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Reformulation of FCC gasoline


N. Viswanadham
a

a,*

, B.S. Negi a, M.O. Garg a, Meenakshi Sundaram b,


B. Sairam b, A.K. Agarwal c

Catalysis and Conversion Process Division, Indian Institute of Petroleum, Dehradun 248005, India
b
Chennai Petroleum Corporation Limited, Chennai, India
c
Centre for High Technology, New Delhi, India

Received 21 February 2006; received in revised form 20 September 2006; accepted 23 September 2006
Available online 23 October 2006

Abstract
FCC gasoline obtained from an Indian renery was analyzed for its quality improvement through catalytic processes. The analysis
indicated the presence of high amount of sulfur, olen and iso-parans in the feed that are not suitable for processing through the hydro
treatment or hydro-isomerization. Detailed studies indicated that majority of iso-paranic and olenic compounds in the feed boil below
60 C. The entire range of gasoline is fractionated into light fraction (IBP-60 C) and heavy fraction (60 C-FBP). Heavy hydrocarbon
fraction exhibited more aromatics and sulfur with comparatively low olens and iso-parans. HDS followed by hydro-isomerization of
the heavier fraction resulted in the formation of C6C9 iso-parans through the saturation of olens and aromatics. Overall, the processed FCC gasoline exhibited more iso-parans with low olens, low aromatics and sulfur, without any loss in octane number.
2006 Elsevier Ltd. All rights reserved.
Keywords: FCC gasoline; Sulfur; Iso-parans

1. Introduction
Motor gasoline is one of the key products obtained from
a petroleum (crude oil) renery. It is a complex mixture of
light hydrocarbons containing 512 carbon atoms and having a boiling range of 40190 C. Gasoline is a blend of several renery streams namely, reformate, FCC gasoline,
visbreaker/coker naphtha, isomerate, alkylate, oxygenate
etc. The product application and customer acceptance set
detailed specications for various gasoline properties,
which in turn determine suitability of a particular fuel for
a specic blend. Today most petroleum reneries are facing
the challenge of producing motor gasoline having all the
desirable properties and also comply with the ever-increasing environmental regulations on automotive emissions
[1,2]. These regulations are aimed to guard against high lev-

els of aromatics (benzene in particular), olens, and sulfur


in the gasoline [35]. In India, presently the concentrations
of aromatics, benzene and olens in gasoline (v/v%) are
restricted to 40, 3 and 20, respectively. In spite of its vital
contribution to the gasoline pool, the FCC gasoline has
its limitation due to the presence of high sulfur and olens.
FCC gasoline being the major component of the motor
gasoline pool has 10002000 ppmw sulfur depending upon
the feed VGO used in a FCC unit [611]. The sulfur limitations in Indian gasoline (<50 ppm) demand the processing
of FCC gasoline. Removal of sulfur and olens can be
achieved by hydro treatment, but this will lead to the huge
octane loss due to the conversion of high octane aromatics
and olens into comparatively low octane n-parans and
naphthenes [1215]. Isomerization is a better option for
octane gain, but the FCC gasoline can not be directly used
for isomerization process due to the following reasons.

Corresponding author.
E-mail addresses: nvish@iip.res.in, nviswanadham@india.com (N.
Viswanadham).

1. Sulfur can deactivate the catalyst by poisoning of active


sites.

0016-2361/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2006.09.016

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2. Low amount of n-parans present in the feed can limits


