Fuel 107 (2013) 432–438

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Fuel
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Cracking and isomerization functionalities of bi-metallic zeolites

for naphtha value upgradation
Sandeep K. Saxena, Nagabhatla Viswanadham ⇑, M.O. Garg
Catalysis and Conversion Process Division, Indian Institute of Petroleum, Council of Scientific and Industrial Research, Dehradun 248 005, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

" Cr ion-exchange on H-BEA followed

by Pt impregnation resulted in LIGHT NAPHTHA (RON : 21.9)
creation of moderate acid sites.
" Cr in H-BEA acts as Pt receptor to P N A
facilitate improvement in dispersion
and reducibility of Pt sites.
N
" Cr promotes isomerization by
P
reducing cracking activity of acid
sites and hydrogenolysis activity of
P
Pt.
" The Pt–Cr–HBEA is suitable for
Catalyst with enhanced moderate acidity
octane boosting of various
and metal dispersion
hydrocarbon feedstocks.
ISO-PARAFFIN RICH GASOLINE
BLEND (RON:65.5 )

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

Article history: Effect of acid and metal functionalities of several mono- and bi-metallic wide pore zeolites such as BEA
Received 14 August 2012 and Y on the cracking and isomerization properties of n-heptane as well as two industrial naphtha feed-
Received in revised form 11 January 2013 stocks have been studied. Among these, the bi-metallic Pt–Cr–HBEA catalyst exhibited appropriate cata-
Accepted 30 January 2013
lytic properties responsible for high isomerization and octane boosting. Detailed studies envision that the
Available online 15 February 2013
role of Cr is bi-functional, namely, to change the acidity of the zeolite support towards the moderate
strength responsible for controlled cracking and to promote the reducibility and dispersion properties
Keywords:
of the Pt for the effective isomerization reaction. This has resulted in enhancement in research octane
n-Heptane
Naphtha
number (DRON) of two industrial naphtha feedstocks with 22 and 43 units increase in RON along with
Cracking negligible amount of aromatics, especially benzene that makes the product suitable for gasoline applica-
Isomerization tions. The catalyst exhibited constant performance in the studied period of 70 h.
Octane number Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction methyl tert-butyl ether (MTBE) has been banned as a gasoline

The lead phase out and new environmental regulations on
gasoline quality left very few options for the processing of indus-
trial naphtha feed stocks containing 5–12 carbon atoms [1]. The
conventional gasoline streams produced from reforming and Fluid
Catalytic Cracking (FCC) processes have limitations for blending
due to their high aromatic content, especially benzene in reformate
and olefins in FCC streams [2,3]. Even the oxygenates such as
⇑ Corresponding author. Tel.: +91 135 2525856; fax: +91 135 2660202.
E-mail address: nvish@iip.res.in (N. Viswanadham).
additive due to its suspicious ground water contamination [4].
An ecologically sound way to improve the quality of gasoline is
through the production of branched paraffins from the n-paraffins
[5–8]. Much work is done on the isomerization of light naphtha
containing C5–C6 paraffins but, the processing of middle naphtha
cut having n-heptane to n-nonane is recently gaining importance
in refinery due to the stringent legislations for advanced liquid
fuels [9,10].
The isomerization process requires a strong acid such as chlori-
nated alumina to favor thermodynamically controlled isomer for-
mation at lower reaction temperatures. However, recently solid

