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Catalysis, Structure & Reactivity

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Kinetic study of alkylation of benzene with ethanol


over bimetallic modified HZSM-5 zeolite catalyst
and effects of percentage metal loading

Abdi Nemera Emana & Shri Chand

To cite this article: Abdi Nemera Emana & Shri Chand (2016) Kinetic study of alkylation
of benzene with ethanol over bimetallic modified HZSM-5 zeolite catalyst and effects
of percentage metal loading, Catalysis, Structure & Reactivity, 2:1-4, 13-24, DOI:
10.1080/2055074X.2016.1198545

To link to this article: https://doi.org/10.1080/2055074X.2016.1198545

© 2016 The Author(s). Published by Informa


UK Limited, trading as Taylor & Francis
Group

Published online: 12 Jul 2016.

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Original Research Paper

Kinetic study of alkylation of benzene with


ethanol over bimetallic modified HZSM-5
zeolite catalyst and effects of percentage
metal loading
Abdi Nemera Emana* and Shri Chand

Department of Chemical Engineering, Indian Institute of Technology Roorkee, Roorkee, Uttarakhand 247667, India

Abstract  Alkylation of benzene with ethanol was analyzed using shape selective boron– C2H5OH
+
C2H5

magnesium bimetallic HZSM-5 (Si/Al = 90) zeolite catalyst. The alkylation of benzene with ethanol HZSM-5 - H2O
+ O
(a)
(b)

(2:1 by volume) produces ethylbenzene as primary product and others like 1, 2-Diethylbenzene, C2H5

1, 4-Diethylbenzene, and xylene mixtures as secondary products. The physiochemical properties Reactants O +

of catalyst were characterized by XRD, BET, TGA, FTIR, NH3-TPD, and FE-SEM. The feed
(c)
and products were analyzed by gas chromatography and mass spectroscopy. B–Mg bimetallic C2H5

catalysts supported on HZSM-5 zeolite catalyst with SAR = 90 were synthesized by the incipient H

wetness impregnation method and examined for alkylation of benzene with ethanol. Total
C2H5 + O

metal loading of 5, 10, and 15% was used for catalyst synthesis. The highest selectivity of
(d)

ethylbenzene (76.22%) was obtained by (Mg + B)-15%-HZSM-5 and the lowest ethylbenzene


+
H
Ethylbenzene

selectivity (49.15%) was obtained by (Mg + B)-5%-HZSM-5 using 2:1 benzene-to-ethanol ratio O

by volume. A reaction scheme with three parallel routes leading to the formation of ethylbenzene,
diethylbenzene, and triethylbenzene was considered for the kinetic study. The kinetic parameters were determined using
Langmuir–Hinshelwood–Hougen–Watson (LHHW)-type kinetic model. LHHW model could satisfactorily correlate the rate
data and this model gives good fit between the experimental and calculated data.

Graphical abstract  Possible mechanism for benzene alkylation with ethanol to form ethylbenzene.
Keywords  Alkylation, HZSM-5, Benzene, Ethanol, Ethylbenzene
Cite this article  Abdi Nemera Emana and Shri Chand: Catal. Struct. React., 2016, 2, 13-24

Introduction and synthetic) is estimated to be about 5 million tons per


year. The annual market for synthetic zeolites and molecular
Porous solids with pores of the size of molecular dimensions, sieves was developed vastly to 1,800,000 ton worldwide in
0.3–2.0 nm in diameter are called molecular sieves. Examples 2008.3
include zeolites, carbons, glasses, and oxides. Some are crys- Alkylation of benzene is a vital reaction in the petrochem-
talline with a uniform pore size and more described in detail ical industry. Benzene alkylation technologies offer improve-
by their crystal structure, for example, zeolites.1 ments in octane number and gasoline volume. Ethylbenzene,
Zeolites are so special when compared to other crystalline diethylbenzene, toluene, and xylenes are important raw mate-
inorganic oxide materials due to a combination of the following rials for many intermediates of commodity petrochemicals
properties: the microporous character with uniform pore dimen- and valuable fine chemicals.
sions, allowing certain hydrocarbon molecules to enter the crys- Ethylbenzene (EB), which is one of the most important
tals while rejecting others based on too large a molecular size, products used as the chemical intermediate, is the main feed-
the ion-exchange properties which allow to perform all sorts of stock for the synthesis of styrene which is then polymerized
ion exchange reactions, the ability to develop internal acidity into polystyrene, a common plastic material.4 Ethylbenzene
which makes the zeolites interesting materials for catalyzing is also used in the chemical industry in the manufacture of
organic reactions, and the high thermal stability of the zeolites.2 acetophenone, cellulose acetate, diethylbenzene (DEB), ethyl
According to International Zeolite Association (2014), until anthraquinone, ethylbenzene sulfonic acids, propylene oxide,
now, there are 218 zeolite framework type codes that have and α-methylbenzyl alcohol.5 Additionally it is used as a sol-
been discovered. Worldwide consumption of zeolites (natural vent, a constituent of asphalt and of naphtha, and in fuels.
Ethylbenzene and xylene mixtures are used in the paint indus-
*Corresponding author, email abdihpch@iitr.ac.in try and in the production of pesticides in agriculture.5

