Energy & Fuels 2006, 20, 1145-1149 1145

Atmospheric Residue Desulfurization Process for Residual Oil

Upgrading: An Investigation of the Effect of Catalyst Type and
Operating Severity on Product Oil Quality
A. Marafi,*,† A. Hauser,‡ and A. Stanislaus†
Petroleum Refining Department and Central Analytical Laboratory, Kuwait Institute for Scientific
Research, P.O. Box 24885, Safat 13109, Kuwait

ReceiVed NoVember 25, 2005. ReVised Manuscript ReceiVed February 11, 2006

Atmospheric residue desulfurization (ARDS) process is extensively used in upgrading of heavy petroleum
oils and residues to more valuable clean environmentally friendly transportation fuels and to partially convert
the residues to produce low-sulfur fuel oil and hydrotreated feedstocks. Graded catalyst systems in multiple
reactors are used in the process in order to achieve hydrodesulfurization (HDS), hydrodemetallization (HDM),
hydrodenitrogenation (HDN), and conversion of residues to distillates at desired levels. The characteristics of
the feedstocks processed in different reactors are significantly different. The quality of the feed entering the
second reactor is strongly dependent on the operating severity in the first reactor and can have an important
impact on the performance of the catalysts in the following reactor with regard to various conversions and
deactivation rate. In the present work, a systematic study was conducted on the effect of two industrial catalyst
types, namely, MoO3/Al2O3 (HDM) and Ni/MoO3/Al2O3 (HDS) catalysts, in the range of 360-420 °C operating
temperature on product quality in hydrotreating straight run Kuwait atmospheric residue. The liquid products
and their asphaltene fractions from different runs were characterized by various techniques including 13C NMR
and elemental analysis, and the effect of catalyst and operating severity on product quality was assessed.
Special attention was paid to the changes in the characteristics of asphaltenes as a function of operating
temperature and catalyst type. The results revealed that, besides the usual heteroatoms removal reactions, such
as HDS, HDM, and HDN, asphaltenes and resins in the residual oil feed were converted to saturates and
aromatics during the hydrotreating process. The aromatic rings in the asphaltenes remaining in the product oil
become more condensed and less alkyl-substituted with increasing operating severity disregarding the types
of catalyst used. The aromaticity and degree of condensation in the product asphaltenes were higher for the
HDM than for the HDS catalyst. The catalyst’s hydrogenation activity appears to play a dominant role in
determining the nature of the asphaltenes in the product oil. Since the quality of the liquid products, particularly
the quality of the residual asphaltenes in the product oil from different catalyst beds, plays a key role in
catalyst deactivation and fuel oil stability, the results are considered to be very valuable for optimization of
the operating conditions as well as on catalyst selection for hydroprocessing of residual oil in an ARDS process.

