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Eng. & Tech. Journal ,Vol.27, No.

7, 2009

Reaction Kinetic ofα-methylstyrene (AMS) Hydrogenation

Zaidoon M. Shakoor* , Mumtaz A. Zablouk* & Adel A. Shuhaib*


Received on: 1/ 9/2008
Accepted on: 26 /1/2009
Abstract
In this research hydrogenation kinetic of alpha-methylstyrene (AMS) on Pd/Al2O3
catalyst was studied. The reaction is mildly exothermic (∆H=-109 kJ/mol). Intrinsic
kinetic law was investigated under wide range of operating conditions 0.1 and 0.2 gm
catalyst loading, 0.5-100 wt% AMS, 10, 15 and 20 bar pressure and 343-373 K
temperature.
The experiment data are fitted to estimate the kinetic parameters for different reaction
mechanisms by using ACM (Aspen Custom Modeler) software. Finally the results of
produced reaction mechanisms are compared with experimental results to obtain the
optimum reaction mechanism.

Keywords: α-methylstyrene, hydrogenation, mechanism, catalytic reaction.

‫ﺩﺭﺍﺴﺔ ﻤﻴﻜﺎﻨﻴﻜﻴﺔ ﺘﻔﺎﻋل ﻫﺩﺭﺠﺔ ﺍﻻﻟﻔﺎﻤﻴﺜﻴل ﺴﺘﺎﻴﺭﻴﻥ‬


‫ﺍﻟﺨﻼﺼﺔ‬
‫( ﻋﻠﻰ‬α-methylstyrene) ‫ﻓﻲ ﻫﺫﺍ ﺍﻟﺒﺤﺙ ﺘﻤﺕ ﺩﺭﺍﺴﺔ ﻤﻴﻜﺎﻨﻴﻜﻴﺔ ﺘﻔﺎﻋل ﺍﻟﻬﺩﺭﺠﺔ ﻟﻤﺎﺩﺓ ﺍﻟﻔﺎﻤﻴﺜﻴل ﺴﺘﺎﻴﺭﻴﻥ‬
‫ ﺤﻴﺙ ﻜﺎﻨﺕ ﻜﻤﻴﺔ ﺍﻟﻌﺎﻤل ﺍﻟﻤﺴﺎﻋﺩ‬.‫ ﻓﻲ ﻤﺩﻯ ﻭﺍﺴﻊ ﻤﻥ ﺍﻟﻅﺭﻭﻑ ﺍﻟﺘﺸﻐﻴﻠﻴﺔ‬Pd/Al2O3 ‫ﺴﻁﺢ ﻋﺎﻤل ﻤﺴﺎﻋﺩ ﻤﻥ ﻨﻭﻉ‬
15 ,10 ‫ ﻭﺯﻥ ﻭﺍﻟﻀﻐﻭﻁ ﺍﻟﻤﺴﺘﺨﺩﻤﺔ ﻜﺎﻨﺕ‬%100-0.5 ‫ ﻏﻡ ﻭﺍﻟﻨﺴﺒﺔ ﺍﻟﻭﺯﻨﻴﺔ ﻟﻤﺎﺩﺓ ﺍﻟﻔﺎﻤﻴﺜﻴل ﺴﺘﺎﻴﺭﻴﻥ‬0.2 , 0.1
‫ ﻋﻠﻤﺎ ﺃﻥ ﺘﻔﺎﻋل ﺍﻟﻬﺩﺭﺠﺔ ﻫﻭ ﺘﻔﺎﻋل ﺒﺎﻋﺙ ﺒﺸﻜل ﻤﻌﺘﺩل ﺤﻴﺙ ﺘﺒﻠﻎ‬.‫ ﻜﻠﻔﻥ‬373-343 ‫ ﺒﺎﺭ ﻭ ﺩﺭﺠﺔ ﺍﻟﺤﺭﺍﺭﺓ‬20,
.(‫ ﻤﻭل‬/‫ ﻜﻴﻠﻭﺠﻭل‬109=∆H) ‫ﻁﺎﻗﺔ ﺍﻟﺘﻔﺎﻋل‬
Aspen )‫ﺘﻡ ﺤﺴﺎﺏ ﺍﻟﺜﻭﺍﺒﺕ ﺍﻟﺨﺎﺼﺔ ﻟﻠﻤﻴﻜﺎﻨﻴﻜﻴﺎﺕ ﺍﻟﻤﻘﺘﺭﺤﺔ ﺒﺎﻻﻋﺘﻤﺎﺩ ﻋﻠﻰ ﺍﻟﻨﺘﺎﺌﺞ ﺍﻟﻌﻤﻠﻴﺔ ﺒﺎﺴﺘﺨﺩﺍﻡ ﺒﺭﻨﺎﻤﺞ‬
‫ ﻓﻲ ﺍﻟﻨﻬﺎﻴﺔ ﺘﻤﺕ ﻤﻘﺎﺭﻨﺔ ﺍﻟﻨﺘﺎﺌﺞ ﺍﻟﻌﻤﻠﻴﺔ ﻤﻊ ﻨﺘﺎﺌﺞ ﺍﻟﻤﻴﻜﺎﻨﻴﻜﻴﺎﺕ ﻭﺒﻌﺩﻫﺎ ﺘﻡ ﺍﺨﺘﻴﺎﺭ ﺃﺤﺴﻥ‬.(Custom Modeler
.‫ﻤﻴﻜﺎﻨﻴﻜﻴﺔ ﻭﺍﻟﺘﻲ ﺘﻌﻁﻲ ﺍﻗل ﻨﺴﺒﺔ ﻤﻥ ﺍﻟﺨﻁﺄ‬

