Catalysis Communications 9 (2008) 1894–1897

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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Enhanced octane boosting reactions of light naphtha on mesoporous ZSM-5

Nagabhatla Viswanadham *, Raviraj Kamble, Sandeep K Saxena, Madhulika Singh
Catalysis and Conversion Process Division, Indian Institute of Petroleum, Dehradun 248 005, India

a r t i c l e i n f o a b s t r a c t

Article history: Mesoporous ZSM-5 with increased surface area and more than a two-fold increase in pore volume has
Received 5 December 2007 been synthesized and evaluated for its activity towards various reactions. This has been successfully
Received in revised form 25 February 2008 exploited to give spectacular increase in production of LPG and aromatics responsible for significant
Accepted 5 March 2008
increase in research octane number of light naphtha.
Available online 18 March 2008
Ó 2008 Elsevier B.V. All rights reserved.

Keywords:
Gasoline
Aromatics
Mesoporous ZSM-5
Hydrogen transfer
Octane number

1. Introduction
Environmental legislations on fuel quality have restricted the
usage of light hydrocarbon fractions of petroleum such as light
naphtha (LN) and natural gas liquid (NGL) for gasoline blending
as these feeds are having high Reid Vapor Pressure (RVP  70)
and low research octane number (65–70). Refinery processes like
catalytic reforming are not effective for feedstocks containing n-
pentane and n-hexane [1]. On the other hand demand for Liquefied
petroleum gas (LPG) is increasing at a growth rate of over 14% per
year in India [2,3]. This situation suggests the need for the value
addition of light alkane feeds by converting them into LPG and high
octane gasoline.
The medium pore ZSM-5 with pore diameter (5.5 Å) is generally
used for the aromatization of light alkanes such as n-propane, n-
butane, n-pentane and industrial feedstocks containing light paraf-
fins such as NGL and LN [4,5]. Different from the above mentioned
processes which convert LPG into aromatics, our aim was to pro-
duce LPG along with aromatics from industrial feedstocks. Recently
we have developed a zeolite based catalyst for the conversion of
NGL/LN into gasoline and LPG [6]. Unlike the dehydrocyclization
reactions that occur in reforming, cracking and remaking of mole-
cules occur on ZSM-5 catalyst [7]. The smaller olefins formed upon
cracking are the source for oligomerization and cyclization reac-
tions that eventually produce aromatics. In addition to aromatics
* Corresponding author. Fax: +91 135 2660202.
E-mail address: nvish@iip.res.in (N. Viswanadham).
production the smaller olefins can also undergo a secondary bimo-
lecular hydrogen transfer reaction (HT) producing both aromatics
and LPG. However the small zeolite pores of ZSM-5 resist this sec-
ondary reaction. To overcome this resistance towards HT reactions
the ZSM-5 having mesopores is used in this study.
There are several methods mentioned in the literature for
producing mesoporosity in ZSM-5. Framework dealumination of
ZSM-5 is generally used for creation of mesopores which increases
its catalytic activity. Earlier Lukaynov’s studies indicated the en-
hanced hydrocarbon conversion reactions of olefins over steam
dealuminated zeolites [8]. The dealumination treatment dissolves
amorphous material and generates mesoporosity but mesoporosity
created may not be uniform and at severe conditions it may even
cause crystal collapse of ZSM-5 [9,10]. The almost striking option
for improving porosity could be the modification of synthesis pro-
cedures of ZSM-5 so as to create mesoporosity during the synthesis
[11]. In one method the mesoporosity is obtained by occlusion of
nano-sized (12–18 nm) carbon particles into the crystal during
the synthesis and subsequently removing them through oxidation
[12,13]. Another method to create mesoporosity can be through
decreasing the size of ZSM-5 crystal to nano range so as to obtain
intercrystalline mesoporosity [14–18]. This method gives an added
advantage of increased surface area and catalytic properties [19–
21].
The development of mesoporosity in ZSM-5 type zeolite with-
out any loss in acidity and crystallinity can be utilized towards
an important octane boosting reaction. In this research note, we re-
port a method for production of high octane gasoline along with
LPG from LN using mesoporous ZSM-5.