1. Introduction
To meet the challenges facing the refining industry, a number
of conventional processes were developed to refine and upgrade
petroleum residues to more valuable transportation fuels or low-
sulfur fuel oil.1,2 Two main routes, namely, carbon rejection
and hydrogen addition, are commonly used for residual oil
conversion and upgrading.1-4 The former one involves thermal
treating of heavy oils in the absence of hydrogen. This causes
large hydrocarbon molecules to crack into smaller molecules,
resulting in the production of distillates and gas. A number of
* To whom correspondence should be addressed. Fax: (+965)3980445.
E-mail: amarafie@prsc.kisr.edu.kw.
† Petroleum Refining Department.
‡ Central Analytical Laboratory.
(1) Gray, M. R. Upgrading Petroleum Residues and HeaVy Oils; Marcel
Dekker: New York, 1994.
(2) Khan, M. R.; Patmore, D. J. Heavy oil upgrading processes. In
Petroleum Chemistry and Refining; Speight, J. G., Ed.; Marcel Dekker:
New York, 1998; pp 149-173.
(3) Babich, I. V.; Moulijn, J. A. Science and technology of novel
processes for deep desulfurization of oil refinery streams: a review. Fuel
2003, 82, 607-631.
(4) Le Page, J. F. Resid and HeaVy Oil Processing; Editions Technip:
Paris, 1992.
technologies such as delayed coking, resid FCC, etc., have been
developed over the years for residual oil upgrading based on
the carbon-rejection route.
The second route, the hydrogen-addition route, involves
contact of the residual oil with hydrogen at high temperatures
and pressures. The high-molecular-weight residual oil feedstock
is cracked and hydrogenated to yield distillate products with
an increased H/C ratio and residual oil with reduced sulfur,
nitrogen, and metals contents. The process can be catalytic or
noncatalytic. In the catalytic hydrogen-addition processes, high-
activity hydrotreating catalysts, such as Ni-Mo/Al2O3 or Co-
Mo/Al2O3, are employed.5-8 These catalysts have functions (i)
to enhance the removal of undesirable contaminants, such as
(5) Furimsky, E. Selection of catalysts and reactors for hydroprocessing.
Appl. Catal., A 1998, 171, 177-206.
(6) Delmon, B. New technical challenges and recent advances in
hydrotreatment catalysis. Catal. Lett. 1993, 22, 1-32.
(7) Topsoe, H.; Clausen, B. S.; Topsoe, N. Y.; Zeuthen, P. Progress in
the design of hydrotreating catalysts based on fundamental molecular insight.
Stud. Surf. Sci. Catal. 1990, 53, 77-102.
(8) Bartholdy, J.; Cooper, B. H. Optimizing hydrotreater catalyst loadings
for the upgrading of atmospheric residues. Catalysts in Petroleum Refining
and Petrochemical Industries 1995; Elsevier: Amsterdam, 1996; pp 117-
124.

10.1021/ef050395d CCC: $33.50 © 2006 American Chemical Society

Published on Web 04/04/2006
1146 Energy & Fuels, Vol. 20, No. 3, 2006 Marafi et al.

