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Title: Heterogeneous Kinetics - Cumene Dealkylation over Cracking Catalyst

Article Type: Full Length Article

Keywords: Heterogeneous Kinetics; Cumene Dealkylation; Cracking Catalyst; Deactivation; Diffusion
Control; Surface area

Corresponding Author: Dr. Hao Sun, Ph.D.

Corresponding Author's Institution: Rice University

First Author: Hao Sun, Ph.D.

Order of Authors: Hao Sun, Ph.D.; Yi Chen, Ph.D.; Coral Isikci; Kathrine Ward; Joe w Hightower, Ph.D.

Abstract: Abstract

Catalytic cracking of hydrocarbons over porous acidic solids is the largest component of modern
petroleum refineries. Amorphous silica-aluminas, originally used in fixed-bed reactors, have been
replaced by highly active and selective zeolite catalysts in fluidized bed systems that include
continuous catalyst transfer between the reactor and a regeneration unit. This experiment uses a
model endothermic reaction, cumene cracking (dealkylation of isopropyl benzene) to demonstrate
quantitatively the kinetics, reaction order, deactivation, mechanism, active site concentration, turnover
frequencies, diffusion control, and surface area. Actually, at least two very "clean" reactions occur
simultaneously. The dealkylation reaction is relatively slow while an exchange between protons
(assumed to be active sites) on the surface of the catalyst, and the hydrocarbons reaction is orders of
magnitude faster. Both reactions were conducted independently in a micro-catalytic pulse reactor by
investigating the effect of temperature and poisoning on kinetics (Arrhenius behavior) and using
isotopic tracers (deuterium and a mass spectrometer) to titrate the protonic sites. Coupled with a
separate BET apparatus for surface area measurement, the true surface reaction rate constants and
turnover frequencies were determined.


Suggested Reviewers: David Shallcross
University of Melbourne, Australia
dcshal@unimelb.edu.au
Editor-in-Chief, Education for Chemical Engineers

Hong Zhao
Tsinghua University
hongzhao@mail.tsinghua.edu.cn
Editorial Board

Robert Hesketh
Rowan University
hesketh@rowan.edu
Editorial Board

Ian Cameron
The University of Queensland, Australia
itc@uq.edu.au
editor




Cover Letter

Regular papers


Dear Editor,

I would like to submit a regular paper to your journal. This article is original, unpublished and
not being considered for publication elsewhere.







Best Regards,
Sincerely Yours,
Hao SUN

Cover Letter
Highlights:

Catalytic reaction --- cumene cracking was conducted independently in a micro-catalytic pulse
reactor.



Students learn how to demonstrate quantitatively the kinetics, reaction order, and surface area etc.



The effect of temperature and poisoning on kinetics was investigated using isotopic tracers to
titrate the protonic sites.



It is found cumene cracking experiments are great introductory for kinetics and reactor design
course.
Research Highlights
1
Heterogeneous Kinetics – Cumene Dealkylation over Cracking Catalyst

Hao Sun*, Yi Chen, Coral Isikci, Kathrine Ward, Joe W. Hightower
*corresponding author email:war.1982@gmail.com
Department of Chemical and Biomolecular Engineering; Rice University; P.O. Box 1892; Houston, TX
77251-1892

Abstract

Catalytic cracking of hydrocarbons over porous acidic solids is the largest component of
modern petroleum refineries. Amorphous silica-aluminas, originally used in fixed-bed reactors,
have been replaced by highly active and selective zeolite catalysts in fluidized bed systems that
include continuous catalyst transfer between the reactor and a regeneration unit. This experiment
uses a model endothermic reaction, cumene cracking (dealkylation of isopropyl benzene) to
demonstrate quantitatively the kinetics, reaction order, deactivation, mechanism, active site
concentration, turnover frequencies, diffusion control, and surface area. Actually, at least two
very “clean” reactions occur simultaneously. The dealkylation reaction is relatively slow while
an exchange between protons (assumed to be active sites) on the surface of the catalyst, and the
hydrocarbons reaction is orders of magnitude faster. Both reactions were conducted
independently in a micro-catalytic pulse reactor by investigating the effect of temperature and
poisoning on kinetics (Arrhenius behavior) and using isotopic tracers (deuterium and a mass
spectrometer) to titrate the protonic sites. Coupled with a separate BET apparatus for surface
area measurement, the true surface reaction rate constants and turnover frequencies were
determined.