the isomer production.
Many research groups are working in this direction to
remove sulfur from FCC gasoline with minimum octane
loss. SCANFiningTM (Selective Cat Naphtha Hydroning), OCTGainTM Exxon Mobil, ISAL Process UOP,
Prime G+ Process IFP, S Zorb Process Philips petroleum, Catalytic distillative desulfurization CDTech, S
Brane (membrane desulphurization) Grace Davison are
some of the examples [1621]. However, each one of these
has its strategic process depending on their feed composition and renery conguration. The processes can be classied into two major groups based on the type of
desulphurization, namely, processes operating with selective HDS viz. SCAN ning, Prime G+ and processes operating with traditional deep desulphurization followed by
isomerization/alkylation viz. Octa-gain, ISAL.
The present work is aimed to upgrade the FCC gasoline
obtained from an Indian renery. The strategy made in the
study is similar to that of ISAL but the catalysts and the
operation conditions are dierent [12]. The ISAL process
uses a CoMoP/Al2O3 associated to a GaCr/H-ZSM-5.
The present study uses an optimized mixture of CoMo/
Al2O3 and NiMo/Al2O3 for HDS followed by an isomerization catalyst prepared by the loading of Pt on a porosity
modied mordenite. The feed was processed by hydrodesulphurization to remove major amount of sulfur and for
the conversion of olens and aromatics into iso-parans.
The composite product obtained after the process exhibited
more iso-paran, less olen, less aromatics and less sulfur
with comparable RON.
2. Experimental
2.1. Feed
The feed exhibited the boiling range of 23.9174.6 C.
The feed was fractionated into two cuts, namely, light fraction (IBP-60 C) and heavy fraction (60 C-FBP). The light
cut rich in mercaptanes is treated for Merox and the heavy
cut is treated for HDS followed by hydro-isomerization.
The products obtained after the processing of the two cuts
were mixed to obtain the composite blend.
2.2. Catalysts
2.2.1. Hydrodesulphurization catalyst
The basic compositions of current hydro-treating catalyst are represented by sulphided forms of nickelmolybdenum and cobaltmolybdenum supported on alumina
represented as NiMo/Al2O3, CoMo/Al2O3.
2.2.2. Isomerization catalyst
Commercial mordenite of Si/Al = 1618, in powder
form, supplied by Sud-Chemie India Ltd was (HM) treated
with 2 N nitric acid solution (1:3 volume ratios) at 373 K

for 2 h, followed by allowing it for cooling at room temperature. The solution was ltered, washed and dried at room
temperature overnight followed by heating at 373 K for
10 h. Extrudates of the samples were prepared by mixing
mordenite and alumina binders in 3:2 wt/wt ratio, followed
by drop-wise addition of 3 vol% glacial acetic acid and
allowing it for peptization for 2 h. The resultant paste
was extruded to 1 mm diameter extrudates that were dried
at room temperature overnight, followed by heating at
100 C for 10 h. All the extrudates were calcined at
500 C for 4 h. Incipient wet method was used for impregnation of 0.3 wt% of Pt, where tetra amine platinum (II)
chloride hydrate (98% Aldrich) salt was used as Pt source.
The sample was calcined and reduced in hydrogen ow
before using it for the isomerization reaction.
2.2.3. Physico chemical properties of catalyst
XRD patterns of parent and acid dealuminated samples
were recorded with a powder X-ray diractometer model
Rigaku Dmax-III B. The measurements were conducted
in a continuous h/2h scan refraction mode using Cu-Ka
radiation. The anode was operated at 30 kV and 15 mA.
The 2h angles were measured from 5 to 60 at a rate of
2/min.
Surface Area and pore size distribution of sample was
determined static volumetrically by physisorption of nitrogen at liquid temperature (77 K) using ASAP2010
Micromeritics (USA) instrument. For measuring surface
are 0.2 gm of sample is taken in a specially designed sample
tube and degassed at 573 K under high vacuum of
106 torr for 4 h. A frit is attached to the mouth of the
sample tube, so that when the sample tube is removed from
preparation mode, it does not allow sample to expose in
atmosphere. Sample is cooled to room temperature under
vacuum and the sample tube is removed from preparation
port and attached to analysis port of the instrument. For
all the samples N2 adsorptiondesorption isotherms were
obtained at 77 K. During analysis, 77 K temperature was
maintained by using liquid nitrogen. High purity nitrogen
and high purity helium were used for obtaining adsorptiondesorption isotherms and for measuring dead space.
Surface area, pore volume and pore size distributions were
obtained by using dierent P/P0 values and applying dierent methods.
Acidity of the sample was characterized by the Setaram
C-80 heat ow micro calorimeter instrument, which has
been attached to a volumetric adsorption unit for probe
delivery. 0.1 g of catalyst was out gassed at 723 K under
vacuum. The micro calorimetric measurement of ammonia adsorption was carried out at 448 K. Dierential heat
of ammonia adsorption was determined by introducing
the small quantities of ammonia on to the out-gassed
sample, till the neutralization of all acid sites occurred
on the catalyst surface. The heat of adsorption evolved
for each dose was calculated from the resulting thermogram and amount of ammonia adsorbed at the initial
and nal pressure.