sulfur, nitrogen, and metals, present in the residual feed by Table 1. KU-AR Feed Characteristics
promoting hydrodesulfurization (HDS), hydrodenitrogenation feed property unit values accuracy %
(HDN), and hydrodemetallization (HDM) reactions, (ii) to API - 12.27 2
accelerate the conversion of the high-molecular-weight com- S wt % 4.30 3
ponents to lighter products, (iii) to promote hydrogenation of N wt ppm 2670 3
the cracked fragments, leading to an increase in the overall H/C CCR wt % 12.20 2
ratio of the products, and (iv) to reduce the coke formation. asphaltene wt % 3.60 2
Ni wt ppm 21 1
The preference between the two routes depends on factors V wt ppm 69 2
such as environmental constraints, feedstock flexibility, and density @15 °C mg/mL 0.9837 0.1
product target. The hydrogen-addition route has the advantage kinematic viscosity @ 50 °C cSt 871. 0.5
to yield products of higher quality than the carbon-rejection route
Table 2. Characteristics of Catalysts Used in the Present Study
does. The distillates and residual oils produced by hydrocon-
version processes have low levels of aromatics, sulfur, nitrogen, catalyst
and other contaminants, and they have better stability. characteristics unit HDM HDS
The atmospheric residue desulfurization (ARDS) process has bulk density g/mL 0.4-0.5 0.6-0.7
been developed for residual oil upgrading following the surface area m2/g 150-200 200-250
hydrogen-addition route. This process is used extensively in average pore diameter Å 150-200 80-100
active metal Mo Ni, Mo
Kuwaiti refineries for the upgrading of petroleum residues.5,9,10 metal content
The process involves hydrotreatment of the residual oil feed in Mo wt % 2-3 7-9
a series of fixed bed reactors loaded with different types of Ni wt % - 2-3
catalysts. Catalysts for such hydrotreating processes are selected metal capacity high medium
on the basis of activity, selectivity, and life-on-stream. The
catalyst life depends on the rate of deactivation by coke and including 13C NMR. Special attention was paid to structural
metal deposits as well as on the sintering of the active phase. changes in the asphaltenes as a function of operating temperature
The performance of the overall ARDS process with regard to for the two types of catalysts. Since the quality of the residual
various reactions, such as HDM, HDS, HDN, asphaltenes asphaltenes in the product oil plays a key role in catalyst
cracking, feed conversion to distillates, and catalyst lifetime, is deactivation and fuel oil stability, the results of the study will
clearly linked to the performance of the catalysts in the different be useful for catalyst selection and for optimization of the
reactors.5,11 In the ARDS process, the characteristics of the operating conditions in the ARDS process. The results presented
feedstocks processed in different reactors are significantly in this paper are part of a broader study on the ARDS process
different. For example, the feed that enters the front reactor is optimization pursued in our laboratories.12-18
original atmospheric residue, whereas the feed to the second
reactor is a demetallized and partially hydrotreated product from 2. Experimental Section
the first reactor. The quality of the feed entering the second 2.1. Materials. The characteristics of the typical feed used in
reactor is strongly dependent on the operating severity in the the refinery ARDS process and in this study, namely, KU-AR, are
first reactor and can have a significant influence on the shown in Table 1. Two industrial ARDS hydroprocessing catalysts,
performance of the catalysts in the following reactor with regard namely, a MoO3/Al2O3 (HDM) catalyst dedicated for metal removal
to various conversion reactions and the catalyst deactivation rate. and a NiMo/Al2O3 (HDS) catalyst intended to remove sulfur, were
Therefore, information about the product quality and the used for conducting the comparison studies. The characteristics of
behavior of a multiple catalyst system under ARDS process both catalysts are presented in Table 2.
conditions are highly desired to optimize the reactor loading 2.2. Hydrotreating Techniques. The hydrotreating experiments
and the operating conditions. To date, information about the were conducted in a fixed-bed reactor unit (Vinci Technologies)
using KU-AR as feed. Experiments were carried out for each
effect of catalyst type and operating severity on the product oil
catalyst individually. A 50 mL of catalyst charge diluted with an
quality, e.g., detailed characteristics of the maltene and asphal- equal amount of carborundum was used for each run. The catalyst
tene fractions are limited. was presulfided by a standard procedure using straight run gas oil
In the present study, performance comparison tests were
carried out on two types of industrial catalysts, namely, an HDM (12) Matsushita, K.; Hauser, A.; Marafi, A.; Stanislaus, A. Initial coke
(MoO3/Al2O3) and an HDS (Ni/Mo/Al2O3) catalyst, that are deposition on hydrotreating catalysts: Part I. Changes in coke properties
as function of time on stream. Fuel 2004a, 83, 1031-1038.
loaded in the front and middle reactors of the commercial ARDS (13) Matsushita, K.; Marafi, A.; Hauser, A.; Stanislaus, A. Relation
process, using atmospheric residue from Kuwait expot crude between relative solubility of asphaltenes in product oil and coke deposition
(KU-AR) as a feed in a fixed-bed pilot plant. The primary in residue hydroprocessing. Fuel 2004b, 83, 1669-1674.
objective of the work was to carry out systematic studies to (14) Marafi, A.; Al-Bazzazi, H.; Al-Marri, M.; Maruyama, F.; Absi-
Halabi, M.; Stanislaus, A. Residual-oil hydrotreating kinetics for graded
assess the quality of the liquid oil products obtained at various catalyst sustems: Effect of original and treated feedstocks. Energy Fuels
reaction temperatures using both types of catalysts. The product 2003a, 17 (5) 1191-1197.
oils were fractionated into maltenes and asphaltenes, and the (15) Marafi, A.; Fukase, S.; Al-Marri, M.; Stanislaus, A. A comparative
study on the effect of catalyst type on hydrotreating kinetics of Kuwaiti
asphaltene fractions were characterized by various techniques atmospheric Residue. Energy Fuels 2003b, 17 (3), 661-668.
(16) Marafi, A.; Stanislaus, A.; Absi-Halabi, M.; Hauser, A.; Matsishita,
(9) Al-Nasser, A.; Chaudhuri, S. R.; Bhattacharya, S. Mina Abdulla K. A comparative studies of an industrial Mo/Al2O3 and Ni-Mo/Al2O3
refinery experience with atmospheric residue desulfurization (ARDS). Stud. catalysts: Deactivation behavior in hydrotreating Kuwaiti atmospheric
Surf. Sci. Catal. 1996, 100, 171-180. residue. Pet. Sci. Technol. 2005, 23, 385-408.
(10) Abbas, A. K.; Chaudhuri, S. R.; Bhattacharya, S. Performance (17) Hauser, A.; Stanislaus, A.; Marafi, A.; Al-Adhwani, A. Initial coke
optimization of atmospheric residue desulphurization units. Proceedings, deposition on hydrotreating catalysts: Part II. Structural elucidation of initial
8th Annual Saudi-Japanese Symposium, Dhahran, Saudi Arabia, November coke on hydrodemetallation catalysts by selective suppression of 13C signals
29-30, 1998; pp 175-189. in solid-state NMR. Fuel. 2005a, 84, 259-269.
(11) Adams, C. T.; Del Peggio, A. A.; Schaper, H.; Stork, W. H. J.; (18) Hauser, A.; Marafi, A.; Stanislaus, A.; Al-Adwani, A. Relation
Shiflett, W. K. Hydroprocessing catalyst selection. Hydrocarbon Process. between feed quality and coke formation in a three-stage atmospheric residue
1989, September, 57-61. desulfirization (ARDS) process. Energy Fuels 2005b, 19, 544-553.
ARDS Process for Residual Oil Upgrading Energy & Fuels, Vol. 20, No. 3, 2006 1147