1.Introduction The presence of the catalyst does not


Many reactions proceed much faster in affect the Gibbs energy of reactants or
the presence of a substance that is not a product therefore it does not affect the
product or reactant in the usual since. This equilibrium constant for the reaction
substance is called a catalyst, and the (Missen et al., (1999)).
process is called catalytic reaction The hydrogenation of α–methyl styrene
( Shuhaib 2008). Catalysts increase the (AMS) to cumene over a palladium on γ–
reaction rate by lowering the energy alumina catalyst is well known system used
requirements for the reaction. Thus, from to understand three-phase reactor
the ability of the catalyst to form bonds for performance under mass transfer limited
reaction intermediates to offset the energy condition (e.g. Cini and Harold (1991),
required to break reaction bonds. Khadilkar et al. (1996), Frank et al. (1999)

* Chemical Engineering Department, University of Technology / Baghdad

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

and Bauer et al. (2005)), because of its that there were no transport limitations at
high intrinsic reaction rates. temperatures below 313 K. They proposed
C6H5C(CH3)=CH2+H2→ C6H5CH- (CH3)2 three rate expressions all based on different
α – methyl styrene cumence mechanisms:
(i) an Eiley-Rideal mechanism.
Germain et al., (1974) used a semi-batch r=
k r K AMS C AMS PH
…… (3)
1 + K AMS C AMS
stirred tank slurry reactor to study AMS
hydrogenation. They observed a reaction (ii) a noncompetitive adsorption process
order of 0.64 when mass transfer resistance of dissociated hydrogen and AMS.
eliminated. Also they observed that the r=
kr K AMS C AMS K H PH
…. (4)
reaction selectivity to cumene is 100 %. (1 + K AMS C AMS )(1 + K H PH )

Mochizuki and Matsui, (1976) studied (iii) a competitive adsorption process of


Styrene hydrogenation in the range of dissociated hydrogen and AMS.
temperature 323-353 K, and hydrogen kr K AMS C AMS K H PH
r= …. (5)
pressure 0.12-0.44 MPa. They observed (1 + K AMS C AMS + K H PH ) 2
that the reaction rate in this conditions is in Lange et al. (1999) considered a
the range 2.5-20 x 10-4 mol/ kgcat. s). noncompetitive adsorption of AMS and
The first order behavior of hydrogen nondissociated H2.
pressure on the styrene hydrogenation rate kr K AMS C AMS K H PH
r= …. (6)
was found by Chaudhari et al. (1986). They (1 + K AMS C AMS )(1 + K H PH )

concluded that the reaction is first order in The experimental investigation of the
hydrogen up to a pressure of at least 30 bar. kinetics of the hydrogenation of a-
Babcock et al. (1957) proposed two rate methylstyrene also was performed by
equations depending on the hydrogen Meille et al. (2002). They expressed the
pressure P H. At low hydrogen pressure, intrinsic reaction rate by the following rate
AMS and dissociated H2 were found to equation:
compete for the same active sites.  E  KH C H
( )
r = k0 ⋅ exp − A  2 2

2
….(7)
krr K AMS C AMS K H PH  RT  1 + KH C H
r= …. (1) 2 2

(1 + K AMS C AMS + K H PH ) 3

Also at higher pressure (above 0.3 2. Thiele modulus and Pore efficiency
MPa), the reaction take place between AMS The Thiele modulus provides a
and atomic H adsorbed on different types of dimensionless ratio to describe the
active sites. influence of the diffusion inhibition for the
kr K AMS C AMS K H PH
r= . …(2) reaction rate.
(1 + K AMS C AMS )(1 + K H PH ) 2
An explicit calculation of Thiele modul
is for simplifying assumptions, since the
\White et al. (1974) used a simplified gas inhibition is much greater than the
rate
inhibition of AMS, a model for a single
expression exhibiting zeroth order in AMS cylindrical pore formed in the reaction A→
and first order in hydrogen (hydrogen product. For the investigated hydrogenation
pressure of 0.4 MPa). of AMS, is zero order for a AMS and first
Cini and Harold (1991) investigated the order with respect to hydrogen (Chaudhari
intrinsic kinetics of the reaction, identifying et al. (1986)) .