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2.3. Reaction studies


The mercaptane removal from the lighter fraction (IBP60 C) of FCC Gasoline was achieved by Merox extraction
RSH Mercaptans NaOHBRSNa Sodium mercaptide H2 O

The hydrodesulphurization of the 60 C-FBP cut was


conducted using the mixture of NiMo/Al2O3 and Co
Mo/Al2O3 catalysts. The reaction temperature and pressure were varied and tested to optimize the conditions for
sulfur removal with minimum octane loss of the feed.
The isomerization reaction was conducted in a xed bed
down ow micro reactor by loading 50 g of catalyst. The
catalyst is reduced in situ at 793 K, 8 kg/cm2 pressure
and hydrogen ow of 1.5 l/g catal./h, for 8 h. Hydroisomerization reaction was performed at a temperature
600 K, at H2/n-hexane molar ratio 2, WHSV of 2.3 h1
and pressure of 20 kg/cm2. The product was analyzed by
gas chromatograph with FID and the analysis column
was made of stainless steel tube packed with chemopack
C18. The conversion and selectivity of the products were
calculated based on the carbon number of the components
and are dened by the formulas given below
products
 100 and
consumed n-hexane
yield% conversion  selectivity

selectivityC%

A blank test was conducted in an empty reactor, which


ascertained that under the conditions used, no reaction
occurred.
3. Results and discussion
3.1. Properties of the feed
The properties of the FCC gasoline have been summarized in Table 1. The data indicates the presence of high
amount of sulfur (1070.7 ppm), olens (bromine number
of 109.3) and di-olens (Maleic anhydride value, MAV =
2.8). The sulfur and olen content of the feed clearly suggests the need for hydrodesulphurization before using it
as gasoline. ASTM analysis data of the feed is also given
in Table 1. The feed exhibited the initial boiling point
(IBP) of 23.9 C and nal boiling point (FBP) of
174.6 C. However, major amount of feed exhibited the
boiling range of 53140 C. The feed exhibited the RON
and MON of 86 and 77, respectively.
Component wise analysis data of the feed is given in
Table 2. The feed has been characterized by 32 molecular
lumps and the type and quantity of hydrocarbon present
in the feedstock have been classied into ve groups
namely, parans, iso-parans, olens, naphthenes and
aromatics. The analysis indicates that the major contribution of feed is from iso-parans (38.8 wt%) and olens
(30.3 wt%). The feed also contains considerable amount
of aromatics (13 wt%) and naphthenes (12.6 wt%). But
the amount of n-parans is very low (4.2 wt%).

Table 1
Feed properties and ASTM distillation

Yield (wt%)
Density at 15 C
Nitrogen
RVP (Kpa)
Bromine No.
MAV
Sulfur (ppm) by XRF
ASTM distillation
IBP C
5 vol%
10 vol%
20 vol%
30 vol%
40 vol%
50 vol%
60 vol%
70 vol%
80 vol%
90 vol%
95 vol%
FBP C
Total recovery vol%
Residue vol%
Loss

Feed

Light fraction

28.0
0.6469

119.2
139.2

337

0.7142
5.5

109.3
2.8
1070.7
23.9
53.0
59.0
63.0
83.4
92.8
102.9
114.5
126.6
139.0
152.0
160.2
174.6
97.8
1.4
0.8

23.9
32.0
32.5
33.5
34.0
34.6
35.3
36.2
37.5
39.4
43.5
48.9
60.0
98.0
1.0
1.0

Heavy fraction
72.0
0.7513
5.5
25.3
64.7
1157
60.0
82.8
88.8
92.4
99.8
106.3
113.9
123.2
132.5
143.0
154.1
161.7
17.0
97.9
1.1
1.0