0016-2361/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.01.076
 S.K. Saxena et al. / Fuel 107 (2013) 432–438
acids are gaining importance to avoid the complications involved
in corrosive chlorine and its leach out with reaction streams
[11,12]. The skeletal isomerization of n-heptane has been studied
over variety of solid acids that includes Pt- or Pd–H-mordenite,
Y-zeolite, Beta zeolite (BEA), SO2
4 /ZrO2, and heteropoly acid cata-
lysts [13,14]. Among them, the large pore Pt–H-BEA catalyst is con-
sidered to be a promising candidate for hydro-isomerization of C7
hydrocarbon feedstocks [15,16]. Nevertheless, the hydrocarbon
conversion and isomer selectivities over Pt–HBEA are still not suf-
ficiently high and research is onto modify the properties of zeolite
supported Pt catalysts [17–20]. Detailed understanding of the reac-
tion mechanism indicates that the main limiting steps in isomer
formation are cracking and hydrogenolysis reactions. Thus, the
three desirable factors for efficient performance of catalyst towards
C7+ isomerization can be summarized as (1) the acidity of zeolite
should be high enough to facilitate low-temperature paraffin acti-
vation with minimum cracking, (2) the metal component should
exhibit efficient dehydrogenation–hydrogenation activity with
minimum hydrogenolysis activity and (3) there should be a bal-
ance between acid sites and metal sites with their uniform distri-
bution on the catalyst. Interestingly, all these three issues seems
to be interdependent as the number and nature of acid sites of
the zeolites influence the nature of metal species formed, its dis-
persion and its strength of interaction with the support.
Hence, the present study is aimed to develop a catalyst with tai-
lor-made properties for the value upgradation of industrial naph-
tha feeds through hydro-isomerization reaction. Two wide pore
zeolites H-Beta (H-BEA) and HY are used for the preparation of var-
ious mono-metallic (Pt) and bi-metallic (Pt–Cr) catalysts, where
sequential loading of Cr and Pt is adopted. The method differs from
that of the Renouprez et al., where co-impregnation method and
sublimation methods are used for the preparation of Cr–Pd sup-
ported silica [21]. The purpose of choosing Cr interaction with
the support followed by Pt in the present study is to change the
properties of acidic support (zeolite) before it comes to interact
with the Pt. Attempts were made to understand the role of various
catalytic properties such as acidity, acid strength distribution, me-
tal dispersion, metal reducibility and their collective effect on the
octane boosting reactions of naphtha feedstocks.
2. Experimental
2.1. Preparation of catalysts
2.1.1. Preparation of Pt–HBEA and Pt–HY catalysts
Commercial zeolites with silicon-to-aluminum atomic ratio
(SAR) of 25 (H-BEA) and 5 (HY) obtained in powder form from
Sud cheime India limited were used as parent samples for extru-
dates preparation. In a typical procedure, 6 g of dry zeolite powder
is mixed with 4 g of alumina powder (binder) and the mixture was
ground well to get uniform mixing, followed by drop wise addition
of 3 vol% glacial acetic acid solution with continuous grinding, till
the formation of a wet paste. Then the paste is allowed for peptiza-
tion at room temperature for 3 h followed by extrusion using a lab
made hand extruder. The wet extrudates are allowed to get dry at
room temperature for 12 h and heated at 100 °C for 4 h followed by
calcination at 500 °C for 4 h. The extrudates are thus used for Pt
impregnation so as to obtain Pt–HBEA and Pt–HY catalysts.
2.1.2. Preparation of Cr–HBEA and Cr–HY catalysts
For the preparation of Cr–HBEA and Cr–HY, the parent H-BEA
and H–Y zeolite powders were refluxed with aqueous solution of
