Documente Academic
Documente Profesional
Documente Cultură
a,*
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-
Corresponding author.
E-mail addresses: nvish@iip.res.in, nviswanadham@india.com (N.
Viswanadham).
0016-2361/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2006.09.016
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
ARTICLE IN PRESS
2
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.
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
ARTICLE IN PRESS
N. Viswanadham et al. / Fuel xxx (2006) xxxxxx
selectivityC%
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
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
ARTICLE IN PRESS
4
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
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
ARTICLE IN PRESS
N. Viswanadham et al. / Fuel xxx (2006) xxxxxx
Table 3
Eect of reaction temperature on product sulfur and octane
S. no
Product
RON
Sulfur (ppm)
1
2
3
4
260
280
300
320
73.5
71.0
68.3
66.2
60
28
22
20
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
ARTICLE IN PRESS
6
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
<10 A
1020 A
20.47
4.19
20100 A
22.74
100200 A
48.58
(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.
200500 A
2.45
>500 A
1.57
Weak acidity
0.55
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
ARTICLE IN PRESS
N. Viswanadham et al. / Fuel xxx (2006) xxxxxx
4.5
Feed
Product
Wt. %
1.5
0
2-me- 2,3-di- 3-mehex me-pen hex
3-ethhex
4-meoct
3-meoct
Hydrocarbon Types
Fig. 2. Types of isomers formed during the octane boosting reaction.
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.
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
ARTICLE IN PRESS
8
References
[1] Kaufmann TG, Kaldor A, Stuntz GF, Kerby MC, Ansell LL. Catal
Today 2000;62:77.
[2] Marcilly C. Stud Surf Sci Catal 2001;135:37.
[3] Song C, Ma X. Appl Catal B: Environ 2003;41:207.
[4] Babich IV, Moulijn JA. Fuel 2003;82:607.
[5] Gatte R, Harding R, Albro T, Chin D, Wormsbecher RF. Am Chem
Soc Prepr Div Fuel Chem 1992;37(1):P33.
[6] Miller JT, Reagan WJ, Kaduk JA, Marshall CI, Kropf AJ. J Catal
2000;193:123.
[7] Hatanaka S, Yamada M, Sadakane O. Ind Eng Chem Res
1997;36:1519.
[8] Wang JFP, He MY. Am Chem Soc Prepr Div Pet Chem
2000;45(4):697.
[9] Myrstad T, Seljestokken B, Engan H, Rytter E. Appl Catal A: Gen
2000;192:299.
[10] Corma A, Martinez C, Gullbrand P. Am Chem Soc Prepr Div Pet
Chem 1999;44(4):490.
[11] Corma A, Martinez C, Ketley G, Blair G. Appl Catal A: Gen
2001;208:135.
[12] Song C. Catal Today 2003;86:211.
[13] Plantenga FL, Leliveld RG. Appl Catal A: Gen 2003;248:1.
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