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

The general equation of Thiele modulus η=


rH 2 . exp
…. (13)
rH
for the hydrogenation AMS reaction, first 2 . int r ,

order states (Meille et al., (2002)): For spherical particles Levenspiel


− rH (1999) developed an equation for the pore
M T = LT . …. (8)
2 , int r

C H .D eff .
2
efficiency in which only depend on Thiele
The characteristic particle size LT for module occurs:
spherical is 1/6 of the ball diameter. 1  1 1 
η=  −  …. (14)
MT  tanh (3. M T ) 3. M T 
For the definition Thiele module is the
intrinsic, that is not directly measurable on
the catalyst particle volume related reaction 3. Experimental Set-Up
rate rH2,intr. The experimental work taken place in
According to Herskowitz et al.(1978) the department of chemical engineering and
the equilibrium concentration of hydrogen plant design-university of Dresden in
in pure AMS is given in equation (9) in the Germany. Figure (1) shows a schematic
range of temperatures 288-347 K. diagram of the experimental set-up. The
ρ  T  mol stirred tank reactor (STR) is operating in
CH =  0.0145 − 1.6985 . 3 ….. (9)
2
bar  K  m semi-batch mode in which the gas phase
Meille et al., (2002) observed that (H2) is feed continuously to the reactor
hydrogen solubility in cumene is the same which contains liquid phase (AMS). The
as that in AMS. Also they used equation (9) experiments were carried out in 5100 fixed
in calculation of hydrogen concentration head bench top reactor with stainless steel
CH2 in the liquid phase containing AMS and cylinder. It was supplied by Parr Instrument
cumene. Company. Pressure and temperature limits
Since rH2 on the solid volume terms is are 100 psi and 225 0C respectively. The
not directly measured, therefore the different sections of the experimental setup
conversion is required. discussed as below.
1 d nH
rH ,exp
= . 2
….. (10)
2
V dt 3.1 Reactor Section
Using the equation (10) follows an The reactor was offered in size of 300
expression for the diffusion inhibited ml with metal cylinder and heated using an
through pores of the solid volume related electrical heating tape wound externally to
reaction rate. the central portion of the reactor where the
r =
(1 − ε ) p dCH .V ….. (11) cat 2 catalyst was placed in the reactor for each
H 2 , exp . R
mcat dt
run. The reactor temperature was controlled
The following description for the thiele by temperature controller.
module is formed from equations (9), (10),
and (11): 3.2 Measuring devices
M =
2 d
.
(1 − ε ) p dC
2
cat
.V .
1
… (12) cat H 2 . int r .
1. Pressure gage
T R
36 m cat dt C H D eff
2
2. A 150 psi gage pressure with a T 316
A direct calculation of the measured stainless steel Bourdon tubes is mounted on
parameters is not possible, so the pores the reactor head using attachment fittings.
efficiency (η) which represent the ratio of 3. Thermocouple A J type
experimental and intrinsic reaction rate, thermocouple in a (1/8) inch diameter
calculated using the following equation:

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

stainless steel sheath is furnished with the Al2O3 particles. The advantage of the
reactor. This thermocouple is inserted into carrier material is its high porosity and in
the head of thermo well and connected to comparison with the active component, low
the thermocouple socket on the rear panel cost. The active layer consists of a
of the temperature controller. washcoat with palladium. The mass
3. Refractometer proportion of active component is 0.3 wt%
For analysis of the liquid samples, the in the used catalyst. Table (4) contains the
refractometer RE 40D Company Metter Characteristic of the used catalyst.
Toledo, was used. The measuring principles The catalyst porosity calculated using
based on the determination of the refractive the following equation:
indexes. The refractive index of the ε =
VL / mcat
(18)
 VL 1 
medium depends on its composition.  
m + ρ 
 cat s 
To calculate the weight percent of AMS
in the solution the following equation was And the catalyst density calculated by
used (Shuhaib 2008)):- following equation:-