chromium (III) nitrate, where, 1.5 g chromium (III) nitrate salt is
dissolved in 1 l distilled water and the resultant solution is added
to 20 g of zeolite powder placed in a RB flask, followed by its
433
refluxing at 100 °C for 2 h, then cooling to room temperature and
filtering with several washings with adequate distilled water. The
wet cake obtained is dried at room temperature followed by drying
at 100 °C for 4 h and then calcined at 550 °C for 4 h. The powder
form of Cr–HBEA and Cr–HY thus obtained are used for extrudates
preparation as per the procedure described in Section 2.1.1.
2.1.3. Preparation of Pt–Cr–HBEA and Pt–Cr–HY catalysts
The extrudates form of Cr–HBEA and Cr–HY obtained from the
procedure described in Section 2.1.2 have been taken to prepare
their respective extrudates followed by impregnation of 0.4 wt.%
of Pt metal adopting the incipient wet procedure, where amount
of Pt salt equivalent of hexa cloroplatinc acid (0.0844 g) is dis-
solved in 7 ml of distilled water and added into the 10 g of extru-
dates drop-wise with uniform mixing. The mixture was kept at
room temperature and was allowed to equilibrate over night. The
sample was dried at room temperature and at 100 °C for 8 h and
the oxide form of the metal was obtained by calcination at
500 °C for 4 h. All the catalysts were in situ reduced at 500 °C under
hydrogen pressure before using them for isomerization reaction.
The amount of Cr and Pt on the final catalyst was observed to be
0.8 wt.% and 0.4 wt.% respectively, on dry basis (measured by ICP).
2.2. Physico-chemical characterization
X-ray powder diffraction (XRD) patterns of all the catalysts
were measured on Rigaku Dmax IIIB equipped with rotating anode
and Cu Ka radiations. The BET surface area [22], pore size and pore
volume measurements were conducted on ASAP 2010 adsorption
unit, Micromeritics Instruments Inc. USA using N2 gas (99.995%
pure). The acidity of the catalyst was measured by temperature
programmed desorption of NH3 (NH3-TPD) using a Micromeritics
chemisorbs 2750 pulse chemisorption system and micro-calori-
metric ammonia adsorption studies using a Tian-Calvet type
heat-flow micro-calorimeter (C-80 model, Setaram, France). Tem-
perature programmed reduction (TPR) is conducted using Microm-
eritics chemisorbs 2750 pulse chemisorption system. Hydrogen
pulse chemisorption experiments were conducted to measure the
dispersion of Pt and Cr metals on the zeolite support. In a typical
procedure, the sample was pretreated with an argon flow of
50 mL/min and a series of pulses of hydrogen (1 mL) were intro-
duced on the sample for adsorption of hydrogen on metal sites at
ambient temperature. A TCD detector analyzed the exit gas from
the reactor to measure the adsorbed hydrogen after each dose.
The pulse adsorption studies were conducted until the TCD gives
two consecutive peaks and the cumulative value of the peaks gave
the total amount of hydrogen consumed by the metal on the cata-
lyst. The following equation is used in a pulse chemisorption anal-
ysis to calculate the percent dispersion.
Vs X SF calc
%D ¼ 100 GMW calc
F N X SM X 22414
%D is the dispersion percent, Vs is volume adsorbed (ml at STP), SF
calc is calculated stoichiometry factor, SM is sample mass (g), FN is
fraction of sample mass of metal N GMW calc is gram molecular
weight.
2.3. Catalyst evaluation studies
5 g of the catalyst bed supported by a-alumina at bottom and
top is loaded in the center of a fixed bed down flow reactor
(220 mm length and 18.5 mm internal diameter) and the Hydro-
isomerization of n-heptane and two industrial naphtha feeds were
performed at the following reaction conditions; tempera-
ture = 250 °C, P = 10 bar, WHSV = 2.3 h1 and H2/HC = 4 mol/mol.
434 S.K. Saxena et al. / Fuel 107 (2013) 432–438