Among the 38.8 wt% of iso-parans, iso-pentane contributes the major amount of 11.8 wt%, followed by isohexane of 10.6 wt%. The isomers of heptane, octane and
nonane are around 5 wt% each. Among the 30.3 wt% olens, the major amount is pentene (12.5 wt%) followed by
hexenes and heptenes. Higher carbon number olens are
negligible. This feedstock is thus expected to give n-parafns of C5C7 range on the hydro treatment and hence
the catalyst capable of facilitating C5C7 isomerization
can be used for the octane boosting of the feedstock.
The aromatic content is of 13 wt%, with majority of
xylenes (6.5 wt%) followed by toluene (3 wt%) and C9+
aromatics (2.6 wt%). Benzene amount is very low
(0.6 wt%). Naphthene content in the feed is 12.6 wt% with
C8 as major followed by C7 and C6. The 4.2 wt% paran in
the feed consists of 1.5 wt% n-pentane, 1.2 wt% n-hexane as
the major components followed by higher parans. Since,
the feed contains very low n-parans, hydro treatment is
favorable for the production of n-parans which are
source for the isomerization.
Overall, the feedstock contains, major amount of sulfur,
olens and di-olens. Hydro treatment of such feed can
cause huge octane loss due to the olen saturation. The
feed is thus fractionated into two fractions, viz. IBP-60
C and 60 C-FBP. Yields of the two fractions are
28 wt% and 71 wt%, respectively.
3.2. Properties of the light and heavy fractions
Properties of two fractions can be read from the data
given in Table 1. The sulfur amount in light and heavy fractions is 337 ppm and 1157 ppm respectively. High amount

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Table 2
Hydrocarbon composition of feed and fractions
Hydrocarbon
types (wt%)

Feed

Light
fraction

Heavy fraction

n-paran
C3
C4
C5
C6
C7
C8
C9
C10

Blend

Before
HDS

After
HDS

After
Isom

4.2

1.5
1.2
0.5
0.7
0.2
0.1

4.6

4.6

4.4

0.6

1.6
0.7
1.5

6.5

2.6

2.8
1.1

10.7
1.4
1.1
2.2
5.3

0.6

0.1

9.0
0.6
0.8
3.4
3.7
0.0
0.3
0.1
0.1

i-paran
C4
C5
C6
C7
C8
C9
C10
C11

38.8

11.8
10.6
5.8
4.8
4.1
1.6
0.1

51.5

31.0
20.5

27.9

5.2
8.5
6.4
3.0
4.8

41.3

0.2
7.1
14.0
12.3
6.2
1.5

53.5
3.8
5.4
21.4
11.8
6.1
2.9
1.9
0.2

52.9
2.7
16.4
18.1
7.2
4.1
2.2
1.8
0.2

Olen
C4
C5
C6
C7
C8
C9
C10

30.3
0.1
12.5
8.7
7.7
0.7
0.5
0.1

43.4

38.5
4.9

7.2

4.2
3.0

5.9

1.0
4.0
0.9

2.5

1.9
0.6
0

14.0
0.3
12.1
0.5
0.9
0.2

Naphthenes
C6
C7
C8
C9
C10

12.6
2.1
3.7
5.2
1.5
0.1

0.5
0.5

8.1
2.1
4.7
1.3

17.2
3.3
8.1
4.3
1.5

14.0
4.5
6.4
2.4
0.5
0.2

10.2
3.3
4.6
1.7
0.3
0.1

Aromatics
C6
C7
C8
C9
C10
C11

13.0
0.6
3.0
6.5
2.6
0.2
0.1

0.0

47.0
0.6
6.0
18.4
18.7
3.3

25.4
0.1
6.1
13.7
3.5
2.0

16.1
1.1
4.5
6.6
3.2
0.7

11.6
0.9
3.6
4.7
1.8
0.6

Others
RON

1.2
86.0

0.0
93.5

5.4
80.5

3.7
71.0

3.2
80.7

2.3
86.1

Total

100

100

100

100

100

100

of sulfur in the heavy fraction indicates the presence of high


boiling range sulfur compounds. Nitrogen is absent in the
light fraction but appeared in heavy fraction. This observation suggests that the nitrogen compounds in the feed are
of high boiling nature. The bromine number is increased
for light and decreased for heavy fraction. The higher bromine number of light fraction indicates the enrichment of
olens in this fraction. The detailed compositional analysis
of the two fractions given in Table 2 helps in understanding
the changes in concentration of various hydrocarbon types.
The light fraction consists of 51.5 wt% iso-parans,
43.4 wt% olens, followed by 4.6 wt% n-parans and