wt AMS =
(n 0
[ ]
+ 0.0005 T 0 C − 20 − 1.4917)
(15)
ρ cat =
1
1
V
(19)
0.0474 + L
ρ s mcat
Further the following equation was used
to calculate the concentration of AMS
4. Intrinsic Kinetics of Hydrogenation
(Shuhaib 2008):-
of AMS
1 1
C AMS = . (16) Surface catalysis is involved in a large
Mwt 1 1 − wt% AMS 1
+
ρ wt% AMS ρ majority of industrial catalytic reactions.
And the conversion of AMS calculated The rate laws developed in this section are
by using the following equation:- based on the following assumptions:
C AMS − C AMS 1. The surface of the catalyst contains a
X AMS = 0
(17)
C AMS 0 fixed number of sites.
3.3 Chemical 2. All the catalytic sites are identical.
1. Liquid:- The liquid used in this work 3. The reactivity’s of these sites depend
is α-methylstyrene. The properties of AMS only on temperature.
and cumene can be seen in Tables (1 and These assumptions are based on the
2). simplest rational explanation of surface
2. Gas:- Two gases was used in the catalytic kinetics and models are formulated
present work which are hydrogen and by Langmuir and Hinshelwood (Missen et
nitrogen, the hydrogen properties can bee al., (1999)). Figure (2) represent
seen in table (3). Nitrogen was used only to Lamgmiur-Hinshelwood mechanism.
discharge the Oxygen in the reactor at start
of each experiment (Reactor flashing). 4.1 Languimer – Hinshelwood (LH)
3. Solid catalyst Kinetics
The catalyst which used in the present By combining surface – reaction rate
work is palladium with γ-Al2O3, The used lows with Langmuir expression for surface
catalyst consists of two-fabric system coverage, the Languimer-Hinshelwood
(carrier material and active component). (LH) rate lows for surface- catalyzed
The carrier material is nearly spherical γ- reactions can be obtained.

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

Although by focus on the intrinsic Where


kinetics of the surface-catalyzed reaction, KA =
KaA
, KH =
KaH 2

the LH model should be set the context of a KdA KdH 2

broader kinetics scheme to appreciate the -r1, -r2 are fast reaction then at
significance of this. equilibrium -r1 = -r2 = 0
A kinetics scheme for an overall Therefore from equation (20)
reaction expressed as below: C =K C C
A.S 1 A (23)A V 1

AMS + H2(g)→Cumene From equation (21)


A=AMS CH .S 2
= K H CH CV (24)
2 2 2 2

C=Cumene
Total concentration of sites vacance
As follows:-
Type 1 C = C + C T1
(25) V1 AS 1
A→A (surface vicinity), mass transfer
Substitution equation (23) into equation
(fast)
(25) will give
H2(g) → H2 (surface vicinity), mass
CT = CV + K AC ACV
transfer (fast) 1

C T = C V [1 + K A C A ]
A (surface vicinity)+S1 ←→ A.S1 Kd A
1 1

CT
∴ CV = (26)
[1 + K CA ]
1
adsorption–desorption (fast) 1
A

H2(surface vicinity)+S2 ←→ H2.S2


Type 2 CT = CV + C H (27)
Kd H 2
2 2 2 .S 2

adsorption–desorption
Substitution equation (24) into equation
A.S1 + H2.S2 → C + S1 + S2 surface
(27) will give:
reactions (slow)
C T = C V + C H .S
The reaction mechanism is derived 2 2 2 2

depending on the following assumptions: C T = C V2 [1 + K H C H ]


2 2 2

1. Reactant AMS and H2 is adsorped CT


CV =
[1 + K ] (28)
2

2
CH
on different vacancy and H2 adsorped as a H2 2

molecule. Sub. equations (23, 24) into equation


2. Surface reaction is limiting step (22) will give
(determining step). K 3 CT C T K H K A C H C A
− r3 =
[1 + K C A ] 1 + KH C H[ ]
1 2 2 2

3. Reaction products is not desorbed. A 2 2

Therefore K = K 3 C T CT 1 2

AMS – adsorption KK A K H C AC H
− r3 =
[1 + K C A ]1 + KH CH [ ] (29)
2 2

A + S1 ←→ A. S1
KdA
A 2 2

 C AS 
− r1 = KaA  C ACV − 
1
(20)
 K A  Also the other mechanisms for
H2 – adsorption hydrogenation of AMS are derived in same
H2 + S2 ←→ H2.S way by using different assumption, this
H dH 2

mechanisms can bee seen in table (5).