1566-7367/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2008.03.011
 N. Viswanadham et al. / Catalysis Communications 9 (2008) 1894–1897
2. Experimental
2.1. Catalyst preparation
The zeolites used in this comparison study were synthesised by
general strategy, i.e., hydrothermal treatment of silica and alumina
precursors along with organic template at optimum temperature
and duration. Only difference in the synthesis procedure is the
choice of silica source, TEOS in case of mesoporous ZSM-5 (MZ)
and silica solution in case of normal ZSM-5 (NZ) and the quantity
of template used. The detailed procedures for the synthesis of NZ
and MZ are described elsewhere [22].
2.2. Catalyst characterization
X-ray powder diffraction (XRD) pattern were measured on Rig-
aku Dmax III B equipped with rotating anode and Cu Ka radiations.
The measurements were conducted in continuous h/2h scan refrac-
tion mode. The anode was operated at 30 kV and 15 mA the 2h an-
gles were measured 5–60° at the rate of 2°/min.
The N2 adsorption desorption isotherms were measured at 77 K
on ACAP Micrometrics USA instrument. Before measurement the
samples were evacuated overnight at 250 °C. The external surface
area, micro pore surface area and pore volume of the samples were
estimated from slopes and intercepts of t-plots derived from N2
adsorption isotherms. Acidity was characterized on heat flow
microcalorimeter model Setaram C-80, attached to a volumetric
adsorption unit for probe delivery. About 0.1 g of catalyst was out-
gassed at 723 K under vacuum.
2.3. Reaction studies
Two model reactions namely, Cumene cracking and esterifica-
tion of cyclohexanol were conducted for measuring acid activity.
Two aromatization reactions, namely n-heptane conversion and
light naphtha conversion were conducted for measuring aromati-
zation activity of catalysts. All the reactions were conducted at
723 K, 10 bar pressure 6 h 1 WHSV feed flow rate and N2/HC molar
ratio of 2.
3. Results and discussion
The XRD patterns of both zeolites nicely illustrate the formation
of ZSM-5 in both cases [22]. The TG/DTG/DTA of MZ shows three
sharp peaks in the indicated temperature ranges 100–150 °C,
200–300 °C and 400–500 °C in case of MZ, and there are only
two peaks in temperature ranges 100–150 °C and 400–500 °C in
case of NZ. The second peak which is an exothermic, is observed
only incase of MZ, but not by NZ. This peak can be assigned to
the TPA+ cations balancing the charge of Si–O groups in the con-
nectivity defects responsible for formation of mesopores [22].
The sample MZ exhibited very high pore volume, micropore
volume and surface area (Table 1). The MZ also exhibited signifi-
cant mesoporosity and this is evident in the adsorption/desorption
isotherm as illustrated by Fig. 1. There is a steep jump in the iso-
therm and a big desorption loop in case of MZ while this particular
Table 1
Catalytic properties and product yields in hydrocarbon conversion
Properties NZ catalyst
Surface area (m2/g) 346
Pore volume (cc/g) 0.18
Micropore volume (cc/g) 0.10
Total acidity (m mol NH3/g) 0.79
Stong acidity (m mol NH3/g with DH > 100 kJ/mol) 0.05
1895
300
300
Volume adsorbed (cm3/g)
200 MZ
200 100
NZ
0
0.96 0.98 1
MZ
100
NZ
0
0 0.5 1
Relative pressure (P/P0)
Fig. 1. N2 adsorption desorption isotherms of normal (NZ) and mesoporous (MZ)
ZSM-5.
feature is absent from the isotherm of NZ. The hysteresis loop of
MZ appears at a high relative pressure (P/P0 = 0.9–1.0) and reflects
intercrystalline voids in the packing of the smaller crystals. Acidity
was obtained with microcalorimetric measurement for ammonia
adsorption carried out at 448 K. Differential heat of ammonia
adsorption was determined by introducing small quantity of
ammonia on to the outgassed sample, till the neutralization of all
acid sites occurred on the catalyst surface. The resulting thermo-
grams for each dose of ammonia gave the heat of adsorption and
pressure change gave the amount of ammonia adsorbed. Thus cat-
alyst MZ shows improved mesoporosity and surface area without
loosing the essential features of ZSM-5, viz., acidity and crystal
parameters.
Acidity and porosity are the two important properties that can
influence the reaction products. Sample MZ exhibited compara-
tively lower acidity, but the strong acid sites are more on this sam-
ple (Table 1). When tested for Cumene cracking, catalyst MZ
exhibited little higher conversions at lower reaction temperatures,
but the conversion levels are similar for both the catalysts at higher
reaction temperatures (Fig. 2a). The catalysts also exhibited similar
trends in cyclohexanol esterification reaction (Fig. 2b). The above
mentioned reaction studies suggest that the acid activities of the
both catalysts are similar. The catalysts are further evaluated for
their activity towards the production of LPG and aromatics from
n-heptane and LN, where, porosity dependent hydrogen transfer
(HT) reactions are expected to influence the product selectivity.
The composition of light naphtha as well as the products ob-
tained over NZ and MZ catalysts are given in Table 2. Based on
the nature, the product has been classified into (1) fuel gas (meth-
ane + ethane), (2) LPG (propane + butane) and (3) aromatics. The
higher product yield exhibited by MZ indicates its higher catalytic
activity as compared to NZ (Table 2). However, the increase is more
significant, almost two-fold, in case of aromatics and LPG and min-
imum in case of fuel gas. The simultaneous increase in aromatics
and LPG in MZ suggests a common intermediate or reaction mech-
anism for the formation of these products. Cracking of paraffins in
to smaller fragments is the primary step in light alkane conversion
over ZSM-5. The olefins thus undergo oligomerization and cycliza-
tion reactions for the formation of aromatics. The dehydrogenation
MZ catalyst of cyclic hydrocarbons and naphthenes needs a hydrogen acceptor,
461
where, the smaller olefins act as hydrogen acceptor. This coupling
0.39 reaction results in the formation of smaller paraffins as a major by
0.13 product along with the aromatics. A scheme for the formation of
0.42 LPG and aromatics through hydrogen transfer (HT) reactions is gi-
0.16
ven in Fig. 3. The high amount of aromatics and LPG obtained over
1896 N. Viswanadham et al. / Catalysis Communications 9 (2008) 1894–1897