Keywords
Heterogeneous Kinetics; Cumene Dealkylation; Cracking Catalyst; Deactivation; Diffusion
Control; Surface area

INTRODUCTION
Catalytic cracking of hydrocarbons over porous acidic solids is the largest component of
modern petroleum refineries (about half a million tons of catalyst sold world-wide per year.)
( Skocpal et al., 2004) Amorphous silica-aluminas, originally used in fixed-bed reactors, have
been replaced by highly active and selective zeolite catalysts in fluidized bed systems that
include continuous catalyst transfer between the reactor and a regeneration unit. This experiment
uses a model endothermic reaction, cumene cracking (dealkylation of isopropyl benzene) to
demonstrate quantitatively the kinetics, reaction order, deactivation, mechanism, active site
concentration, turnover frequencies, diffusion control, and surface area. The experiment is
performed at Rice usually by junior students as a part of the introductory Kinetics and Reactor
*Manuscript
Click here to view linked References
2
Design course near the end of the fall semester. Each group of students is required to submit a
joint formal report that is graded by the professor.
Actually, at least two very “clean” reactions occur simultaneously. The dealkylation reaction
is relatively slow while an exchange between protons (assumed to be active sites) on the surface
of the catalyst, and the hydrocarbons reaction is orders of magnitude faster. Both reactions can
be studied independently in a micro-catalytic pulse reactor (Kokes et al., 1955) by investigating
the effect of temperature and poisoning on kinetics (Arrhenius behavior) and using isotopic
tracers (deuterium and a mass spectrometer) to titrate the protonic sites. Coupled with a separate
BET apparatus for surface area measurement, students can determine the true surface reaction
rate constants and turnover frequencies. In our experience, this is the most comprehensive
undergraduate catalysis module in existence today.
EQUIPMENTS AND EXPERIMENTS
The kinetics and isotopic tracer parts are carried out in the micro-catalytic pulse reactor.
Basically, the unit involves a gas chromatograph with an upstream plug flow reactor containing
the catalyst where temperature can vary independently. The He carrier gas stream first passes a
heated reactor inlet port where liquid reactants are introduced with a syringe and instantly
volatilized, through a catalyst bed where the reactions occur, past a calibration port, and into the
GLC column where the reaction products are separated before exiting through a thermal
conductivity cell for quantitative analysis. A removable trap immersed in liquid nitrogen can
collect benzene peaks as they emerge from the detector. Subsequently, the collected benzene is
transferred to a high vacuum system containing a small mass spectrometer (a residual gas
analyzer with unit mass resolution to e/m > 100) for isotopic analysis.
Moreover, both deactivation and reaction order test are involved in the kinetic experiment. 8
pulses of cumene were passed successively over a 0.25 g sample of a commercial amorphous
silica-alumina (88% silica, known in the industry as Houdry M-46) in a 0.5 cc plug flow reactor
equipped with a centered thermocouple well. The pulses began at 622 K (pulses -2, -1, and 0)
with others following at decreasing temperatures to 554 K (pulses 1 - 7), then back up to 622 K
(pulse 8) to measure deactivation (see Table 1). The reaction order is tested by varying the pulse
size of cumene feed and noting its effect on conversion under otherwise constant conditions.
Surface area is measured with a homemade “Ennis-type” system (Ennis et al., 1965) (Figure 1),
where nitrogen gas flows under choked flow conditions (which assures constant velocity) into a
previously evacuated and isolated sample tube submerged in liquid N
2
. Once the (constant) flow
rate is determined by measuring the linear pressure rise with time into a calibrated volume, time
measurements are used to calculate the volume of gas adsorbed on a sample at a given pressure
after dead volume corrections are made. The N
2
flow rate is sufficiently slow (about 0.5 cc-
STP/sec), so that temperature equilibrium is maintained at each measurement which allows the
static BET theory (Brunauer et al., 1938) can be applied to determine the specific surface area
and other adsorption constants.
ASSUMPTIONS AND CALCULATIONS
Kinetics
The dealkylation reaction is assumed to be irreversible (Murakami et al., 1968) under our
experimental conditions and first order in cumene. For first order reactions the fractional
3
conversion should be independent of initial concentration, therefore, the assumption of first order
was tested in kinetics experiment. In addition, we assume that the whole system is isothermal
and the input and output stream have constant density, because large inert concentration exists in
the reactor.
Considering those assumptions mentioned above, and the reactor behave like a Plug Flow
Reactor (PFR), therefore, the design equation in this case is
( )
( / )
h h Cu
ln 1
E RT
k Z e f t t
÷
- = - = ÷ ÷ (1)
where k
h
is the observed pseudohomogeneous reaction rate constant, τ is the space time under
reactor conditions, and f
Cu
is the fractional conversion of cumene. Taking the ln of both sides to
remove the exponential gives the linearized form
( ) ( ) ( ) ( )
Cu h
ln ln 1 ln / 1/ f Z E R T t ÷ ÷ = - ÷ - (
¸ ¸
(2)
Normally, the activation energy E and pre-exponential factor Z
h
can be determined easily by
making a series of cumene conversion measurements at different temperatures, T, at constant
space time and catalytic activity. Unfortunately, in this case neither is constant. τ increases with
decreasing reactor temperature even molar flow rate and total pressure are constant. This means τ
must be adjusted for each pulse i, viz.