The product obtained in gas and liquid forms has been analyzed by 0.007
Gas Chromatography. (a) Pt-HBEA
(b) Cr-HBEA
0.006 (c) Pt-Cr-HBEA
3. Results and discussion
0.005
(c)

TCD SIGNAL ( a.u.)

3.1. Properties of monometallic and bi-metallic zeolite supported
catalysts 0.004

3.1.1. Framework interaction of chromium species

The XRD patterns of all the samples (Fig. 1A and B) exhibit a
very low background signal and sharp reflections indicating that
the structure is retained even after the metal loading. However,
three distinguished changes in the patterns were observed on
BEA after the Cr loading, namely, (i) the band at 43–44° 2h value
is disappeared (ii) two additional bands are observed at 40 and
45° 2h, and (iii) the intensity of band at 27° 2h is suppressed. After
introducing second metal Pt, there is no further change in XRD, and
Cr–HBEA as well as Pt–Cr–HBEA samples exhibited similar XRD
patterns. This phenomenon clearly envisions the chemical interac-
tion of the Cr species with the framework of the H-BEA zeolite and
is expected to cause changes in the acidic properties of the H-BEA
support and metallic properties of Pt in Pt–Cr–HBEA catalyst.
On the other hand the metal loaded H–Y zeolite samples did not
exhibit any such structural changes in XRD, and the patterns of H–
Y, Cr–HY and Pt–Cr–HY are almost similar. The specific changes ob-
served only in case of Cr loaded on H-BEA may be due to its specific
framework structure, composition (Si/Al) and porosity suitable for
the interaction with Cr species.
3.1.2. Metal reducibility studies
H2 TPR profiles of mono metallic and bi-metallic BEA are mea-
sured to understand the role of Cr on the reducibility of the Pt.
As illustrated in Fig. 2. Pt–HBEA displayed the hydrogen consump-
(A)
Pt-Cr-HBEA
INTENSITY (CPS)
0.003
(b)
0.002
0.001 (a)
0
0 200 400 600 800 1000 1200
Fig. 2. TPR patterns of mono and bi-metallic HBEA.
tion peaks at 500 °C and 800 °C. The broad peak 500 °C also indi-
cates the merging of several peaks, which suggests the reduction
of Pt ions in various oxidation states (+4, +3, +2 and +1) into the
zero oxidation state. The high temperature (800 °C) peak may be
due to the reduction of the support interacted Pt species. Similarly,
Cr–HBEA displayed two hydrogen consumption peaks at 450 °C
and 560 °C that are assigned to the reduction of Cr ion in +3 and
+2 oxidations states into the zero oxidation state. However, the
Pt–Cr–HBEA bi-metallic catalyst exhibited only a single peak at
about 480 °C and the high temperature peaks representing the
reduction of Cr+2 and Pt+2 into their zero oxidation states are com-
pletely disappeared in this sample. This may be due to the interac-
tion between Cr+2 and Pt+2 species to give low temperature
reducible Pt–Cr species at 480 °C. This is in accordance with the
earlier studies describing the possible interaction of Cr-related acid
with the Pt species to form Pt–Cr species [23,24]. Further, the
merge of this bi-metallic Pt–Cr peak with that of monometallic

Cr+3 and Pt+4 species resulted in the appearance of a single broad

reduction peak ranging from 400 °C to 800 °C with its peak tip at
Cr-HBEA
480 °C. Thus, the single peak of Pt–Cr–HBEA is indicative of the
strong interaction between Cr and Pt which resulted in significant
Pt-HBEA improvement in reducibility of Pt species.

H-BEA 3.1.3. Metal dispersion studies

The Pt dispersion data of the Cr-free as well as Cr-loaded H-BEA
5 10 15 20 25 30 35 40 45 50 55 60 and HY zeolites are given in Table 1. In the absence of Cr, the Pt–
HBEA exhibits the Pt dispersion of about 54% which is increased
to 89% in Pt–Cr–HBEA. Since, the interaction of Pt species with
the acid sites of support is known [25,26], such metal acid interac-
tion is expected to change with the changes in properties of the
(B) support. Hence, in the present study, the interaction of Pt with
Pt-Cr-HY the Cr–HBEA is expected to be different from that of the HBEA.
INTENSITY (CPS)

The H2 TPR (temperature program reduction) results in Fig. 2 have

Cr-HY indeed indicated the presence of new peak in Pt–Cr–HBEA repre-
senting Pt–Cr species. This observation supports earlier studies
indicating the possible interaction of Cr-related acid sites such as
Pt-HY
[Cr(OH)2]+ with Pt species in the formation of the Pt–Cr species.
H-Y
Thus, the enhanced Pt dispersion observed in presence of Cr can
be ascribed to the interaction of Pt with the Cr species or with
the Cr modified H-BEA support [27–29].
5 10 15 20 25 30 35 40 45 50 55 60

3.1.4. Changes in acidity and acid strength distribution

Fig. 1. X-ray diffraction patterns of zeolite samples (A) BEA zeolite based samples The NH3-TPD profiles of monometallic and bimetallic zeolites
(B)Y zeolite based samples. are given in Fig 3. The changes in acidity patterns of H-BEA upon
 S.K. Saxena et al. / Fuel 107 (2013) 432–438 435