0.5 wt% naphthenes. On the other hand, the heavy fraction


contains 27.9 wt% iso-parans, 7.2 wt% olens and
47.0 wt% aromatics. Relative distribution of the various
hydrocarbon types into the two fractions indicates presence
of more iso-parans and olens in the light fraction and
more aromatics and sulfur compounds in the heavy fraction. That means most of the iso-parans and olens present in the feed are of low boiling compounds and hence
enriched in the light fraction. The light and heavy fractions
exhibited the RON of 93.5 and 80.5, respectively.
Presence of 337 ppm sulfur with 139.2 bromine number
of light fraction indicating the presence of olens and mercaptane sulfur that needs to be removed. This cut was treated with Merox for reducing the mercaptanes and the
sulfur level was brought down from 337 ppm to less than
10 ppm. The heavy fraction contains 47 wt% aromatics,
27.9 wt% iso-parans followed by 8.1 wt% naphthenes,
7.2 wt% olens and 4.4 wt% n-parans.
The heavier fraction containing high sulfur, high aromatics, low iso-parans and low olens is suitable for
hydro treatment due to the following reasons.
1. The low olen content in the feed restricts the hydrogenation of olens to parans and hence octane loss will
be minimized.
2. The aromatic rich fraction can undergo hydrogenation
and ring opening of aromatics to form naphthenes and
iso-parans.
Though the octane loss is expected in the process of olen saturation, yet the n-parans formed in this process can
be a good source for the isomerization reaction. The low
sulfur and high paran gasoline obtained after HDS was
used for the hydro-isomerization reaction to improve the
octane number.
3.3. Hydrodesulphurization of heavy fraction
Hydrodesulphurization studies were conducted with
60 C-FBP fraction to reduce the sulfur with minimum
octane loss. For this purpose, the experiments were carried
out at various reaction conditions and the catalyst as well as
process conditions were optimized. The basic compositions
of current hydro-treating catalyst are the sulphided forms of
nickelmolybdenum and cobaltmolybdenum supported
on alumina represented as NiMo/Al2O3, CoMo/Al2O3.
The commercially available catalysts were used for the purpose of sulfur reduction with minimum octane loss.
Hydrodesulphurization studies were conducted to understand the eect of various reaction parameters on the sulfur
removal and octane loss. Out of various reaction parameters, reaction temperature played signicant role on the
octane values with negligible changes on the sulfur level
(Table 3). At 260 C, the product exhibited 73.5 RON with
the octane loss of about 10 units. But, sulfur concentration
could not reach below 50 ppm at these conditions. Above
this temperature the product exhibited low amount of sulfur

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Table 3
Eect of reaction temperature on product sulfur and octane
S. no

Reaction temperature (C)

Product
RON

Sulfur (ppm)

1
2
3
4

260
280
300
320

73.5
71.0
68.3
66.2

60
28
22
20

Reaction conditions: Pressure = 20 bar, LHSV = 2.2 h1, Gas to Oil


ratio = 80/100 (l/l).