i 0 i
(622/ ) T t t = - (3)
where 622 K (349 °C) is the reference temperature used to calculate τ
0
. Moreover, changes in
the observed rate constant k
h
reflect changes in the activity as the catalyst is poisoned with time
on stream under otherwise identical conditions. Either /both E
act
or/and Z
h
could be affected by
deactivation. In this case, we assume that E
act
is not affected (the “chemistry” is essentially the
same) and Z
h
takes the deactivation “hit” (due perhaps to a decrease of available active sites
through coke deposition). By assuming the deactivation is spread equally over the n pulses, thus,
the pre-exponential factor for each successive pulse i becomes

i/n
hi h0 hn h0
*( / ) Z Z k k = (4)
By plugging the corrected τ
i
[Eq. (3)] and Z
hi
[Eq. (4)] into Eq. (2) and applying the equation to
each pulse i independently, Eq. (2) becomes

( ) ( ) ( )
i/n
Cu,i 0 i h0 hn h0 i
ln ln 1 ln (622/ )* ( / ) / * 1/ f T Z k k E R T t
( ( ÷ ÷ = ÷
¸ ¸ ¸ ¸
(5)
which can be rearranged to the linearized form

( ) ( ) | | ( ) ( )
Cu,i i hn h0 0 h0 i
ln ln 1 ln(622/ ) i/n ln( / ) ln / * 1/ f T k k Z E R T t
(
÷ ÷ ÷ ÷ = ÷
¸ ¸
(6)
The only variables are the independent temperature and the resulting measurable f
Cu
for each
pulse i. Both E
act
and Z
h0
can be determined from the slope and intercept of the linearized
Arrhenius plot as shown in Figure 2.
Isotopic Tracers
Protons on the surface of the catalyst are traditionally thought to be responsible for the acidic
dealkylation reactions. (Haensel et al., 1954) When pulses of benzene are passed over the silica-
alumina catalyst under conditions used in these experiments, the benzene is recovered 100%
4
intact without any measurable cracking. However, if the injected benzene is fully deuterated
(C
6
D
6
), mass spectral measurements on the recovered benzene show that the product has
undergone massive exchange with the surface protons to essentially statistical equilibrium during
the <1 second contact time in the reactor. Measurements are made on parent peaks in the e/m
mass range from 78 (C
6
H
6
) to 84 (C
6
D
6
) under conditions where fragmentation is minimal.
Corrections are made for naturally occurring
13
C in the benzene.
The observed H/D distribution may also be compared with a statistical distribution calculated
by using a modified binomial equation. (Lide et al., 1974) The number of atoms exchanged in a
single benzene molecule during a pulse, φ, is
( )
j
j
6 j d ¢ = ÷
¿
j 0,1,..5, 6 =
j
1 d =
¿
0 6 ¢ < < (7)
where d
j
is the fraction of benzene molecules eluted with j D atoms. The total number of H
atoms exchanged from the surface into the gas phase, Σ
H,g
, is