 C H .S 
− r2 = K aH C µ CV −  2
(21)
 KH 
2 2 2

 2
4.2 Catalyst activation
Surface reaction Activation means treating the catalyst to
A.S1+H2.S2 ←→ C+S1+S2 k− 3 S its full capacity before any experiment.
 C c CV CV  There are three options to activation
rg = K3 C A. S C H 2 .S2
− 
1 2
(22)
 
1
K3
(without activation, wet activation, and dry

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

activation). A wet activation means that the (Figure (5)). It can bee seen that at pressure
catalyst in a cumene liquid in the reactor up to 20 bar the reaction shows a first order
and the hydrogen was feed to it. The behavior in hydrogen. This type of behavior
disadvantage of this procedure is that the was anticipated and is common for
concentration of hydrogen in the liquid is hydrogenation reaction. At higher hydrogen
limited. For this reason, a dry activation pressure the reaction rate levels off. This
was used always, in dry activation the behavior of hydrogen on the catalyst
catalyst in the reactor and hydrogen was surface (in that case the reaction rate no
feed. The advantage of the dry activation is longer increases once the catalyst surface is
that the catalyst can be enabled for several fully occupied with hydrogen). Fitting such
tests. Langmuir-Hinshelwood expressions to the
Therefore, in this work a dry activation observed pressure dependency did not
is used. In figure (3) its clear the difference produce acceptable results. (Nijhuis et al.,
of the color between treated catalyst and (2003)).
untreated. All the mass transfer coefficients are
proportional to the hydrogen pressure, and
5. Results and discussion increasing hydrogen pressure will enhance
Table (6) contains all of the the mass transfer rates and then the reaction
experimental sets. rate.
5.1 Effect of temperature
Experiments have been performed at 5.3 Effect of catalyst loading and size
different temperatures (343-373 K0). From The measured reaction rate at
these experiments an Arrhenius plots has temperature (363 0K) is proportional to the
been constructed to determine the apparent catalyst weight (0.1 and 0.2 gm) of catalyst
activation energy of the reaction. (see experiment 7 and 13) and it can be
The rate in this figure is corrected using seen that the difference between them from
a first-order assumption for decreasing figure (6).
hydrogen pressure as a result of increasing The reaction rate was increased with
vapor pressure with temperature. For uses increasing the amount of catalyst, because
range, the reaction rate reaction increased the increasing in surface area for the
with increasing temperature because the reaction and increasing vacancy
mass transfer coefficients (KGL, KLS, KGS) concentration. The two experiments (5 and
are proportional directly to the diffusivity 15) at the same operating condition accept
and hence direct proportional to the the particle size of the catalyst was different
temperature. (4.28 and 37.36 μm). The rate of reaction
When temperature increases the reaction decreasing with increasing particle size
rate constant further increased, therefore the  1 
because of decreasing in surface are  aα 
reaction rate increase (see Figure 4).  dp 
where (a) is the surface area. The activity
5.2 Effect of pressure obtained with smaller particles was
Experiments were performed at different approximately 40% higher than that of the
hydrogen partial pressure to determine the larger catalyst particles (see Fig. 7).
reaction order for the reaction in hydrogen

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

Figure (9) represent a plot of sum of


5.4 Effect of stirring speed square error for each mechanism. The
Experiments (7 and 14) at the same experimental data with the greatest
operating condition but at different of correspondence was attained by two
stirrer speed (1400 and 1000 rpm) different expressions for the reaction
respectively. mechanism (mechanism 3 and 4, table 7).
Figure (8) show different reaction rates 7. Conclusion
at different stirrer speed. It can be seen that Hydrogenation of AMS on Pd is very
at a stirrer speed 1400 rpm the reaction rate fast reaction, and this leads to mass-transfer
is faster than that at 1000 rpm, indicating limitations, most often internal, or external.
that hydrogen dissolution were limiting the Therefore the stirrer speed is not
reaction. Increasing the stirrer speed give sufficiently affected on the reaction rate
high performance of mixing and there is no such as the other conditions (temperature,
concentration gradient and increasing pressure and catalyst weight).
solubility of hydrogenation AMS. In the present study, there are two most
represented kinetic expressions for AMS
hydrogenation as following.
6. Mechanism and kinetic mode kK A K H C AC A
(1 + K C )
− rAMS = 2 2

3
Based on the Langmuir-Hanshelwood A A + KH C H 2 2

theory and depending on the literature, kK A K H C AC A


(1 + K C )(1 + )
− rAMS = 2 2

2
various models were proposed to describe A A KH CH 2 2

the reaction mechanism. The mechanisms


These two mechanisms and there
vary in assumptions, such as number of
estimated parameters can be used in future
different activated catalyst sites, the status
to study the behavior of AMS
of hydrogen and the rate-controlling step.
hydrogenation in the monolith reactors or
The kinetic parameter estimation was
trickle bed reactors.
performed with the ACM (Aspen Custom
Modeler) software.
Notation
The Arrhenius equation represent the
C: Concentration (mol/m3)
dependence of the reaction rate constant K
D: Diffusivity (m2/s)
on the temperature. With this equation from
dp: Particle mean diameter (m)
two measuring points in different
Ea: Activation energy (J/mol)
temperatures the activation energy (EA) of
Kr: Rate constant (m/s)
the reaction was calculated.
Ko: Preexponential factor (m/s)
 E 
K = K 0 . exp  − A  (30) Ki: adsorption equilibrium constant of
 R.T 
component (-)
And to describe the adsorption the van't
KGL: gas-Liquid volumetric mass-
Hoff equation used. With this equation a
transfer coefficient (1/s)
correlation between temperature and
KLS: Liquid-Solid volumetric mass-
adsorption equilibrium constants Ki and
transfer coefficient (1/s)
change in enthalpy of adsorption ΔHads for
KGS: Gas-Solid volumetric mass-transfer
component i.
coefficient (1/s)
 ∆H ads 
K i = K i 0 . exp −  (31) MT: Thiele modulus (-)
 R.T 

