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1159
University of Pannonia, Dep. Hydrocarbon & Coal Proc., H-8201 Veszprm, PO Box:
158, Phone: +36 88/624413, Fax: +36 88/624520, E-mail: hancsokj@almos.unipannon.hu
b
Chemical Research Centre, Institute of Chemistry, Hungarian Academy of Sciences,
Budapest, P.O. Box 17, H-1525, Hungary, E-mail: kallo@chemres.hu
Abstract
The main motivation of the development of hydrodearomatization of middle distillate is
the growing demand for high quality (low sulphur-, nitrogen- and aromatic content) gas
oils for transportation and for economical production of light olefins (ethylene,
propylene). The results of hydrodearomatization of different sulphur and nitrogen
containing real gas oils from Hungarian and Russian crudes on Pt,Pd/USY zeolite,
amorphous Pt,Pd/SiO2-Al2O3 and Pt,Pd/Al2O3 catalysts with different ratio of Pd/Pt are
presented. Additionally, the effect of sulphur and nitrogen contents of feeds and process
conditions on HDA, HDN and HDS activities was studied. The Pt-Pd/USY catalyst
having Pd/Pt atomic ratio of 4:1 was the most active in hydrodearomatization of high
sulphur and nitrogen containing feeds. At favourable process conditions excellent
quality (sulphur: 1-6mg/kg, nitrogen: 1-3 mg/kg and aromatic content: 5-15%, cetane
number: 53-56) diesel fuel blending component can be produced with high gas oil yield,
which is an excellent feed for steam cracking either.
Keywords: hydrodearomatization, zeolite, noble metal, gas oil
1. Introduction
Sulphur content of diesel fuels has been reduced in the World (in EU from 2005:
<50(<10) mg/kg) [1]. Reduction of the aromatic content of diesel fuels is also relevant,
because aromatic hydrocarbons have low cetane number, contributing to the increase of
vehicle HC and PM emissions. For these reasons, in recent years, sulphur and nitrogen
tolerant (up to 50-200) precious metal catalysts have attracted much attention for the
hydrogenation of aromatics in diesel fuels. In case of monometallic noble metal
catalysts (e.g. Pt or Pd), the sulphur content in the feedstock must be strictly reduced
(10 ppm) before the catalyst comes in contact with the feedstock [2,3]. Bimetallic
catalysts (e.g. Pt-Pd/USY) and/or appropriate acidic support can be used to increase the
sulphur tolerance, which depends on electron deficiency of noble metal particles [4,5].
The tolerance to nitrogen is also an important issue because most petroleum feedstocks
contain basic nitrogenous compounds [6,7], which are strongly adsorbed at catalyst
support. The main goal of our experiments was to find Pt,Pd/support catalysts for
hydrodearomatization of up to 300 ppm sulphur and up to 200 ppm nitrogen containing
gas oils from Hungarian and Russian crudes.
2. Experimental
2.1. Apparatus
The experiments were carried out in a high-pressure reactor system [8].
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J. Hancsk et al.
2.2. Materials
The investigated catalysts [9] were Pt-Pd/USY zeolite (SiO2/Al2O3 ratio: 33.5, total- and
mesopore surface areas 650 m2/g and 51 m2/g, total metal content: 0,9%, Pd/Pt mass
ratio: 6:1 to 1:3, dispersion: 0.41-0.55, acidity: 0.20 mmol/g). Metal contents and Pd/Pt
ratios are summarized in Table 1. As reference catalysts bimetallic Pt-Pd/SiO2-Al2O3
(platinum-content: 0.3%, palladium-content: 0.6%, Al2O3 content: 15%, surface area:
292 m2/g, dispersion: 0.41, acidity: 0.18 mmol/g) and Pt-Pd/-Al2O3 (platinum-content:
0.3%, palladium-content: 0.6%, surface area: 182 m2/g, dispersion: 0.35, acidity: 0.12
mmol/g) were used.
2.3. Methods
Pd-, Pt-, Al- and Si-content of catalysts was measured by ICP apparatus. The surface
area was calculated by BET-plots and t-plots. Metal dispersion was determined from the
amount of chemisorbed CO and acidity was determined from the chemisorbed NH3.