© 2016 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group.
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted
use, distribution, and reproduction in any medium, provided the original work is properly cited.
Received 29 March 2016; accepted 31 May 2016
DOI 10.1080/2055074X.2016.1198545 Catalysis, Structure & Reactivity  2016   VOL. 2   NOS. 1–4 13
Emana and Chand  Kinetic study of alkylation of benzene with ethanol over bimetallic modified HZSM-5 zeolite catalyst and effects of percentage metal loading

+
C 2 H5
ethanol over bimetallic-modified HZSM-5 zeolite catalyst and
C2H5OH
effects of percentage metal loading.
HZSM-5 - H2O
+ O Experimental
(a)
(b)
Materials
C2H5
The chemicals and gases used in the experiments were
obtained from different manufacturers and suppliers. ZSM-5
Reactants O +
zeolite in protonic and powder form with SAR-90 was obtained
from Sud-Chemie India Pvt. Ltd. Benzene used in the experi-
ments was >99% pure. Boric acid (99.5% pure) and benzene
for the present study were obtained from RFCL limited, New
(c)
Delhi, India. Pure ethanol (99.9%) was supplied by Merck
KGaA, Germany. Magnesium nitrate (99% pure) was supplied
C 2 H5 by HiMedia laboratories Pvt. Ltd. Mumbai, India.

H
Catalyst preparation
C2H5 + O
HZSM-5 SAR = 90 obtained from Sud-Chemie India Pvt. Ltd
was in protonic form so that no further transformation activ-
(d) ities were done except catalyst was calcined at 550 °C for 5 h
to be activated. Boron–magnesium bimetallic catalysts were
+ prepared by the incipient wetness impregnation method. In
H
Ethylbenzene this method, desired amount of metal precursors (H3BO3 and
Mg(NO3)2·6H2O) were dissolved in deionized water and cal-
O culated amount of HZSM-5 zeolite catalyst was added to this
solution under stirring. Total metal loading for bimetallic cata-
lysts was as 5, 10, and 15 wt%. The zeolite powder so obtained
Figure 1  Possible mechanism for benzene alkylation with
was pelletized at 10 tonne/cm2 pressure and broken into small
ethanol to form ethylbenzene
pieces in the size range of 0.3–0.5 mm. The fraction in this size
range was used in the reactor for the activity test runs.
Several researchers have proposed the alternative catalytic
reaction pathways for the production of ethylbenzene. The
catalytic reaction which uses ethanol for benzene alkylation, Experimental setup
instead of ethene, would eliminate the ethene production step The catalytic experiments were carried out in a fixed bed;
and, therefore, leading to the commercial and environmen- continuous down flow tubular quartz (0.6-cm I.D and
tal benefits in the ethylbenzene manufacturing.6 In addition 66-cm long) reactor placed inside a microprocessor-con-
to the intrinsic scientific interest, the direct use of ethanol trolled furnace (Metrex Scientific Instruments Pvt. Ltd, New
(instead of ethene) in the manufacture of ethylbenzene also Delhi) which was preceded by a pre-heater and followed
has economic significance in those countries like Brazil and by a condenser. The same reactor tube was used in all the
India, where biomass-derived alcohol is an additional feed- experiments. In a typical run, about 0.7 g of catalyst (which
stock for the manufacture of chemicals (see Fig. 1). occupied 6 cm height of the reactor) was charged into the
Several studies have been reported regarding benzene reactor and the reaction was carried out at atmospheric
alkylation using unmodified zeolites like HZSM-5, Beta, HY, pressure using bimetallic HZSM-5 catalyst. The catalysts
mordenite, TNU-9, SSZ-33, ZSM-12, MCM-22, and ITQ-227–12 activated for one hour in an atmosphere of nitrogen before
as well as HZSM-5 modified with phosphorous and boron.6 the experimental runs were started. The benzene ethanol
Venuto et al.9 had shown that although Linde-type X and Y mixture of 2:1 ratio introduced with the help of a metering
zeolites exchanged with rare earth ions catalyze the alkylation pump at rate of 0.4 ml/min and vaporized in the pre-heater
of benzene with ethanol, the catalyst aging was severe leading before contacting the catalyst. The reactant vapors along
to catalyst deactivation in a few hours. Junhui Li et al.13 had with nitrogen entered the reactor, which was electrically
performed alkylation of benzene with ethanol for the synthe- heated. The flow rate of the nitrogen carrier gas was 0.5 lit-
sis of ethylbenzene over parent zeolites and zeolites modified ers per minute. The products vapors, along with unreacted
with La2O3, such as HMCM-22, HBeta, and nano HZSM-5. reactants, were condensed in the condenser and the liquid
In the reaction of converting benzene to ethylbenzene, samples collected were analyzed in a gas chromatograph
HZSM-5 zeolite has been used as a catalyst. It is well known and mass spectroscopy with a 30 m × 0.32 mm (0.25 μm film
that the alkylation reaction of benzene in the presence of an thickness) Elite-1 capillary column (Perkin Elmer) using a
acid catalyst belongs to a carbenium ion type mechanism. The flame ionization detector (FID). The program used was as
alkylation of benzene with ethanol produces ethyl benzene as follows. Initial oven temperature was 70  °C then held for
primary product and others like diethylbenzene and xylene 2 min. After that the temperature was increased to 200 °C
mixtures as secondary products (see Fig. 2). This research with a ramp rate of 10 °C/min. Again it stayed at 200 °C for
focused on the kinetic study of alkylation of benzene with 1 min. The Detector and Injection temperature was 250 °C.