Absence of C10 iso-parans may be due to the increased


cracking activity of the molecule. However olens are not
decreased in the HDS product indicating the occurrence
of selective HDS of aromatics in the feed mixture. Formation of olens from the ring opening of cyclic hydrocarbons
on HDS catalyst is also responsible for a slight increase of
olens in the HDS product. This situation makes the process advantageous as the aromatics are selectively converted into iso-parans during the process.
3.4. Octane boosting through isomerization

(<28 ppm). At the varied temperatures from 280 C to


320 C, the HDS product exhibited very negligible variation
of sulfur (from 28 ppm to 20 ppm) .There is also a decrease in
octane number with reaction temperature and the lowest
RON observed is 66.2 at 320 C. In the studied range of reaction temperatures, ecient sulfur removal with minimum
octane loss was observed at 280 C. The product exhibited
28 ppm sulfur and 71 RON at this temperature. This octane
loss needs to be regained through the isomerization reaction.
The dissolved H2S in hydrodesulphurized gasoline product was stripped with N2. and the product obtained after
HDS was analyzed for its detailed composition. The
changes in concentrations of various hydrocarbon types
after HDS can be read from the data given in Table 2,
where the aromatic content is decreased from 47.0 wt%
to 25.4 wt% after HDS. On the other hand, the amount
of iso-parans, naphthenes and n-parans are increased
to 41.3 wt%, 17.2 wt%, and 6.5 wt%, respectively. A slight
decrease in olen amount was also observed after HDS.
It is interesting to note that majority of the reactive species is aromatics followed by olens The decrease in aromatic and olen contents after HDS clearly indicates
their saturation to naphthenes, parans and iso-parans.
Increase in iso-paran content also indicates the formation
of iso-parans through saturation and ring opening of
aromatics. The data given in Table 2 indicates that the
increase in isomers is due to the formation of C7C9 isomers after HDS. Since, the concentration of C7C9 n-parafns is very low in the heavy fraction, the formation of C7
C9 iso-parans from n-parans can be ruled out. Hence,
the possible source for iso-paran must be aromatics or
naphthenes in the feed. This aspect can be further veried
from the changes in concentrations of individual aromatics
after HDS. Among aromatics, C9 aromatics followed by C8
aromatics were decreased after the HDS suggesting their
conversion to iso-parans. Increase of C8 and C9 naphthenes in HDS product also supports the aromatic saturation
and the formation of isomers through naphthene intermediates. This clearly suggests the occurrence of the ring
opening of C7C9 aromatics/naphthenes during the HDS
Thus, the formation of isomers during HDS can be represented as follows.
C7 C10 aromatics ! C7 C10 naphthenes
! C6 C9 iso-paraffins

In spite of the formation of iso-parans, there has been


decrease in the total octane of the feed after HDS due to
the saturation of olens and aromatics to form naphthenes
and n-parans. The reaction was conducted using PtPd/
mordenite catalyst to improve the octane by n-paran
isomerization. The mordenite used in the catalyst preparation is an acidity and porosity modied mordentie, which
has been proven to have benecial eect on n-hexane isomerization [22,23].
3.4.1. Physico-chemical characteristics of catalyst
The properties of dealuminated H-mordenite catalyst
used for conducting isomerization reaction are given in
Table 4. The mordenite exhibited the increase in Si/Al ratio
from 18 to 39 after acid treatment indicating the framework dealumination. The XRD patterns given in Fig. 1
indicate that the mordenite structure is protected during
the dealumination. There is a slight increase in the intensity
of low angle peaks (below 10) due to the decrease in
hydrophilic nature of the dealuminated mordenite [22].
The phenomenon of the inuence of framework alumina
on the intensity of XRD lines is also observed in case of
ZSM-5 [24]. The catalyst was characterized for BET surface area, micro pore volume, pore size distribution, acidity
and Pt dispersion. As can be seen from Table 4, the catalyst
exhibits 291 m2/g surface area even after the addition of
40 wt% binder alumina.
The total surface area can be distinguished as external and
internal (inside micro pores) surface area, where, the values
measured indicates the major contribution of the micro pore
area. The pore volume in pores is 0.4734 cm3/g. Among the
volume in the pores of various sizes that are present in the
mordenite (micro pore), alumina (mesopore), the pores of
contributes maximum area followed by micro
100200 A
pores. The pore size distribution indicates that around
20% volume is in pores is contributed by pores of less than
diameter. Opening of the side pockets of mordenite
10 A
was also observed by acid dealumination (measured below
) [22,25]. These pores can be ascribed to the micro pores
10 A
in the zeolite mordenite. The alumina binder exhibits a wide
to greater than
range of pores with diameters form 20 A