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

LT: Particle size (m) [4] Cini, P., Harold, M. P. "Experimental


Mwt: Molecular weight (gm/mol) Study of the Tubular Multiphase
P: Pressure (bar) Catalyst", AIChE J., 37, 997, (1991).
r: rate of reaction (mol/s.kg.catalyst) [5] Chaudhari, R. V., Jaganathan, R.,
R: Gas law constant (J/mol·K) Kolhe, D. S., Emig, G. and Hofmann,
T: Temperature (K) H., "Kinetic modeling of a complex
V: Volume (m3) consecutive reaction in a slurry reactor:
wt%: Weight fraction (-) hydrogenation of phenyl acetylene",
X: Conversion (-) Chemical Engineering Science, 41(12):
Greek Letters 3073-81, (1986).
ε: Holdup [6] Frank, M. J. W., Kuipers, J. A. M.,
η: Catalyst effectiveness factor Versteeg, G. F., Van Swaaij, W. P. M.
ρ: Density (kg/·m3) "The performance of structure packings
Subscripts in tricklebed reactors", Trans. Inst.
AMS: α-methylstyrene Chem. Eng., 77, 567,( 1999).
cat: catalyst [7] Germain, A. H., Lefebvre, A. G.,
C: Cumene L’Homme, G. A. "Experimental Study
eff:effective diffusivity. of a Catalytic Trickle-Bed Reactor",
exp:experimental Chem. React. Eng., II, Chapter 13, 164,
G: gas (1974).
H: Hydrogen [8] Khadilkar, M. R., Wu, Y. X., Al-
Int: intrinsic Dahhan, M. H., Dudukovic, M. P.,
L: Liquid Colakyan, M. "Comparison of Trickle-
P: Particle Bed and Upflow Reactor Performance
Pd: Palladium at High Pressure: Model Predictions
R: Reactor and Experimental Observations",
S: Solid Chem. Eng. Sci., 51, 2139, (1996).
[9] Meille, V., de Bellefon, C. and
References Schweich, D., "Kinetics of a-
[1] Shuhaib A. A., "α–Methyl Styrene methylstyrene hydrogenation on
Hydrogenation In a Batch and Single Pd/Al2O3", Ind. Eng. Chem. Res.,
Channel Monolithic Reactors", Ph.D. 41(7): 1711–1715, (2002,).
Thesis (2008)
[10] Missen, R., Mims, Ch., and Saville, B.,
[2] Babcock, B. D.; Medjell, G. T., Hougen,
"Introduction to chemical reaction
O. A.,"Catalyzed Gas-Liquid Reactions
engineering and kinetics", Wiley J., and
in Trickling-Bed Reactors", AIChE J.
Sons, Inc., New York, (1999).
,3, 366, (1957).
[11] Mochizuki, S. and Matsui, T., "
[3] Bauer, T., Guettel, R., Roy., S.,
Selective hydrogenation and mass
Schubert, M., Al-dahhan, M. and
transfer in a fixed-bed catalytic reactor
Lange, R., "Modelling and Simulation
with gas-liquid concurrent upflow",
of the Monolithic Reactor for Gas-
A.1.Ch.E. J. 22, 904-909, (1976).
Liquid-Solid Reactions", Trans
[12] Lange, R.; Gutsche, R.; Hanika, J.
IChemE, Part A, (July 2005).
"Forced Periodic Operation of a

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

Trickle-Bed Reactor", Chem. Eng. Sci., [15] Herskowitz, M.; Morita, S.; Smith, J.
54, 2569, (1999). M. "Solubility of Hydrogen in R-
[13] Levenspiel, O., "Chemical Reaction Methylstyrene", J. Chem. Eng. Data,
Engineering", (3rd ed.). New York, 23, 227, (1978).
(1999). [16] White, D. E.; Litt, M.; Heymach, G.
[14] Nijhuis, T.A., Dautzenberg, F.M. and J. "Diffusion-Limited Heterogeneous
Moulijn, J.A., "Modeling of monolithic Catalytic Reactions on a Rotating Disk. I.
Hydrogenation of R-Methylstyrene", Ind.
and trickle-bed reactors for the Eng. Chem. Fundam. 13,143, (1974).
hydrogenation of styrene", Chem Eng
Sci, 58(7): 1113–1124, (2003).