14 Catalysis, Structure & Reactivity  2016   VOL. 2   NOS. 1–4


Emana and Chand  Kinetic study of alkylation of benzene with ethanol over bimetallic modified HZSM-5 zeolite catalyst and effects of percentage metal loading

+
C2H5
C 2 H 5OH
HZSM-5 - H 2O
+ O
(a)
(b)

C2H 5

Reactants O +

(c)

C2H5

H
C 2H 5 + O

+
(d)
C2H 5 +
(e)
+
O H
Ethylbenzene

O
C 2H 5
C2H 5

+ O C 2H 5

(f)
C 2H 5
Diethylbenzene
+
H

Figure 2  Possible mechanism for benzene alkylation with ethanol to form diethylbenzene

Flow rate of air, hydrogen, and nitrogen were 450, 45, and Surface Area and Porosimetry (ASAP-2020) system. Prior to
45 ml/min, respectively. Nitrogen was used as carrier gas the analysis, the samples were degassed at 250  °C for 8  h
and the split ratio was 1:50. From gas chromatography under vacuum. The surface area of all the samples was ana-
results, the selectivity and yield of ethylbenzene in the lyzed employing the multi point Brunauer–Emmett–Teller
product were calculated. The conversion of benzene was (BET) method using adsorption data at the relative pressure
also noted for bimetallic HZSM-5 catalysts (Fig. 3). (P/Po) range of 0.05–0.3. Pore size distribution was determined
using the Barret–Joyner–Halenda (BJH) method considering
the desorption branch.
Catalyst characterization X-ray diffraction (XRD) analysis was performed in order to
The catalysts were characterized by various methods including determine the phase structure of the catalyst and crystallinity.
surface area measurement, X-ray diffraction, temperature- The spectra were recorded with a Bruker AXS D8 advance dif-
programmed desorption, inductive-coupled plasma-mass fractometer using Cu-Kα monochromatized radiation source
spectroscopy, scanning electron microscopy, and transmission (λ = 1.5418 Å), Ni filter, and 40 kv at the two theta interval of
electron microscopy. 5–50° with scan speed of 1°/min. The average crystallite size of
N2 adsorption–desorption isotherm measurements were the catalysts was determined using Scherrer formula (D = 0.90
performed at −196  °C using a Micrometrics Accelerated λ/β cos θ, where β is the full width at half-maximum height

 Catalysis, Structure & Reactivity  2016   VOL. 2   NOS. 1–4 15


Emana and Chand  Kinetic study of alkylation of benzene with ethanol over bimetallic modified HZSM-5 zeolite catalyst and effects of percentage metal loading

Branch Fitting

Benzene + Ethanol TC
T
Heater

Reactor
Computer
Valve

Pump

Hot Water

Cold Water
Nitrogen Cylinder GC-MS
Condenser

Figure 3  Schematic diagram of temperature-controlled down flow tubular reactor used for alkylation of benzene with ethanol

(FWHM) and θ is the diffraction angle from the line width of a Tecnai G2 20 S-Twin (FEI Netherland) microscope equipped
the respective XRD peaks. with EDAX. The samples were prepared by dispersing in abso-
The acidic properties of catalysts were measured by ammo- lute ethanol using an ultrasonic bath and evaporating a drop
nia temperature-programmed desorption (NH3-TPD). NH3-TPD of resultant suspension onto the carbon-coated copper grid.
measurements in the temperature range from room temper- Infrared spectra were obtained at 4  cm−1 resolution on
ature to 650 °C were performed in Micromeritics ChemiSorb Nicolet 6700 series FTIR Spectrometer. The infrared cell used
2720 equipped with a TCD. Prior to each experiment, zeolite was fitted with KBr windows. A sample of the zeolite powder
catalyst samples were put in a quartz cell with U shape and was accurately weighed and mixed with around 300 mg KBr
pretreated, in situ, for 1 h at 250 °C in a flow of nitrogen (>99%) and then passed into a 10 mm diameter wafer at 15 tonnes/
of 20 ml/min. After cooling to 25 °C, adsorption of ammonia cm2 pressure. This wafer was placed in the IR cell. The IR cell
was carried out in a flow of ammonia and helium mixture of spectra were recorded at room temperature in air. Background
40 ml/min. After the catalyst surface became saturated, it was IR correction for air was also made.
kept for some time to remove the excess of ammonia. The Thermogravimetric analysis was conducted in order to
temperature-programmed desorption was carried out with determine the thermal stability of the zeolite framework and
a linear heating rate of approximately 10 °C/min from 25 to weight loss occurring from zeolite lattice during heating. TGA
650 °C in a flow of helium (>99%) of 20 ml/min. The NH3 that was conducted on SII 6300 EXSTAR using air as carrier gas
desorbed was measured by a thermal conductivity detector. at 200  ml/min on a 10  mg of sample. The TGA of modified
Total B and Mg metal contents in prepared catalysts were and unmodified HZSM-5 heated from ambient temperature
determined by inductive-coupled plasma-mass spectrometer to 1000 °C in temperature progression of 10 °C/min has been
(ICP-MS). Approximately 15 mg of catalyst and 2 ml of aqua done.
regia (0.5 ml nitric acid and 1.5 ml of hydrochloric acid) were
placed together in a 15 ml glass vial fitted with a Teflon lined Results and discussion
cap, and digested in an oven at 100 °C for 2 h. Then the samples
Effect of physicochemical properties
were prepared by dilution with Millipore water to required
concentrations (<1 ppm). Perkin–Elmer Elan DRC-e ICP-MS was X-ray diffraction
used for the elemental analysis. XRD patterns of magnesium–boron bimetallic HZSM-5 zeo-
To explore the morphology and composition of the cata- lite catalysts are given in Fig. 4. X-ray powder diffraction was
lysts, scanning electron microscopy (SEM) images were col- employed to determine the value of relative crystallinity (RC).
lected using Quanta scanning electron microscope (Model The commercial zeolite, HZSM-5 was assumed to have 100%
200 PEG, USA) equipped with energy dispersive X-ray spectra crystallinity. The determination of the value was based on the
(EDX). Catalyst sample was dispersed uniformly on the sample area of the characteristic peaks in the 2θ range from 22.5° to
holders and coated with gold using sputter coater (Edwards 25°. XRD analysis was carried out using powder diffractometer
S150) and then SEM images were taken at an acceleration (Bruker D8) at Institute Instrumentation Centre (IIC), Indian
voltage of 20  kV under vacuum. The morphologies of pre- Institute of Technology Roorkee. Cu-Kα (λ = 1.5417 Å, 40 kv
pared catalysts were also analyzed by transmission electron and 30 mA) was used as anode material and the range of scan-
microscopy (TEM). TEM investigations were carried out using ning angle (2θ) was kept between 5° and 50° with scan speed