( )
6 6
benzene/pulse Atoms Ex / C D Molecule
H g
*n ¢ =
¿

(8)
where n is the molecular number.
Similarly, the number of D atoms remaining in the gas phase is the same as Eq. (8) except that
φ is replaced by (6 – φ), viz.
( )
( )
6 6
benzene/pulse)
Atoms Not Ex / C D Molecule D g
6 *n ¢ = ÷
¿ (

(9)
Thus, the ratio φ/(6 – φ) gives the ratio of H/D in the gas phase, which is assumed to be the
same as on the catalyst if they are statistically equilibrated. A value of unity means that there was
precisely the same number of H atoms initially on the surface as D atoms introduced in the C
6
D
6

pulse.
To test for isotopic equilibration, the observed distribution of H and D atoms in the partially
deuterated benzene can also be compared with that of statistical equilibrium by plugging the φ-
value into the modified binomial Eq. (10) for each isotopic species j. Where P (j, 6, φ/6) is based
on the number of permutations one can have for each isotopic species for a given φ-value, viz.
( ) ( ) ( )
( ) j 6 j 6
j, 6, / 6 6 / 6 1 6 / 6
j
P ¢ ¢ ¢
÷ | |
= ÷ ÷ ÷ ( (
| ¸ ¸ ¸ ¸
\ .
(10)
where
( ) ( )
6
6!
j 6 j ! j !
| |
=
|
÷
\ .

For example, when φ = 3 (i.e., H/D ratio=unity), this equation gives the fractions of d
0
, d
1
,
…d
6
that are proportional to the familiar binomial ratios in a symmetric statistical binomial
distribution expected for a 50/50 H/D mixture, viz, 1, 6, 15, 20, 15, 6, 1. Students also learn how
to correct the raw deuterium distribution data for ~1.1%
13
C in carbon. Fragmentation is
minimal.
BET Surface Area Measurement
If the flow rate of N
2
is constant and adsorption equilibrium is achieved, isotherms of N
2

adsorbed on porous materials can be obtained from measurements of pressure vs. time into a
5
packed bed immersed in liquid N
2
. The volume adsorbed (usually expressed as V
a
(cc-STP)) at a
given pressure P is the product of the flow rate and the flow time to reach that pressure after
corrections are made for the dead volume. The linearized BET equation (Brunauer et al., 1938)
relating V
a
to P is
( ) ( ) ( ) ( ) ( ) ( )
0 a 0 m m 0
/ / 1 / 1/ 1 / / P P V P P V C C V C P P ÷ = + ÷ ( (
¸ ¸ ¸ ¸
(11)
P
0
is the vapor pressure of N
2
at its boiling point (~atmospheric pressure), V
m
is the monolayer
adsorbed gas quantity, and C is the BET constant which is related to the heat of adsorption of N
2

in the first layer, λ
1
, viz.

1 L
ln RT C ì ì = + (12)
λ
L
is the heat of adsorption for the second and higher layers. Eq. (11) can be plotted as a
straight line with the left side of the equation and (P/P
0
) according to experimental results.
Subsequently, V
m
and C can be evaluated from the slope and intercept of the BET plot.
Finally, the specific surface area is obtained from V
m
by assuming each N
2
molecule occupies
16.2 Å
2
from the equation
( )
g m
4.36* / Sample Wt in g S V = (13)
RESULTS
Kinetics
Kinetic data from Table 1 are plotted in Figure 2 according to Eq. (6). Using values of k
h,0