Table (1) properties of AMS and cumene (Shuhaib(2008))


Property Symbol Unit AMS C
Moleculer weight Mwt g/mol 118.18 120.2
0
Boiling point TB K 438.5 425.6
0
Critical temperature Tc K 654 631.1
Critical pressure Pc bar 34 32.1

Table (2) AMS and C density as a function temperature (Shuhaib(2008)).


Property Component Unit Correlation
Density AMS g/l 920.89348 – 0.86311 T
Density C g/l 878.49298 – 0.83719 T

Table (3) hydrogen properties (Shuhaib(2008)).


Properties Sample Unit Quantity
Molecular weight Mwt g/mol 2
Acentric Factor ω - - 0. 218
Critical temperature TC Ko 33.2
Critical pressure PC Bar 13
Boiling point TB Ko 20.3
Critical molar volume υC Cm3/mol 60
Molar volume at normal pressure υ Cm3/mol 25.77
Relative temperature Trel K 0.61144

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

Table (4) Characteristic of catalyst

Active component Palladium (Pd)


Associated material γ – Al2O3
Palladium weight percent wt% 0.3
Specific area m2/g 210
Micro pore volume (r<10nm)[cm3/g] 0.71
Micro pore volume (10nm ≤ r ≤50nm)[cm3/g] 0.02
Micro pore volume (r>50nm)[cm3/g] 0.01
Catalyst density 0.58
Porosity (-) 0.74

Table (5) Variety of rate expressions for different assumptions


Entry Assumption Rate expression
1. A is adsorbed − rAMS =
kK A K H C AC H 2 2

(1 + K AC A )(1 + K H C H )
H2 is adsorbed (molecular) in different 2 2

2. A is adsorbed − rAMS =
kK A K H C AC A
2 2

(1 + K A C A + K H C H ) 2
H2 is adsorbed (molecular) 2 2

3. A is adsorbed − rAMS =
kK A K H C AC A 2 2

H2 is atomic desorbed (1 + K AC A + K H C H ) 3 2 2

4. A is adsorbed − rAMS =
kK A K H C AC A 2 2

H2 is atomic desorbed in different (1 + K AC A )(1 + K H C H ) 2 2 2

5. A is not adsorbed − rAMS =


kK H C AC H
2 2

H2 is atomic desorbed (1 + K H C H ) 2
2 2

6. A is not adsorbed − rAMS =


kK H C AC H
2 2

(1 + K H C H )
H2 is adsorbed (molecular) 2 2

7. A is adsorbed − rAMS =
kK A K H C AC H
2 2

(1 + K A C A )
H2 is not adsorbed
8. - kK AC A K H C H
− rAMS =
2 2

(1 + K AC A )(1 + K H C H ) 2 2

9. - kK AC A K H C H
− rAMS =
2 2

(1 + K AC A + K H C H ) 2 2 2

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

Table (6) Set of experiments


T(Co) P(bar) mcast(gm) n(rpm) VR(ml)
70 10 0.1 1400 200
70 15 0.1 1400 200
70 20 0.1 1400 200
80 10 0.1 1400 200
80 15 0.1(4.28 μm) 1400 200
80 20 0.1 1400 200
90 10 0.1 1400 200
90 15 0.1 1400 200
90 20 0.1 1400 200
100 10 0.1 1400 200
100 15 0.1 1400 200
100 20 0.1 1400 200
90 10 0.2 1400 200
90 10 0.1 1000 200
80 15 0.1(37.36 μm) 1400 200

Table (7) Kinetic parameters using (ACM) program

Entry Mechanism Kinetic Unit Quantity


parameter
1 − rAMS =
kK A K H C AC H
2 2
EA KJ/mol 34.059
(1 + K AC A )(1 + K H C H ) 2 2 Ko mol/gm.min 2.96764×107
∆H ads. A KJ/mol -14.6361
Ko A L/mol 1.94061×10-3
∆H ads. H 2
KJ/mol -1.9837×10-4
Ko H 2
L/mol 0.0914643
2 − rAMS =
kK A K H C AC A
2 2
EA KJ/mol 32.1518
(1 + K A C A + K H C H ) 2
2 2 Ko mol/gm.min 2.1015×107
∆H ads. A KJ/mol -16.1253
Ko A L/mol 1.30063×10-3
∆H ads. H 2
KJ/mol -0.0405814
Ko H 2
L/mol 0.0659305
3 − rAMS =
kK A K H C AC A
2 2
EA KJ/mol 34.427
(1 + K AC A + K H C H ) 2 2
3
Ko mol/gm.min 2.30198×107
∆H ads. A KJ/mol -17.4871
Ko A L/mol 1.35032×10-3
∆H ads. H 2
KJ/mol -0.0414532
Ko H 2
L/mol 0.067506
EA KJ/mol 39.2601