16 Catalysis, Structure & Reactivity  2016   VOL. 2   NOS. 1–4


Emana and Chand  Kinetic study of alkylation of benzene with ethanol over bimetallic modified HZSM-5 zeolite catalyst and effects of percentage metal loading

Figure 4  X-ray Diffraction patterns of unmodified and


magnesium–boron-modified HZSM-5 zeolite (SAR = 90)

Figure 5  TGA graphs of magnesium–boron-modified and


unmodified HZSM-5 zeolite
Table 1 Relative crystallinity and crystal size of magnesi-
um–boron-modified and unmodified HZSM-5 (SAR = 90)

Table 2 Percent weight loss of magnesium–boron bimetal-


Crystal Relative lic-modified and unmodified HZSM-5 zeolite catalysts from
No Type of catalyst size (Å) crystallinity (%) ambient temperature to 1000 °C
1 HZSM-5 12.9 100
No Name of catalyst Weight loss (%)
2 (Mg + B)5%-HZSM-5 12.9 106.8
3 (Mg + B)10%-HZSM-5 12.9 100.2 1 HZSM-5 (SAR=90) 5.1
4 (Mg + B) 15% B-HZSM-5 12.9 63.0 2 (Mg + B)-5%-HZSM-5 6.6
3 (Mg + B)-10%-HZSM-5 7.5
4 (Mg + B)-15%-HZSM-5 7.6

of 2θ  =  1º/min. The powder XRD patterns (Fig. 4) of all the


four samples exhibited well-resolved diffraction peaks, which Thermogravimetric analysis
were characteristic of the MFI framework structure. The high Thermogravimetric analysis of HZSM-5 modified by bimetal-
intensity of peaks in the XRD patterns indicated that the zeo- lic magnesium–boron is shown in Fig. 5. Thermogravimetric
lite samples were highly crystalline materials and the highest analysis was conducted in order to determine the thermal
diffraction peaks were seen at 2θ = 23°. There was no mismatch stability of the zeolite framework and weight loss occurring
in the pattern of peaks for all the samples in Fig. 4, so no other from zeolite lattice during heating. TGA was conducted on SII
phase formations have been found. 6300 EXSTAR instrument using air as carrier gas at 200 ml/min
As we can see from Table 1, the crystal size of the modified on a 10 mg of sample. Figure 5 presents the TGA of modified
and unmodified HZSM-5 was the same but the relative crys- and unmodified HZSM-5 heated from ambient temperature to
tallinity was higher for (Mg + B)5%-HZSM-5 and (Mg + B)10%- 1000 °C in temperature progression of 10 °C/min. The portion
HZSM-5, while the lower relative crystallinity was observed for of the curve up to 100 °C is normally linked with the weight
(Mg + B)15%-HZSM-5. loss due to moisture content of the catalyst, whereas, the por-
The average crystal sizes were estimated using the Scherrer tion of the curve from 100 to 1000 °C is assigned to the weight
equation. loss due to the removal of hydrocarbon, moisture contained
k𝜆 inside the pores, and coke formation. From the experimen-
D= (1) tal investigation, it is seen that high percent weight loss is
𝛽 cos 𝜃
demonstrated by magnesium-boron modified catalysts. As
where D is the crystal size, k is a constant (0.99), λ is the X-ray the amount of percent metal loading is increased the weight
wavelength (λ = 0.1542 nm), β the peak width at a half-height lost by the catalysts is also increased, particularly at higher
(in radians), and θ is the Bragg’s angle of diffraction. temperatures as shown in the Table 2.
Hs
%XRD Relative Crystallinity of HZSM − 5 = × 100% FTIR analysis
Hr (2)
Infrared spectra were obtained at 4 cm−1 resolution on Nicolet
where Hs = peak height for the sample, and Hr = peak height 6700 series FTIR Spectrometer. The infrared cell used was fit-
for the reference sample. ted with KBr windows. A sample of the zeolite powder was