(0.486 sec
-1
) and k
h,8
(0.394 sec
-1
) to determine the deactivation per pulse from equation
( ) ( )
1/8 1/8
act / h8 h0
1 / 1 0.394/ 0.486 0.026
pulse
D k k = ÷ = ÷ = (14)
Students are required to plot three curves based on Arrhenius equation Eq. (6), individually
focus on different terms on the left side of the equation. The first curve is based on the classical
value with no correction, and the second is corrected for catalyst poisoning and the third is
corrected for both catalyst poisoning and flow rate changing with temperature. Due to the
measurement error, the data are not ideal linear, therefore, a linear fitting with the third curve
was executed, and the related degree of the correlation (R
2
= 1) is very high and acceptable. Only
the fully corrected curve is shown in Figure 2.
From the slope and intercept in Figure 2, the activation energy and unpoisoned preexponential
factor were found to be E
act
= 74.66 kj/mole and Z
h0
= 9.12*10
5
sec
-l
.
Pulses -2, -1, and 0 all showed very similar conversions of 0.383, 0.372 and 0.367 even though
pulse -1 (1 μl) was only half as large as pulses -2 (2 μl) and 0. It proves that first order is a very
close approximation to reality.
Isotopic Tracers
Benzene recovered from a single 2 μl pulse of C
6
D
6
gave the isotopic composition shown in
Figure 3 and a value of φ = 2.92 when passed over 0.25 g of catalyst at 622 K. Also shown is the
statistical distribution expected for φ = 2.92 from Eq. (10). The similarity between the observed
and statistical distributions supports the assumption that statistical equilibrium was reached
6
during the contact time of less than one second. According to Eq. (8), this gives a value of
7.17*10
19
H atoms originally on 0.25 g of catalyst, or 2.87*10
20
H atoms per gram of catalyst.
Surface Area
Based on the raw data (not shown) of Pressure vs. Time for a 2.0 g charcoal sample and the
4.0 g silica-alumina catalyst, isotherms (Figure 4) are generated by subtracting the “dead
volume” time from “isotherm time” required to reach a specific pressure and multiplying that
time by the calibrated constant flow rate. Finally, these data are plotted according to the
linearized BET Eq. (11) in Figure 5. The values of S
g
, C and λ
1
are found from the slope and
intercept of the plots with combination of Eq. (12) and Eq. (13).
It is interesting to note that while the silica-alumina catalyst sample gave a very linear BET
curve with a positive intercept, the charcoal plot deviated from linearity beyond P/P
0
> 0.28 and
resulted in a negative intercept when all the data were included in a “best straight line.” This is
due to the limited number of adsorbed N
2
layers charcoal can accommodate with its extremely
narrow pore sizes (almost a Langmuir-type monolayer). To avoid the negative intercept for
charcoal, only the first few data points (up to P/P
0
≈ 0.28, or ~ monolayer coverage) were
included in the “best fit” line.
From the BET plots in Figure 5, the specific surface areas S
g
of the silica-alumina catalyst and
charcoal adsorbent are 359.7 m
2
/g and 610.4 m
2
/g respectively. With corresponding C-values of
203 and 142.2, the heats of adsorption of N
2
in the first layer are 18.58 kj/mole and 17.7 kj/mole
respectively.
DISCUSSION
All calculated parameters are summarized in Table 2. The true surface reaction rate constant
per unit surface area, k
s
, is another parameter that can be determined through equation
( ) ( ) ( ) ( )
4 7
s0 h0 T g bed
* / * 0.486*0.783 / 359.7*10 *0.556 1.9*10 cm/ sec k k S c µ
÷
= = = (15)


ε
T
is the total void fraction of the catalyst bed (1 – ρ
bed

true
), which ρ
true
is determined from the
weighted averages of the densities of silica and alumina in the catalyst, 88% and 12%
respectively. Because k
s0
is so small, the only way for this catalyst to be effective is to have a
large, available surface area.
Moreover, the density of sites is 7.98*10
13
H/cm
2
or about 125 Å
2
/H atom. An initial average
turnover frequency can be calculated from the cumene molecules injected in pulse zero, the
fractional conversion, the holding time in the reactor, and the number of active sites through the
equation

| |
( ) ( )
Cu Cu 0 T H atoms/0.25 g cat.
18 19
1
* / * *
= 8.65*10 *0.367 / 0.939*0.783*7.17*10
0.06cumene molecules / site*sec
TF n f n t c
÷
( =
¸ ¸
=