500 A. Among these, the pores of diameter between 100


and 200 exhibited 48.58% of pore volume, followed by those
. Our earlier studies on metal dispersion indiof 20100 A
cated the role of mesopores of alumina on promoting the

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Table 4
Physico-chemical properties of Pt/H-Mordenite
BET surface area (m2/g)
Micro pore area (m2/g)
External surface area (m2/g)
Pt dispersion (%)
Total pore volume (cm3/g)

291.6
158.5
133.1
78
0.4734

Pore size distribution (volume percent)

<10 A
1020 A
20.47
4.19

20100 A
22.74

100200 A
48.58

Micro calorimetry (Acidity in m.mol ammonia ads./g. catal)


Total acidity
Strong acidity
Medium acidity
1.48
0.36
0.57

(b)

(a)

20

40

60

80

2
Fig. 1. X-ray diraction patterns of parent and dealuminated mordenite.
(a) Parent mordenite and (b) Mordenite after acid dealumination.

Pt metal dispersion, where, the pores with diameter 100


were observed to accommodate the Pt ions on the cat200 A
alyst. The catalyst also exhibited 78% Pt dispersion that is
believed to be satisfactory value to obtain an active catalyst.
This further supports the suitability of support property on
the Pt dispersion. The acidity measured by ammonia adsorption indicates the total acidity of 1.48 m mol ammonia/g
catal, where, the strength of the acid sites are arbitrarily categorized in to strong, medium and weak acid sites based on
the heat of adsorption values, i.e., <100 kJ/mol, 75100 kJ/
mol and <75 kJ/mol, respectively. Generally, the sties with
heat of adsorption >75 kJ/mol are considered as the acid
sites associated with the framework aluminum of the zeolite
[26]. The values measured for the present catalyst indicate
about 65% sites with heat of adsorption >75 kJ/mol.
3.4.2. Isomerization of hydrotreated fraction
The detailed analysis data of the heavy fraction before
and after isomerization has been given in Table 2. The results
indicate considerable increase in the iso-paran from
41.3 wt% to 53.5 wt% that is responsible for the octane gain
from 71.0 to 80.7 RON.. The data indicates that the major
contributors to iso-paran pool of the product are
2-methyl-pentane (9 wt%), 3-methyl-pentane (7 wt%),
3-methyl-hexane (5 wt%). However, the comparison of the
isomer concentrations in the feed and product clearly indi-

200500 A
2.45

>500 A
1.57

Weak acidity
0.55

cated the increase is mainly due to the formation of isomers


of iso-hexane followed by iso-heptanes, iso-octanes and
iso-nonanes. The concentration of iso-hexane has been
increased from 7.1 wt% to 21.4 wt% after the reaction. Since,
the n-C6 amount is very minimal in the feed the formation of
iC6 must be occurred from the aromatics/naphthenes.
The concentrations of various isomers of heptane to
nonane contributed to isomer pool are as follows, where,
the concentrations in wt% are given in parenthesis; 2methyl hexane (3.4), 3-methyl hexane (4.2), 2,2,3-trimethyl
pentane (1.1), 2-methyl heptane (2.8), 3-methyl heptane
(3.6), 3-methyl hexane (2.3) and 3-methyl octane (2.5).
Overall, there is an increase in concentrations of 12
branched parans through HDS and isomerization reaction. The increase in concentration of various iso-parans
can be seen from Fig. 2. Total increase in the yield of these
isomers is 15.1 wt% based on the product.
Overall, the product obtained after HDS and isomerization has exhibited high amount of iso-parans. The results
given in Table 2 indicate a two-stage formation of isomers
from 60 C-FBP fraction, namely, (1) formation of C7C9
iso-parans by HDS (through ring opening of aromatics/
naphthenes), and (2) formation of iC6 on mordenite based
catalyst (through cracking and isomerization) It is important to recollect that the feed contains olens of C5C7
hydrocarbons and the aromatics of C7C9 hydrocarbons.
The detailed analysis of the isomerization product indicated
the formation of C7C9 iso-parans that clearly supports
their formation from aromatics rather than from olens.
Also there was an increase in naphthene component
such as methyl cyclo-hexane (MCH), ethyl cyclo-pentane,
and 1t, 2-DM cyclo-pentane. The concentration of C3C5
parans also increased to some extent (4.2 wt%) due to
the cracking reaction on the acidic mordenite catalyst.
Overall, the changes occurred in the concentration of
various hydrocarbon types in 60 C-FBP fraction can be
visualized from Fig. 3. The major observation is the
increase in iso-parans with simultaneous decrease of aromatics in the feed with HDS and isomerization reactions.
The aromatic content in the feed has been decreased from
47 wt% to 16.1 wt% (65.7% decrease). The olen content is
also decreased from 7.2 wt% to 2.5 wt% (65.3% decrease).
Though, the decrease in aromatics is seemingly higher,