 Catalysis, Structure & Reactivity  2016   VOL. 2   NOS. 1–4 17


Emana and Chand  Kinetic study of alkylation of benzene with ethanol over bimetallic modified HZSM-5 zeolite catalyst and effects of percentage metal loading

Figure 7  Ammonia Temperature-Programmed Desorption


(NH3-TPD) of magnesium–boron-modified and unmodified
HZSM-5 (SAR = 90) zeolite
Figure 6  FTIR Spectra of bimetallic magnesium–boron-
modified and unmodified HZSM-5 (SAR = 90) zeolite
of HZSM-5 has decreased after modification with bimetallic
magnesium–boron. This may be due to the deposition of
accurately weighed and mixed with around 300 mg KBr and bimetals on the outer surface of the catalyst deactivating the
then passed into a 10 mm diameter wafer at 15 tonnes/cm2 active sites. A significant change in acidic sites was observed
pressure. This wafer was placed in the IR cell. The IR cell spec- for (Mg + B)-15%-HZSM-5 zeolite catalysts.
tra were recorded at room temperature in air. Background IR Strong acid sites are the main cause for alkylation reaction.
correction for air was also made. If they exist on the surface of catalysts in large quantity they
The IR structural studies of zeolite have been carried out in facilitate further alkylation of ethylbenzene with ethanol to
the infrared region of wave number 400–4000 cm−1, because diethylbenzene and other undesired products. So that it is
fundamental vibrations of SiO4, AlO4, or TO4 units are contained desirable to reduce the amount of strong acid sites. There is a
in this region. In the KBr pellet technique, a small amount of shift in peak temperature for curve (b) (Fig. 7) due to reduction
the solid sample was mixed with powdered KBr and pressed in strong acidic sites and emerging of weak acid sites due to
into pellet. metal loading (Table 3).
The band at (i) 545 cm−1 is assigned to the highly distorted
double five membered rings present in the ZSM-5 structure, Field emission scanning electron
(ii) 3739, 3660, and 3490 cm−1 are assigned to weak, medium,
microscope
and strong Brønsted acid sites, respectively, (iii) 1700 cm−1 to
The morphology of the zeolite samples was evaluated by Field
water bond, (iv) 800 cm−1 to Al–O bond, and (v) 1350 cm−1 to
Emission Scanning Electron Microscope (FE-SEM) using ULTRA
Si–O–Si bond, etc (Fig. 6).
plus. Scanning Electron Microscopic images of the samples
are shown in Fig. 8.
Ammonia temperature-programmed
desorption (NH3-TPD) BET surface area
The ammonia temperature-programmed desorption was con- Table 4 shows the surface area and pore volume of unmodi-
ducted according to the procedure stated in section Catalyst fied and modified HZSM-5 zeolite catalysts. The surface area of
characterization. From the NH3-TPD experiments (Fig. 7), it HZSM-5 (SAR = 90) was 347 m2/g. It can be found from Table 4
could be concluded that two types of acid sites were present that the surface area of support was reduced significantly after
in H-ZSM-5: weak acid sites corresponding to desorption at metal impregnation. Among the modified support catalysts,
low temperature and strong acid sites corresponding to des- the surface area of (Mg + B)-5%-HZSM-5 catalyst was high-
orption at high temperature. It was observed that the acidity est (318 m2/g) and the surface area of (Mg + B)-15%-HZSM-5

Table 3 Ammonia Temperature-Programmed Desorption (NH3-TPD) of magnesium–boron-modified and unmodified HZSM-5


(SAR = 90) zeolite

No. Type of catalyst Weak acid sites conc. (mmol/g) Strong acid sites conc. (mmol/g)
1 HZSM-5 (SAR=90) 2.21 6.80
2 (Mg + B)-5%-HZSM-5 3.49 5.05
3 (Mg + B) −10%-HZSM-5 6.99 0.74
4 (Mg + B) −15%-HZSM-5 0.67 2.03

18 Catalysis, Structure & Reactivity  2016   VOL. 2   NOS. 1–4


Emana and Chand  Kinetic study of alkylation of benzene with ethanol over bimetallic modified HZSM-5 zeolite catalyst and effects of percentage metal loading