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

4 kK A K H C AC A
− rAMS = 2 2
Ko mol/gm.min 3.24741×107
(1 + K AC A )(1 + K H C H ) 2
∆H ads. A
2 2

KJ/mol -19.0777
Ko A L/mol 3.40568×10-3
∆H ads. H 2
KJ/mol -2.19613×10-4
Ko H 2
L/mol 0.0746463
5 − rAMS =
kK H C AC H
2 2
EA KJ/mol 38.0635
(1 + K H C H ) 2 2 2 Ko mol/gm.min 1.54852×107
∆H ads. H 2
KJ/mol -2.48624×10-4
Ko H 2
L/mol 0.0501713
6 − rAMS =
kK H C AC H
2 2
EA KJ/mol 40.8385
(1 + K H C H )
2 2 Ko mol/gm.min 2.74084×107
∆H ads. H 2
KJ/mol -1.6939×10-4
Ko H 2
L/mol 0.082637
7 − rAMS =
kK AC AC H EA KJ/mol 45.103
(1 + K CA )
2

A Ko mol/gm.min 2.1026×107
∆H ads. A KJ/mol -10.6116
Ko A L/mol 0.0309901

8 kK AC A K H C H EA KJ/mol 49.4625
− rAMS =
2 2

(1 + K AC A )(1 + K H C H ) 2 2
Ko mol/gm.min 3.00966×107
∆H ads. A KJ/mol -13.012
Ko A L/mol 0.017507
∆H ads. H 2
KJ/mol -0.00847844
Ko H 2
L/mol 0.570943
9 kK AC A K H C H EA KJ/mol 46.0789
− rAMS =
2 2

(1 + K AC A + K H C H ) 2 2
2 Ko mol/gm.min 4.98754×107
∆H ads. A KJ/mol -8.09857
Ko A L/mol 0.0248671
∆H ads. H 2
KJ/mol -4.76242
Ko H 2
L/mol 0.0355481

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

Figure (1) Experimental set-up.

Figure (2) Lamgmuir-Hinshelwood- mechanism. (Missen et al. 1999)

0.8
Conversion [-]

0.6

T=100 C
0.4 T=90 C
T=80 C
0.2 T=70 C

0
0 10 20 30 40 50 60 70 80
Time [min]

Figure (3) catalyst, right hand (treated) –Left (untreated)

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

1.00

0.80
Conversion [-]

0.60

P=30 bar
0.40 P=20 bar
P=15 bar
0.20 P=10 bar

0.00
0 10 20 30 40 50 60 70 80
Time [min]

Figure (4) Effect of temperature on conversion (P=10 bar, RS=1400, Mcat=0.1 gm)

0.8
Conversion [-]

0.6

0.4

Mcat=0.2 gm
0.2 Mcat=0.1

0
0 5 10 15 20 25 30 35 40
Time [min]

Figure (5) Effect of pressure on conversion for STR


(T=80 C , S.S=1400 rpm , Mcat=0.1 gm)

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

0.8
Conversion [-]

0.6

0.4

Mcat=0.2 gm
0.2 Mcat=0.1

0
0 5 10 15 20 25 30 35 40
Time [min]

Figure (6) Effect of mass of catalyst on conversion for STR


(P=20 bar, T=80 C, S.S=1400 rpm)

1.00

0.80
C o n versio n [-]

0.60

0.40

dp=4.28"
0.20
dp=37.36"

0.00
0 10 20 30 40 50 60 70 80
Time [min]
Fig. (7): Effect of particle diameter on conversion for STR
(P=15 bar, T=80 C, S.S=1400)

Figure (7) Effect of particle diameter on conversion for STR


(P=15 bar, T=80 C, S. S=1400)

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Eng.& Tech. Journal ,Vol.27, No.7, 2009 Reaction Kinetic of α -methylstyrene
(AMS) Hydrogenation

0.8
Conversion [-]

0.6

0.4 Stirrer speed=1400 rpm

Stirrer speed=1000 rpm


0.2

0
0 10 20 30 40 50 60 70 80
Time [min]

Figure (8) Effect of stirrer speed on conversion for STR


(P=10 bar, T=90 C, Mcat=0.1 gm)
0.9

0.8

0.7 Figure (8) Effect of stirrer speed on conversion for STR


Sum of square error

0.6
(P=10 bar, T=90 C, Mcat=0.1 gm)

0.5

0.4

0.3

0.2

0.1

0
1 2 3 4 5 6 7 8 9
Mechanism No.

Figure (9) Sum of the square error vs mechanism

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