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4.5

Feed

Product

Wt. %

1.5

0
2-me- 2,3-di- 3-mehex me-pen hex

3-eth- 2,5-di- 2,2,3pen me-hex tri-mehex

2-me- 4-meth- 3-mehept


hept
hept

3-ethhex

4-meoct

3-meoct

Hydrocarbon Types
Fig. 2. Types of isomers formed during the octane boosting reaction.

nents. The nal composition of the composite blend can be


compared with the composite blend to see the compositional changes of the FCC gasoline. Overall, there is a
signicant increase in iso-parans, with little increase in
n-parans and naphthenes in the composite blend. The
concentration of olens and aromatics is also decreased
in the blend. However, the RON of the blend (86.1) is comparable with that of the feed (86.0). Hence, the overall
change can be considered as the reformulation of FCC gasoline towards less aromatics, olens and more isomers with
no loss in octane number.
Fig. 3. Changes in concentration of ve hydrocarbon types after HDS and
isomerization reactions. P = parans, i-P = iso-parans, N = naphthenes, O = olens, and A = aromatics.

the percent decrease of olens and aromatics (given in


parenthesis) clearly suggests almost similar reactivity of
the olens and aromatics. In the present case, the low
amount of olens is in the feed may be responsible for its
lesser contribution to the formation of isomers. There is
a little increase in n-parans with simultaneous decrease
in olens was also occurred. On the other hand, presence
of higher amount of aromatics in the feed is responsible
for the formation of iso-parans through the hydrogenation of aromatics as shown below.
aromatics ! naphthenes ! iso-paraffins
The increase in naphthenes in the feed fraction after
HDS and isomerization reactions also supports the formation of isomers through the naphthenic intermediate.

4. Conclusions
The FCC gasoline has been reformulated by converting
the aromatics and olens in the feed into iso-parans via
HDS and hydro-isomerization using porosity modied
mordenite based catalyst. The formation of isomers was
occurred in two stages namely, (1) formation of C7C9
iso-parans by ring opening of naphthenes/aromatics by
HDS and (2) formation of iC6 through cracking and isomerization on the mordenite based catalyst. Considerable
amount of aromatics and olens in the feed have been successfully converted into iso-parans. There is a slight
increase in the concentrations of n-parans and naphthenes that are believed to be intermediates in the conversions of olens and aromatics in to iso-parans.
However, the octane loss occurred by decrease in olens
and aromatics has been completely recovered by the formation of iso-parans.

3.5. Blended product analysis


Acknowledgement
The Merox treated lighter fraction (A) was nally combined with the hydrodesulpurized and isomerized heavy
fraction (B) to make composite blend (A+B). Table 2 contains the properties of the fractions and blend along with
the detailed compositional analysis of hydrocarbon compo-

Our sincere thanks to CHT, New Delhi, and CPCL,


Chennai for providing nancial support for carrying out
the research work. Our thanks to the analytical team at
IIP.

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8

N. Viswanadham et al. / Fuel xxx (2006) xxxxxx

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Please cite this article in press as: Viswanadham N et al., Reformulation of FCC gasoline, Fuel (2006), doi:10.1016/j.fuel.2006.09.016