Figure 8  Fe-SEM image of bimetallic and unmodified HZSM-5 zeolite catalyst

Table 4 BET surface area of different types of HZSM-5 (SAR = 90) catalysts

Type of catalyst BET surface area External surface area Total pore volume Average pore width
(m2/g) (m2/g) (cm3/g) (4V/A by BET) (Å)
Unloaded HZSM-5 347 144 0.34 24.15
(Mg+B)-5%-HZSM-5 318 125 0.30 24.44
(Mg+B)-10%-HZSM-5 285 108 0.21 24.53
(Mg+B)-15%-HZSM-5 268 87 0.19 24.70

catalyst was the lowest (268 m2/g). Total pore volume of the ethylbenzene, p-xylene, m-xylene, o-xylene, and diethylben-
unmodified HZSM-5 zeolite catalysts was also reduced after zene. The gaseous products contained negligible amount of
modification. This may be due to the deposition of metal cat- hydrocarbon gases (ethane, methane, ethylene, etc.).
ions used for modification. The following equations were used to check the activity
of the catalysts:
Performance of bimetallic and unmodified
Benzene conversion %XB
( )
HZSM-5 (SAR = 90) catalyst (3)
Moles of benzene converted
In the present study, the performances of HZSM-5 catalyst with = × 100
Moles of benzene in the feed
a silicon-to-aluminum ratio of 90 for the alkylation reaction of
Ethylbenzene yield %YEB
( )
benzene with ethanol were studied. Experiments were carried
out in a fixed catalytic bed down flow reactor at a constant feed Moles of ethylbenzene obtained (4)
(benzene and ethanol mixture 2:1 by volume) rate of 0.4 ml/ = × 100
Moles of benzene converted
min and a carrier gas (N2) flow 0.5 liters per minute (lpm). The
WHSV of benzene and ethanol mixture as feed was 32.6 h−1. Ethylbenzene selectivity %SEB
( )

Nitrogen was used as carrier gas to activate the catalyst. The Moles of ethylbenzene(desired product) formed
products of the reaction were analyzed by gas chromato- = × 100
Moles of all products formed
graph. Liquid products contained benzene, ethanol, toluene, (5)

 Catalysis, Structure & Reactivity  2016   VOL. 2   NOS. 1–4 19


Emana and Chand  Kinetic study of alkylation of benzene with ethanol over bimetallic modified HZSM-5 zeolite catalyst and effects of percentage metal loading

Figure 9  Yield of ethylbenzene by bimetallic modified and


unmodified HZSM-5 SAR = 90 for benzene-to-ethanol ratio 2:1
Figure 11  Conversion of benzene by bimetallic modified and
unmodified HZSM-5 SAR = 90 for benzene-to-ethanol ratio 2:1

facilitates further reactions. The highest conversion of benzene


was under taken by unmodified HZSM-5. When we compare
bimetallic-modified HZSM-5 zeolite catalysts, the highest
metal loading gave best result in terms of selectivity of ethylb-
enzene while the lowest metal loading is best in terms of yield
of ethylbenzene and benzene conversion. These results are
related with the physicochemical properties of the catalysts
such as pore size and surface acidity. Pore size, surface area,
and total acidity of catalysts decreased as percentage metal
loading increased.

Kinetic study
This section discusses the kinetic study of alkylation reaction
of benzene with ethanol over (B–Mg)-15%-HZSM-5 zeolite cat-
alyst. The kinetic experiments were carried out in the presence
Figure 10  Selectivity of ethylbenzene by bimetallic modified of (B–Mg)-15%-HZSM-5 catalyst since it was the most active
and unmodified HZSM-5 SAR  =  90 for benzene-to-ethanol and selective catalyst among all the catalysts examined. The
ratio 2:1 kinetic experiments of the alkylation of benzene with ethanol
were carried out in fixed bed tubular reactor in the tempera-
ture range from 300 to 500 °C and atmospheric pressure. The
From our experimental investigation, we were observed that kinetic study was done using different weight hour space
when HZSM-5 zeolite catalyst modified by different percent- velocities from 5 to 32.6  h−1. Nitrogen to feed ratio 4.2 and
age metal loading, it affects performance of the catalysts such feed ratio (benzene to ethanol) 2:1 were used. The reaction
as yield, selectivity, and conversion. From our previous work, data were used to calculate the initial reaction rate and acti-
we had seen that bimetallic boron–magnesium modified is vation energy. The kinetic model used to fit the data was the
better than monometallic either boron or magnesium-modi- Langmuir–Hinshelwood–Hougen–Watson (LHHW) model.
fied HZSM-5.14 For this reason, this work focuses on the kinetic
study of bimetallic-modified HZSM-5 and effect of percentage
Kinetic model development
metal loading. The performances of bimetallic modified and
unmodified HZSM-5 catalyst for a benzene-to-ethanol ratio 2:1 Langmuir–Hinshelwood–Hougen–
by volume are shown in Figs. 9–11. It was observed that the Watson (LHHW) model
highest yield of ethylbenzene (45.03%) was obtained at 450 °C Reaction mechanism for alkylation of benzene with ethanol
using unmodified HZSM-5. However, the highest ethylben- can be represented by the following steps which are used to
zene selectivity (76.22%) was observed when the catalyst was derive the rate equations.
modified with (Mg + B)-15%-HZSM-5. This happened due to Step 1: Adsorption
decrease in pore size and surface acidity of the catalyst which Adsorption of ethanol (E) on the surface of vacant sites (S):

20 Catalysis, Structure & Reactivity  2016   VOL. 2   NOS. 1–4


Emana and Chand  Kinetic study of alkylation of benzene with ethanol over bimetallic modified HZSM-5 zeolite catalyst and effects of percentage metal loading