(16)
From those data it is also possible to investigate the influence of internal diffusion on the
catalyst performance. This is accomplished by calculating the Weisz-Hicks criterion Φ
s
based on
the Thiele diffusion modulus for spherical particles, (Satterfield et al., 1970) viz.
7

( )
2
s eff h0
* R D k u = (17)
where the particle radius R = 0.0299 cm is determined from the particle size (average of 20-40
mesh), and the effective diffusion coefficient D
eff
= 0.0012 cm
2
/sec is taken from Satterfield’s
(Satterfield et al., 1970) classic book. For this system at 622 K, Φ
s
= 0.36. The value less than
unity indicates the reaction rate is not severely limited by internal diffusion constraints.
In real refinery operations, the average time catalyst particles stay in the reactor is the order of
90 seconds before they become deactivated and must be transported to the regenerator for
reactivation and preheating. Each pulse in this system stays in our fixed bed reactor less than one
second and causes a loss of about 2% of the catalyst's activity. This means that our catalyst must
be regenerated after it has been used by about half a dozen groups. Thus, the contact time in our
system before regeneration is comparable to the 90 seconds residence time in the real industrial
world.
CONCLUSIONS
Through this experiment, the students are exposed to many of the concepts in heterogeneous
catalysis. They experimentally determine Arrhenius parameters in reaction kinetics, reaction
order, catalyst deactivation, number/nature of active sites, turnover frequencies, surface areas,
and diffusion limitations in a reaction that models the most important process in a modern
petroleum refinery, catalytic cracking. In addition, the students must make extensive use of
handbooks (Perry’s, CRC), Satterfield's book, and safety/toxicology (Sax’s book), (Sax et al.,
1963) etc. They gain experience in applying the Binomial Equation to a real system. While this
experiment is highly specialized, it gives students a good idea about how general concepts can be
applied in important situations.
ACKNOWLEDGMENTS
We are grateful for internal funds from the Dean of Engineering and the Chemical and
Biomolecular Engineering Department for funds and many students whose patience work has
made the development of this experiment possible.
REFERENCES
Brunauer, S., P.H. Emmett, and E. Teller, 1938. “Adsorption of Gases in
Multimolecular Layers,” J. Am. Chem. Soc., 60, 309
Ennis, W.B., 1965. private communication, Gulf Oil
Haensel, V., chapter in Adv. In Catal. III, 1954.Academic Press, New York
Kokes, R.J., H. Tobin, Jr., and P.H. Emmett, 1955. J. Am. Chem. Soc., 77, 5860
Lide, D.R., 1994. editor, CRC Handbook of Chemistry and Physics, Fifth Ed., CRC
Press, Ann Arbor
Murakami, Y., T. Hattori, and T. Hattori, 1968.“Study on the Pulse Reaction
Technique: II. Dealkylation and Disproportionation of Cumene,”Journal of Catalysis,
10(2), 123-127
8
Perry, R.H. and C.H. Chilton, 1973. Chemical Engineers’ Handbook, McGraw-Hill, New
York
Satterfield, C.N., 1970.Mass Transfer in Heterogeneous Catalysis, MIT Press,
Cambridge
Skocpal, 2004. private communication, Albemarle Chemical
Sax, N. Irving, ed., 1963.Dangerous Properties of Industrial Materials, Second Ed.,
Reihhold Publishing, New York





Figure 1 “Ennis-type” System in Surface Area Measurement
1.60 1.65 1.70 1.75 1.80
-2.5
-2.0
-1.5
-1.0
-0.5
0
7
4
6
5
3
2
1



l
n
[
-
l
n
(
1
-
f
C
u
,
i
)
]

-

l
n
(
6
2
2
/
T
i
)