Table 1 form additional acidic species such as [Cr(H2O)n]3+ and [Cr(OH)2]+

Physico-chemical properties of various zeolites. that may be responsible for the enhancement of acidity observed
Catalysts Surface area Pore volume Pt dispersion Total acidity in Pt–Cr–HBEA.
BET (m2/g) (Cm3/g) (%) (m mol/g) On the other hand, such phenomenon of changes in acidity is
H-BEA 578 0.2451 – 0.88 not observed in case of metal loaded H–Y zeolite samples
Pt–HBEA 564 0.2357 54 0.92 (Fig. 3B) indicating that Cr or Pt metal ions did not show consider-
Cr–HBEA 556 0.2397 – 0.86 able interaction with H–Y zeolite framework and is in accordance
Pt–Cr–HBEA 543 0.2265 89 1.70
H–Y 716 0.3418 – 1.10
with the XRD patterns discussed earlier. Overall, the XRD and
Pt–HY 710 0.3242 38 0.95 TPD results envision the interaction of Cr specifically with HBEA
Cr–HY 700 0.3105 – 1.08 but not with the H–Y.
Pt–Cr–HY 708 0.3001 66 1.15 Hence, a special focus is given to the detailed characterization of
Acidity determine by micro-calorimetric studies. acidity of H-BEA zeolite based catalysts. The strong acidity peak
Heat of adsorption of ammonia (kJ/mol). observed in TPD is indeed indicates a cumulative concentration
Strong > 100, medium = 100–75, weak < 75. of a range of acid sites falling in strong and medium strength re-
gion. In order to gauge the acidity in little accurate manner, the
metal loaded H-BEA samples are also analyzed by micro-calorime-
try method (Table 1). The Microcalorimetric data is in complete
(A) 0.09 agreement with that of the TPD, where the total acidity is increased
Pt-Cr-HBEA in Pt–Cr–HBEA. However, the acid strength distribution of Pt–Cr
TCD SIGNAL (a.u.)

HBEA is entirely different from that of the Pt–HBEA. For the conve-
0.06 nience of comparison, Microcalorimetric acidity is arbitrarily clas-
sified into strong, (>100 kJ/mol) medium (100–75 kJ/mol) and
Cr-HBEA weak (>75 kJ/mol) acidity (Fig. 4). It is interesting to see that the
0.03 H-BEA increase in acidity of Pt–Cr–HBEA is due to the increase in medium
acid sites. Overall, the present study indicates the effective interac-
tion of Cr with the framework of H-BEA that is resulted in the (1)
0
creation of additional acid sites especially with medium strength,
0 200 400 600 800 1000 (2) improvement in reducibility and (3) Pt dispersion in the Pt–
Cr–HBEA. These findings are different from the earlier studies of
Liu et al., where they observed the increase in number and strength
of strong acid sites by presence of Cr species and different TPR pro-
0.04
(B) files of the bi-metallic catalyst [14]. The difference observed may
H-Y be due to the difference in framework composition of the H-BEA
Pt-HY
chosen in our studies. The change in catalytic properties observed
0.03
TCD SIGNAL (a.u.)

Pt-Cr-HY by introduction of chromium prior to the Pt loading on H-BEA can

be explained from the Scheme 1A, where the new route of catalyst
preparation is compared with that of the traditional route. As seen
0.02
in the traditional route the direct impregnation of the Pt onto the
H-BEA may give heterogeneous metal distribution due to the inter-
action of Pt with the zeolite hydroxyls. Whereas, the prior loading
0.01
of Cr onto H-BEA gives the formation of Cr–HBEA sites which can
act as metal receptors for the second metal Pt and such interaction
gives uniform distribution of chromium interacted Pt. Such inter-
0
0 200 400 600 800 1000 actions of Cr species with H-BEA on one hand and its interaction
with the second metal Pt on the other are expected to facilitate
changes in acidic properties of H-BEA and dispersion, reducibility
Fig. 3. TPD patterns of zeolite samples (A) H-BEA zeolite based samples (B) H–Y properties of the Pt, which was indeed observed in the present
zeolite based samples. study.