C C k7
( )
k1
E + S ⇌ E.S −r7 = k7 CDEB.S − DEB S , K7 =
( )
(6)
k−1 K7 k−7 (20)
Adsorption of benzene (B) on the surface of the vacant sites (S):
k2 C C k8
( )
B + S ⇌ B.S −r8 = k8 CTEB.S − TEB S , K8 =
( )
(7) (21)
k−2 K8 k−8
Step 2: Surface Reaction where K1, K2, K3, K4, K5, K6, K7, and K8 are the equilibrium con-
Surface reaction between adsorbed ethanol and benzene stants for respective reactions.
on the active surface of catalysts is presented by It is assumed that the surface reaction is the rate
k3
controlling step, and then the rate of surface reactions are
E.S + B.S ⇌ EB.S + W.S (8) given as follows,
k−3
From equation (16),

−r3 = k3 CE.S CB.S


( )
(22)
k4
EB.S + E.S ⇌ DEB.S + W.S (9) From equation (17),
k−4

−r4 = k4 CEB.S CE.S


( )
(23)

k5
From equation (18),
DEB.S + E.S ⇌ TEB.S + W.S (10)
−r5 = k5 CDEB.S CE.S
( )
k−5 (24)
Step 3: Desorption If the adsorption and desorption steps are very fast, then
k6
the concentrations of adsorbed species can be calculated
EB.S ⇌ EB + S (11) by assuming that the adsorption and desorption steps are at
k−6
equilibrium. The concentration of adsorbed species can be
obtained as follows:
k7
From equation (14),
DEB.S ⇌ DEB + S (12) r1
k−7
= 0, CE.S = K1 CE CS (25)
k1

k8
From equation (15),
TEB.S ⇌ TEB + S (13) r2
k−8
= 0, CB.S = K2 CB CS (26)
k2
From equation (6–13), the rate equations can be represented
as From equation (19),
C k1 r6 CEB CS
( )
−r1 = k1 CE CS − E.S , K1 = = 0, CEB.S =
( )
(14) (27)
K1 k−1 k6 K6
From equation (20),
C k2 r7 CDEB CS
( )
−r2 = k2 CB CS − B.S , K2 = = 0, CDEB.S =
( )
(15) (28)
K2 k−2 k7 K7
From equation (21),
C C k3 r8 CTEB CS
( )
−r3 = k3 CB.S CE.S − EB.S W.S , K3 = = 0, CTEB.S =
( )
(16) (29)
K3 k−3 k8 K8
On substituting these values in surface reaction rates
C C k4 −r3 = k3 K1 K2 CE CB CS2
( ) ( )
(30)
−r4 = k4 CEB.S CE.S − DEB.S W.S , K4 =
( )
(17)
K4 k−4

k4
(−r4 ) = K C C C2 (31)
K6 1 EB E S
C C k5
( )
−r5 = k5 CDEB.S CE.S − TEB.S W.S , K5 =
( )
(18)
K5 k−5
k5
(−r5 ) = K C C C2 (32)
K7 1 DEB E S
CEB CS k6
( )
−r6 = k6 CEB.S − , K6 = Now, the total concentration of active sites on the surface, CT,
( )
K6 k−6 (19) can be expressed as the sum of concentration of all sites on

 Catalysis, Structure & Reactivity  2016   VOL. 2   NOS. 1–4 21


Emana and Chand  Kinetic study of alkylation of benzene with ethanol over bimetallic modified HZSM-5 zeolite catalyst and effects of percentage metal loading

which reactants and products are adsorbed and the concen-


o
tration of vacant sites which yields, −ΔGads,i
( )
Ki = exp (41)
CT = CS + CE.S + CB.S + CEB.S + CDEB.S + CTEB.S RT
(33)
o
where ΔGads,i is the Gibbs free energy for adsorption of spe-
cies i under standard conditions (298 K and 1 atm) which is
CT o
further related to the change of enthalpy ΔHads,i and change
CS = CEB CDEB CTEB (34)
1 + K1 CE + K2 CB + K6
+ K7
+ K8
o
of entropy ΔSads,i of adsorption as follows:
o
ΔGads,i o
= ΔHads,i − T ΔSads,i
o
(42)
Substituting equation (34) into equation (30–32), then
From equations (41) and (42),
( ) k3� CE CB
−r3 = ( )2 (35)
CEB CDEB CTEB o o
1 + K1 CE + K2 CB + ΔSads,i ΔHads,i
( )
+ + Ki = exp
K6 K7 K8 − (43)
R RT

k3� = k3 K1 K2 CT2 Alternatively, the above equation (43) can be represented with
the centered temperature form as:
k4� CE CEB 1 1
( ( ))
Ki = exp Di − Fi
( )
−r4 = ( − (44)
CEB CDEB CTEB
)2 (36) T To
1 + K1 CE + K2 CB + K6
+ K7
+ K8
where D = ads and F = ads
ΔS ΔH
R R
If we assume that the adsorption of water and nitrogen
k4 K1 CT2 does not compete with the adsorption of hydrocarbons,
k4� =
K6 the influence of water and nitrogen adsorption could be
neglected. With these assumptions, the rate equations, equa-
( ) k5� CE CDEB tions (35) and (36) become
−r5 = ( )2
1 + K1 CE + K2 CB +
CEB
+
CDEB
+
CTEB
(37) ( ) k3� pE pB
K6 K7 K8 −r3 = (
pEB pDEB
)2 (45)
1 + K1 pE + K2 pB + K6
+ K7