Light naphtha
a 100
Converson (wt.%)

Fuel gas
75
Olefins LPG
NZ
50 MZ

25 Oligomers Aromatics

0
150 220 290 360 430 500 LPG
Reaction Temperature (ºC) Naphthenes HT

b 80
NZ MZ
Olefins
Conversion (%)

60
Fig. 3. Schematic representation for role of hydrogen transfer reactions in the fo-
rmation of LPG and aromatics.
40

20 aromatics with very low yields of olefins, obtained on MZ, clearly

suggests the enhanced occurrence of HT reactions on catalyst MZ.
0 However, light naphtha contains several hydrocarbon types
0 200 400 600 800 such as naphthenes, paraffins and iso-paraffins and the reactivity
Reaction Time (min) of pure paraffins may differ from that of the light naphtha. In order
to see the effectiveness of the catalysts towards n-paraffin conver-
Fig. 2. Performance of catalysts in (a) Cumene cracking and (b) cyclohexanol est- sion, a model compound n-heptane was chosen. Catalyst MZ again
erification with acetic acid. exhibited enhanced hydrogen transfer reactions identified by high
yields of LPG with low yields of olefins in the product (Table 2).
Table 2
Product yields in hydrocarbon conversion reactions 4. Conclusion
Hydrocarbon composition LN feed Product on Product on
(wt.%) NZ MZ In conclusion, we have discovered that the presence of mesop-
Reaction 1. Light naphtha conversion ores in ZSM-5 can dramatically boost the octane number of light
Fuel gas (C1 + C2) 0.0 8.6 12.5 alkane feedstocks such as LN by facilitating hydrogen transfer reac-
LPG (C3 + C4) 0.5 18.2 36.5 tions between olefinic intermediates and cyclic intermediates to
C5 + paraffins 27.8 17.4 4.6 obtain enhanced yields of aromatics and LPG. This catalyst enables
Isoparaffins 32.7 18.1 15.2
Olefins 0.2 20.3 3.7
the process more effective for the light alkane upgradation in terms
Naphthenes 29.0 4.4 0.4 of product quality and economics.
Aromatics (Benzene) 9.8 (4.9) 13.0 (1.7) 27.1 (0.4)
Total 100.0 100.0 100.0
Acknowledgements
RON 67.8 85.3 108.5
Reaction 2. n-Heptane conversion
R.K. acknowledges Council of Scientific and Industrial Research
Hydrocarbon composition n-Heptane Product on Product on
(wt.%) feed NZ MZ
(CSIR), India for awarding the Junior Research Fellowship (JRF).
Conversion – 95.0 92.0
Fuel gas (C1 + C2) – 17.3 1.8 References
LPG (C3 + C4) – 37.6 54.9
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