-

(
i
/
n
)
l
n
(
k
h
n
/
k
h
0
)
1000/T
i

The value of the left side of Eq.6
Linear fit curve
Y=-8.98X+13.66
R
2
=1

Figure 2 Arrhenius Plot based on Eq. (6)
Capillary
Bypass
N
2

OilVacuum
Pump
P
u

Calibrated
Volume
P
Sample
Figure
78 79 80 81 82 83 84
0.0
0.2
0.4
0.6
0.8
1.0


N
o
m
a
l
i
z
e
d

f
r
a
c
t
i
o
n

o
f

m
o
l
e
c
u
l
e
s

w
i
t
h

j

D

a
t
o
m
s
Benzene molecular weight, g/mole
Observed
Statistical

Figure 3 Observed and Statistical Distributions of C
6
D
6
Composition
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35
0
50
100
150
200


P/P
0
charcoal
Si-Al-O
N
2

A
d
o
s
o
r
b
e
d

(
c
c
-
S
T
P
/
g
)

Figure 4 Nitrogen Adsorption Isotherms
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4


Y=3.03X+0.015
R
2
=0.9979
Y=3.53X+0.025
R
2
=0.9996
1
0
0
0
(
P
/
P
0
)
/
[
V
a
(
1
-
P
/
P
0
)
]

P/P
0
Charcoal
Linear fit
Si-Al-O
Linear fit




Figure 5 Linearized BET Plots


Table 1 Kinetic Data from Cumene Dealkylation over Silica-Alumina
Pulse No. T
i
/ K f
Cu,i
k
h,i,
/ sec
-1
ln[-ln(1-f
Cu
)] ln(622/T
i
) (i/8)ln[(k
h8
/k
h0
)
-2 622 0.383 0.513 -0.728 0 --
-1* 622 0.372 0.494 -0.765 0 --
0** 622 0.367 0.486 -0.781 0 0
1 613 0.304 0.380 -1.013 0.015 -0.026
2 604 0.246 0.291 -1.264 0.029 -0.052
3 594 0.204 0.232 -1.476 0.046 -0.079
4 584 0.162 0.176 -1.735 0.063 -0.105
5 573 0.124 0.130 -2.021 0.082 -0.131
6 564 0.095 0.096 -2.304 0.098 -0.157
7 554 0.067 0.066 -2.667 0.116 -0.184
8 622 0.310 0.394 -0.992 0 --
* 1 μl pulse of cumene; all others 2 μl; ** Activity = unity

Table 2 Summary of All Calculated Parameters
Parameter Value
Space time τ
0
= V
R
/u
0
at reactor conditions, 30 psig, 622 K (sec) 0.941
Contact time under standard reactor conditions, 30 psig, 622 K (sec) 0.758
First order reaction rate constant before poisoning, k
h0
(sec
-1
) 0.486
First order reaction rate constant after poisoning by 8 pulses, k
h8
(sec
-1
) 0.394
Activation energy corrected for flow changes and deactivation, E
act
(kj/mole) 74.66
Initial pre-exponential factor (unpoisoned), Z
h0
(sec
-1
) 9.12*10
5

Fraction of activity poisoned per pulse, D
act/pulse
0.026
Unpoisoned true surface reaction rate constant, k
s,0
(cm/sec) 1.9*10
-7

Total active sites, Σ
h0
(H atoms/g catalyst) 2.87*10
20

Concentration of active sites (H/cm
2)
7.98*10
13

Area occupied by each H atom (Å
2
/H) 125
BET surface area of silica-alumina catalyst, S
g
(m
2
/g) 359.7
BET constant for silica-alumina, C 203
Heat of adsorption of N
2
in first layer for silica-alumina, λ
1
(kj/mole)
18.58
BET surface area of charcoal, S
g
(m
2
/g) 610.4
BET constant for charcoal, C 142.2
Heat of adsorption of N
2
in first layer for charcoal, λ
1
(kj/mole)
17.7
TF, Turnover frequency(cumene converted/H atom*sec
-1
) 0.077
Average Weisz-Hicks diffusion control parameter, Φ
s
0.36



Table