3.2. Isomerization reaction studies

step wise loading of Cr and Pt are given in Fig 3A. All the samples
exhibited two peak pattern with low temperature and high
temperature desorption of ammonia representing the weak and
strong acidity in the samples. However, there is a difference in
acidity pattern of the samples in terms of peak position and the
peak area. For H-BEA and Pt–HBEA, the acidity patterns are almost
identical, but Cr–HBEA exhibited the shifting of the high tempera-
ture peak to the little lower side. This may be due to the interaction
of the Cr with the acid sites of the H-BEA and is in accordance with
the XRD and TPR results discussed above. But, it is interesting to
see that there is a significant enhancement in both strong and
weak acidity of the Pt–Cr–HBEA. Such an increase in acidity ob-
served after loading of the second metal Pt may be due to the
strong interaction of Pt with Cr and simultaneous decrease in inter-
action between Cr and H-BEA support. The decrease in interaction
of Cr with H-BEA may allow the Cr species to undergo hydrolysis to
3.2.1. Performance of catalysts in n-heptane isomerization
The n-heptane conversion along with detailed composition of
the product obtained on various catalysts is given in Table 2.
Among these, the two bi-metallic catalysts exhibited higher con-
versions and isomerization yields due to the presence of additional
acid sites created by Cr species. However, the increase is signifi-
cantly higher in case of Pt–Cr–BEA as it is evidenced by improve-
ment in acidity, reducibility and metal dispersion properties.
Detailed product pattern on Pt–HBEA and Pt–Cr–HBEA can be com-
pared to realize the concept of Cr promoter effect. The performance
of Pt–Cr–HBEA catalyst can be measured based on three parame-
ters, namely (i) nC7 conversion (2) total isoparaffins and (3) RON
of the product. The product slate on Pt–HBEA and Pt–Cr–HBEA in-
deed indicates superior performance of Pt–Cr–HBEA catalyst in all
three aspects. The concentration of paraffins are lower by about 25
436 S.K. Saxena et al. / Fuel 107 (2013) 432–438

(A) 80
Reactant Product

60
RON

40

20

0
Heptane Naphtha-1 Naphtha-2
FEED

(B) 80

60
YIELD (wt%) / RON

i-Paraffins
RON
40
Scheme 1. (A) Effect of Cr-exchange on acidic and metallic properties of Pt–Cr–
HBEA. (B) Reaction pathways for formation of isoparaffins from naphtha feedstocks.

20
0 ates may also lead to the formation of branched paraffins with
10 20 30 40 50 60
TIME (h)
Fig. 4. Isomerization performance of Pt–Cr–BEA catalyst. (A) Octane boosting of
various feedstocks. (B) Time-on-stream performance of the catalyst.
units and that of isoparaffins are higher by about 25 units on the
Pt–Cr–HBEA that clearly emphasizes the occurrence of effective
conversion of n-paraffins to their corresponding branched
paraffins. The resultant liquid product obtained on Pt–Cr–HBEA
exhibited 64.7 RON compared to 44.5 RON obtained on Pt–HBEA.
Thus the Cr induced changes in acidity and metal functionality
observed in Pt–Cr–HBEA are collectively contributed to the higher
n-heptane conversion with minimum cracking and enhanced iso-
mer formation.
3.2.2. Performance of Pt–Cr–HBEA catalyst for various industrial
naphtha feed stocks
The composition of two industrial naphtha feed stocks and the
products obtained on Pt–Cr–HBEA catalyst are given in Table 3.
In both the naphtha feedstocks, the common thing observed is
the decrease in paraffins with simultaneous increase of isoparaf-
fins envisions the occurrence of isomerization reaction. The aro-
matics present in both the feedstocks have completely
converted, but the concentration of naphthenes is slightly in-
creased in the product. This situation clearly suggests that the
aromatic saturation is more facile than the naphthenes ring
opening on the catalyst at the reaction conditions studied. The
possible pathways for the transformation of paraffins, naphthenes
and aromatics into isoparaffins have been depicted in Scheme 1B.
The main reaction is the direct isomerization of n-paraffins to the
corresponding branched paraffin. The cracking of the intermedi-
70 lower carbon number. For the transformation of naphthenes
and aromatics there are three reaction routes available, namely,
1. ring opening of naphthenes 2. cracking of intermediates and
3. oligomerization of fragments. Ring opening of naphthenes
can form either n-paraffins or isoparaffins, cracking can yield
the paraffins and isoparaffins of lower carbon number, and the
oligomerization can give the hydrocarbons of higher carbon num-
ber. The lower as well as higher isoparaffins obtained in the pres-
ent study clearly envisions the occurrence of cracking and
oligomerization reactions also. However, the formation of iC4–
iC6 is very low and its higher RON values contribute to the fuel
quality. The production of isoparaffins is proportionate to the
n-paraffin content in the two feedstocks and the product with
complete removal of aromatics and enhanced octane is suitable
for the gasoline blending applications.
Overall, the increase in RON of the product is governed by the
nature of feed and it’s RON (Fig 4A). For n-heptane, the total isopar-
affins obtained are 73.5 wt.% with octane boosting of 64.7 units
(from RON zero to RON of 64.7). For naphtha-1, the isomer yield
is 58.1 wt.% and that makes the octane boosting 22.6 units (RON
of naphtha-1 is 43.8). At the same reaction condition, the catalyst
exhibited octane boosting of naphtha-2 to about 43.6 units (from
RON of 21.9–65.5). The results suggest that the catalyst is potential
for the octane boosting of the industrial paraffin containing feed-
stocks even in the presence of considerable amount of naphthenes
and aromatics to produce aromatic-free, isoparaffin-rich gasoline
blending stock suitable for fuel applications.
3.2.3. Long time performance of Pt–Cr–HBEA catalyst
The long time performance Pt–Cr–HBEA for the isomerization of
naphtha-1 feed has been studied as this feedstock contains high
 S.K. Saxena et al. / Fuel 107 (2013) 432–438 437