k5 K1 CT2
k5� = k3� = k3 K1 K2 CT2
K7
( ) k4� pE pEB
It is important to note that the adsorption of water is negli- −r4 = (
pEB pDEB
)2 (46)
gible. Hence, KW equals to zero in the above surface coverage 1 + K1 pE + K2 pB + K6
+ K7
expressions.
For each temperature, the space–time-conversion data
have been analyzed and the rates of reaction were obtained
by the differential analysis of the plug flow reactor equation: k4 K1 CT2
k4� =
K6
dX
robs = ( / B ) (38)
W FBO equation (37) was ignored due to low amount of TEB.
The partial pressures in the above equations are related
to the conversion and total pressure P by the following
dXB ri A (bulk density)
( )
relationship:
= (39)
dZ FBO
1 − xB P
( )
pB = ( (47)
7.8 + xB
)
where robs  =  experimentally observed rate of reaction of B,
W = mass of the catalyst, B = benzene, XB = fractional benzene
conversion, FBO = feed rate of benzene, z = bed length, and 0.5 − xB P
( )
A = bed cross sectional area. pE = ( (48)
7.8 + xB
)
The intrinsic rate constant can be expressed according to
the Arrhenius equation:
xB P
( )
pEB = ( (49)
−E 7.8 + xB
( ) )
k = ko exp (40)
RT
Conventionally, the temperature dependence relations of the xB P
( )
adsorption equilibrium constants can be expressed according pDEB = (
7.8 + xB (50)
)
to the following thermodynamic relations:

22 Catalysis, Structure & Reactivity  2016   VOL. 2   NOS. 1–4


Emana and Chand  Kinetic study of alkylation of benzene with ethanol over bimetallic modified HZSM-5 zeolite catalyst and effects of percentage metal loading

Table 5 Estimated kinetic and adsorption constants


Conclusions
Constants T = 350 °C T=400 °C T=450 °C
From the present study on the performance of magnesi-
k′3 (kg mol/kg cat h) 11.23 13.12 15.00
k′4 (kg mol/kg cat h) 25.60 30.25 35.10 um–boron-modified HZSM-5 (SAR  =  90) catalysts and its
K1 (L/mol) 0.42 0.34 0.23 kinetic study, the following conclusions can be made:
K2 (L/mol) 0.58 0.49 0.37
K6 (L/mol) 67.00 63.00 60.00 (1) During alkylation of benzene with ethanol using either
K7 (L/mol) 49.00 47.00 44.00 modified or unmodified HZSM-5 catalysts, ethylben-
zene was the primary product, while diethylbenzene,
triethylbenzene, toluene, and xylene mixtures were
Table 6 Estimated parameter values also observed in the product.
Kinetic parameter (2) For boron–magnesium bimetallic-modified HZSM-5,
Activation energy, Pre-exponential factor, the highest selectivity of ethylbenzene (76.22%) was
Constants Ea (kJ/mol) ko (kg mol/kg cat h) obtained by (Mg  +  B)-15%-HZSM-5 and the lowest
k′3 14.3 169.85 ethylbenzene selectivity (49.15%) was obtained by
k′4 15.4 479.19 (Mg  +  B)-5%-HZSM-5 using 2:1 benzene-to-ethanol
(L/mol)
K1 22.68 5.36 × 10−3 ratio by volume
K2 165.6 2.36 × 10−2 (3) The highest selectivity of ethylbenzene was obtained
K6 4.49 28.02 by bimetallic modified HZSM-5 due to synergetic
K7 21.44 1.12 × 103
effect.

)2
k3� 0.5 − xB 1 − xB P 2 ∕ 7.8 + xB
( )( ) (
( )
−r3 = ( ( ( ) x x
)( ( )))2 (51)
1 + K1 0.5 − xB + K2 1 − xB + KB + KB P∕ 7.8 + xB
) (
6 7

k3� = k3 K1 K2 CT2

)2
k4� 0.5 − 0.5xB 1 − xB P 2 ∕ 7.8 + xB
( )( ) (
( )
−r4 = ( ( ( ) x x
)( ( )))2
1 + K1 0.5 − xB + K2 1 − xB + KB + KB P∕ 7.8 + xB (52)
) (
6 7

(4) A reaction scheme with three parallel routes leading


k4 K1 CT2
k4� = to the formations of ethylbenzene, diethylbenzene,
K6
and triethylbenzene considered for the kinetic study.
In order to estimate the unknown parameters in equations (51) The kinetic parameters were determined using LHHW-
and (52), the differential equations were solved by the Fourth– type kinetic models. LHHW model could satisfactorily
Order Runge–Kutta method (MATLAB ODE 45 subroutine). As correlate the rate data and this model gives good fit
the rate equation is nonlinear with respect to unknown param- between the experimental and calculated data.
eters, a nonlinear regression program based on Marquardt’s
algorithm was used to obtain a mathematical fit for the above Acknowledgment
rate equation by minimizing the objective function for the We thank Hydrocarbon and Instrumentation Analysis labo-
residual sum of squares. ratories, Chemical Engineering Department, and Institute
Instrumentation Centre, IIT Roorkee for their unlimited sup-
n
)2 port in analyzing the samples.
Yi − Yi�

(53)
(
𝜙=
i=0
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24 Catalysis, Structure & Reactivity  2016   VOL. 2   NOS. 1–4