2.4. Feeds and Process parameters
The feedstocks were prehydrogenated real gas oil fractions with different aromatic,
sulphur and nitrogen contents from Hungarian and Russian crudes. Their important
properties are summarized in Table 2.
Hydrodearomatization (HDA) was investigated on the mentioned catalysts in
temperature range 260-360C, at total pressures 35-80 bar, hydrogen to hydrocarbon
ratios (H2/HC thereafter) 200-1000 Nm3/m3 and liquid hourly space velocity (thereafter
LHSV) 0.75-4.0 h-1. The experiments were carried out on catalysts of steady-state
activity, in continuous operation.
Table 1. The total metal contents and Pd/Pt ratios of the Pt-Pd/USY catalysts
Properties
Pd/Pt mass ratio
Pd/Pt atomic ratio
Pd content, %
Pt content, %
Total metal content, %
Dispersion
A
0.8370
5
<1
24.3
21.9
2.4
50
184-356
B
0.8361
152
8
32.7
29.5
3.2
50
167-361
Feeds
C
D
E
F
0.8328 0.8607 0.8425 0.8498
280
190
302
320
14
58
153
203
25.7
38.4
32.6
34.5
21.4
26.8
25.4
26.4
4.3
11.6
7.2
8.1
49
48
47
47
205-363 220-375 210-368 212-367
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catalysts should be attributed to the higher acidity of these supports ensuring higher and
more uniform metal dispersion enabling stronger adsorption of aromatics, than in the
case of Pt-Pd/Al2O3 catalyst having additionally the lowest surface area. However, there
was considerable difference between the surface areas of Pt-Pd/USY and Pt-Pd/SiO2Al2O3 catalysts (650 m2/g and 292 m2/g) but the difference between their HDA activities
was only 10-15% under similar process parameters. In addition, the acidity of USY is
higher than that of amorphous silica-alumina thus the adsorption of aromatics is higher.
Thus the reason of slightly higher HDA activity may be the slower permeability of
zeolitic pores than that of silica-alumina.
60
20
HDA, %
50
40
15
30
10
20
5
25
70
10
0
0
260
280
300
320
340
360
Temperature, C
Pt(0.3%)-Pd(0.6%)/USY
Pt(0.3%)-Pd(0.6%)/SiO2-Al2O3
Pt(0.3%)-Pd(0.6%)/SiO
2 -Al2 O3
Pt(0.3%)-Pd(0.6%)/g-Al2O3
Pt(0.3%)-Pd(0.6%)/-Al2 O3
Figure 1. Effect of the temperature on the HDA activity of the investigated catalysts
(feed A, P = 45 bar; LHSV: 1.0 h-1, H2/HC: 600 Nm3/m3)
120
300
100
250
80
200
60
150
40
100
20
50
Sulphur content, %
HDS, %
The HDS activity of investigated catalysts decreased in the order Pt,Pd/USY zeolite>
Pt,Pd/SiO2-Al2O3> Pt,Pd/Al2O3 (Fig. 2). Using Pt(0.3%)-Pd(0.6%)/USY catalyst the
HDS activity considerably increased in the temperature range of 260-320C, but further
increase of the temperature has negligible effect. The attainable sulphur content
reduction was always remarkably lower for Pt(0.3%)-Pd(0.6%)/SiO2-Al2O3 catalyst.
0
260
280
300
320
340
360
Temperature, C
Pt(0.3%)-Pd(0.6%)/USY
Pt(0.3%)-Pd(0.6%)/SiO2-Al2O3
Pt(0.3%)-Pd(0.6%)/SiO
2 -Al2 O3
Pt(0.3%)-Pd(0.6%)/g-Al2O3
Pt(0.3%)-Pd(0.6%)/-Al
2 O3
Figure 2. Effect of temperature on the HDS activity of the investigated catalysts (feed
C, P = 60 bar;LHSV: 1.0 h-1, H2/HC: 600 Nm3/m3)
The Pt(0.3%)-Pd(0.6%)/-Al2O3 catalyst had the lowest HDS (8-23%, sulphur content
of products changed between 257-210 mgS/kg) activity attributed to the lowest acidity
of the catalyst support.
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J. Hancsk et al.
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