Table 2 10 h. As shown in Fig 4B, the isoparaffin yields and RON values
n-Heptane isomerization performance on various catalysts. are comparable on this catalyst at all the reaction intervals indicat-
Composition/catalysts Pt–HBEA Pt–Cr–HBEA Pt–HY Pt–Cr–HY ing the stability of active sites even in presence of aromatics in the
Conversion (wt.%) 56.5 82.0 51.8 63.7 feed.
Product yield (wt.%)
Paraffins 46.0 21.9 50.2 39.3 4. Conclusions
C3 1.6 – – 1.2
C4 – 2.1 – 0.9
C5 0.4 1.0 0.1 0.5
Introduction of Cr prior to Pt on H-BEA zeolite enhances acid
C6 0.5 0.8 1.9 0.4 sites of medium acid strength (measured by heat of adsorption of
C7 43.5 18.0 48.2 36.3 ammonia of about 100 kJ/mol) and improves the metallic proper-
Total i-paraffins 53.8 73.5 47.3 57.0 ties such as reducibility and dispersion of Pt. These factors collec-
iC4 – 6.1 – 6.7
tively contribute to the effective isomerization of paraffins with
iC5 0.6 1.7 2.1 1.1
iC6 1.3 2.8 0.1 1.2 minimum cracking on the Pt–Cr/BEA useful for octane boosting
iC7+ 51.9 62.9 45.1 48.0 of the low value industrial naphtha feedstocks. The formation of
2,2 Di methyl pentane 4.0 6.8 3.2 3.0 small amount of lower isoparaffins (iC4–iC6) along with higher iso-
2,4 Di methyl pentane 3.2 6.7 0.3 3.1
paraffins improved the octane boosting of the product. The product
2,2,3 Tri methyl butane 0.7 0.9 – 0.5
3,3 Di methyl pentane 2.8 – – –
with its low benzene, low aromatic and high octane properties is
2 Methyl hexane 13.7 19.9 18.1 17.5 suitable for gasoline blending applications.
2,3 Di methyl pentane 5.5 6.7 4.2 4.3
3 Methyl hexane 19.6 20.8 19.0 18.7
3Eethyl pentane 1.8 0.2 0.1 0.1
Acknowledgement
2,2,4 Tri methyl pentane – 0.2 – 0.2
2,2 Di methyl hexane 0.5 0.4 0.2 0.5 We acknowledge the contributions of Dr. Manoj Kumar, Mr. Jag-
2,5Di methyl hexane 0.1 – – – dish Kumar, Dr. Sanath Kumar, Mr. Amit Sharma and Mr. Rajiv Pan-
2,4 Di methyl hexane – 0.3 – 0.1
war of IIP in catalyst characterization and reaction studies at IIP.
Naphthenes 0.2 4.6 2.5 2.3
Unidentified 0.0 0.0 0.0 1.4
Total 100.0 100.0 100.0 100.0 References
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