analysis of gas samples vented from the unit. T h e runs were continued. in most cases, until either the limit of the bellobvs travel \vas reached or the reaction had practically reached equilibrium. .4fter each run the unit was vented and purged thoroughly \vith hy-Jrogen, until the chromatograph showed the vented gas to be free of hydrocarbons. T h e unit was then pressured to 85 p.s.i.g. with hydrogen and left standing overnight with the reactor at 500' F. Four 0.25-gram charges of catalyst were tested. T h e first three were deactivated, after short periods of testing, by hydraulic oil which entered the system via the rupture disks. T h e rupture disks were then eliminated and the final catalyst charge \vas installed. T h e final catalyst charge showed high but variable activity in the first 15 runs, during which it was held at 500' F. I h e activity was then stabilized by heating the catalyst from 500' to 900' F. over a 5-hour period, under 90-p.s.i.g. pressure in a static hydrogen atmosphere. No further variations in activity were noticed until run 41 21, when the test program was essentially completed. T h e data reported here were all obtained with this stabilized catalyst charge, except for the first two runs made with the second catalyst charge, which \teere at a comparable activity level. I t is believed that the activity fluctuations observed with the fourth charge may have resulted from incomplete reduction of the catalyst. Conventionally, this catalyst is treated in the reactor with hydrogen at 800' F. or higher to reduce the platinum to metallic form; however in the present work, until the stabilization, the fourth charge had not been exposed to hydrogen above 600' F. \Vhatever the cause? the activity did become stable when the catalyst \vas exposed to hydrogen at the normal reduction temperature of 900' F . Further study of these activity effects is warranted.
Calculations

The amounts of hydrogen and benzene charged for each run were determined by volume and weight, respectively. T h e complete inventory of the unit at each sampling time was calculated lrom the measured ratio of the cyclohexane and benzene concentrations, assuming a well-mixed system and correctiiig for the material removed in the gas samples. S o products other than cyclohexane \vere found. The material balances checked within i- 576 for all runs reported here.

Before each run the gas space in the unit was purged thoroughly with hydrogen, and the bellows were positioned. T h e unit was then filled with hydrogen to the desired operating pressure, the circulation pump was started, the pressure-control

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Figure 2.

6 8 IO 12 W/F, GM. CAT./(GM. MJHR.)

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Figure 3. of feed

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0.6 0.8 1.0 1.2 W/F, GM. CAT./(GM. MJHR.)

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Catalyst response tests made b y varying amount

Activity tests on stabilized catalyst charge

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Figure 4.

Integral conversion data at 500" F.

Figure 6. Reaction rates at 500" F. and initial H2-benzene ratio of 12.0

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Integral conversion data at 600" F. Figure 7. Reaction rates at 600" F. and initial H2-benzene ratio of 12.0

The rate of reaction, r, per unit mass of catalyst was calculated from the relation
r =

f dt W

dx

(1)

Results

which holds for a perfectly stirred batch system. Here T1' is the mass of catalyst, t is time, x is fractional conversion of benzene, and f is the instantaneous molar in'ventory of benzene and cyclohexane in the system. The derivative d x l d t , a t the mean of successive measured conversions, rvas approximated by Ax/&. Tests of 24-hour duration without catalyst showed no detectable conversion ; hence no correction for thermal effects was needed. The state of the fluid was nearly uniform throughout the catalyst bed a t any given time. Even a t the unusually high reaction rate of 1.O gram-mole hr. -l gram-' encountered in run 5022, the calculated temperature differences ( 3 )were only 4" C. from bed inlet to outlet, 0 . 7 ' C. from the gas stream to the particle surface, and 1" C. inside the particle. The corresponding mole fraction differences were less than 0.001 from bed inlet to outlet, and less than 0.0002 from the gas stream to the particle surface, for each of the three species. The calculated effects of diffusion inside the particles were somewhat greater, a n effectiveness factor of 0.9 \vas estimated for run 5022 from diffusion and pore size distribution data obtained by Johnson (2) on this catalyst. For the runs a t loizer pressures, the differences bet\veen gas-stream and internal particle conditions were even less significant. The only serious problem in evaluation of reaction conditions was the pressure drop, which sometimes reached 107, of the reactor pressure. The reaction conditions lvere reported ( 3 ) in terms of the average stream pressure and temperature in the reactor, and the gas composition was reported as analyzed.
26
l&EC FUNDAMENTALS

Integral-conversion data obtained with the stabilized catalyst are plotted in Figures 2, 3, 4,and 5. The abscissa of these plots is labeled as JP','F, where

"=so;
F

to emphasize the similarity between these plots and the corresponding ones for isothermal plug-flow reactors ( 7 ) . This choice of abscissa is also motivated by the fact that the local slope of the x us. Lb'/F curve for any of the runs is equal to the reaction rate? r? of Equation 1 at that point in the run, The H , / H C ratio sho\vn in each case is the initial value for the run. Activity test data on the stabilized catalyst are shown in Figures 2 and 3. The reproducibility of the measurements: made a t intervals between other runs in the program, is evident. Equally good agreement was found in repeated testing at other conditions. The catalyst activity was essentially constant: except for a possible drop of about 5% between run 41 17 and the later runs (4121> 5012, and 5011) sho\vn in Figure 3. Therefore, all results in this paper are presented as observed, without activity corrections. Tests of the transient response of the catalyst to changes in gas composition are shown in Figure 3. The four runs shown were all made on the same catalyst charge, xvith operating conditions comparable except for the initial amount of reaction mixture. I n this way the time required to attain a given conversion \vas varied over a 2.5-fold range. rvith runs 5012 and 5011 taking the longest. The results for x i ~ s .[I7,F

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Figure 8.

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Reaction rates at zero comersion

Figure 9. Equilibrium constants for reaction 3 Hz ( 9 ) benzene (9) cyclohexane (9)

in the four runs agree well, particularly for runs 4121, 5012, and 5011, which were made consecutively. Therefore it is believed that, a t least u p to this level of reaction rate (0.2 grammole hr.-l gram-) and conversion (0 to 30y0), the present data may be used for steady-state reactor design. Figures 4 and 5 give integral conversion data for various operating conditions. E,ach line represents a single conthuous run in the batch unit, of 2 to 8 hours duration. In view of the transient-response results mentioned above, these curves should also represent the Performance of isothermal, steady-state, plugflow reactors lvith catalyst charge I17and benzene feed rate F. Figures 6 and 7 give reaction rates obtained by difference from successive points of the unsmoothed integral-conversion data. T h e large effect of pressure on the reaction rate is evident. T h e data are smosoth enough in most cases to allow easy estimation of initial reaction rates and equilibrium conversions. The change in shape of {.he curves \vith pressure indicates that the reaction does not have a definite order with respect to benzene. Figure 8 sho\vs the effects of several variables on the initial reaction rate. A hundredfold increase in reaction rate is observed in going from 2- to 13-atm. total pressure. The data at 500 F. show a complicated pressure dependence which is believed to be due to a change in the dominant reaction mechanism as the pressure is increased. T h e reversal of the temperature dependence (and perhaps the dependence on H2/HC ratio) at about 4-atm. total pressure also suggests a kinetically complicated reaction. Further measurements will be made to delineate these effects before proposing a reaction rate equation. Equilibrium data obtained from the reaction rate plots are given in Figure 9. These fall between the correlations of API Project 44 ( J ) and of Prigogine, Outer, and Herbo (5)!somewhat closer to the latter.
Conclusions

T h e data given here are believed applicable to steady-state reactor design. This conclusion is based on the results in Figure 3. which show no significant trend Lvith catalyst-feed ratio. I n general, if irreversible catalyst activity changes can be neglected, the reaction rates in a batch recycle unit will approach the steady-state fixed-bed catalyst performance as the catalyst-feed ratio approaches zero. T h e results a t high catalyst-feed ratios, on the other hand. will depend on the transient response of the catalyst to changes in the reaction environment; this region of operation was avoided here but offers interesting possibilities for future investigation. T h e hydrogenation of benzene is kinetically complicated. Additional experiments are needed to determine more completely the dependence of the rate on pressure and composition; this will be done in the near future. now that the reactor system has been rebuilt.
Acknowledgment

James P. Hutchins gave valuable assistance in the development and operation of the reaction system. Fellowship support was provided by the Visking Corp., Sinclair Research. Inc.. and Wisconsin Alumni Research Foundation. Computing services were financed by the University Research Committee and the National Science Foundation. Samples of RD-150 catalyst were supplied by Engelhard Industries, Inc., and by Sinclair Research, Inc.
literature Cited
(1) Hougen, 0. A . , \Vatson, K. M., Chemical Process Prin-

T h e utility of a batch recycle system has been demonstrated for studies of a stable catalyst. Close control over the reaction conditions was obtained. Feed consumption and attendant feed purification problems \cere minimized Each run yielded a n integral-conversion curve from zero to near equilibrium conversion and reaction rate data (by differentiation) over the same range.

ciples, Part 111, \Viley, New York, 1947. (2) Johnson, M. F. L., Sinclair Research, Inc., Harvey, Ill., private communication, 1960. (3) Korbach, P. F., Kinetics of the Vapor-Phase Hydrogenation of Benzene on a Platinum-Alumina Catalyst, Ph.D. thesis, University of LVisconsin, Madison, \Vis., 1962. (4) Natl. Bur. Std. Circ. (U. S.), bashington, D. C., API Research Project 44, Table 5y (Nov. 30. 1945) and 7y (April 30,
10671
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(5) Prigogine, I., Outer, P., Herbo, CI., J . Phys. & Coiiozd Chem. 52, 321 (1948). (6) Yoshida, F., Ramaswami, D., Hougen, 0. A , A.1.Ch.E. J . 8 , 5 (1962).

RECEIVED for review June 3: 1963 ACCEPTED September 9 , 1963

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