Table 3. Run Conditions for Temperature Effect Studies Table 4. Reaction Temperature Effect on the Liquid Product
Quality in Hydrotreating of KU-AR over HDM and HDS Catalysts
process parameter unit range/value
temperature
temperature °C 360-420
pressure bar 120 parameter unit 360 °C 380 °C 400 °C 420 °C
LHSV h-1 1
HDM Catalyst
H2/oil ratio mL/mL 570
S wt % 3.23 2.79 2.62 1.55
time on stream h 120
N wt ppm 2600 2570 2486 2255
CCR wt % 10.50 9.52 8.54 6.83
containing 3 wt % dimethyl disulfide (DMDS) before injecting the asphaltenes wt % 2.22 1.68 1.21 -
feed. After the presulfiding, conditions for each run were adjusted V wt ppm 35 23 11 6
to desired operating temperature, pressure, hydrogen flow rate and Ni wt ppm 12 10 8 4
liquid Hourly Space Velocity (LHSV). Table 3 shows the various density @ 15 °C g/mL 0.9837 0.9655 0.9609 0.9225
operating conditions for the studies. During the course of each run, HDS Catalyst
product samples were collected after 120 h and analyzed for sulfur, S wt % 1.38 1.08 0.56 0.22
metals (V and Ni), nitrogen, asphaltenes, Conradson carbon residue N wt ppm 2510 2430 1960 1780
(CCR), viscosity, density, and distillate yield using standard methods CCR wt % 7.56 6.95 4.76 3.66
for petroleum product evaluation.19,20 asphaltenes wt % 2.93 2.40 1.75 1.32
2.3. Product Analysis. The product oils from hydrotreating V wt ppm 26 22 12 5
Ni wt ppm 10 8 6 4
experiments at various temperatures were separated into maltenes density @ 15 °C gm/mL 0.9737 0.9510 0.9444 0.9100
and asphaltenes applying the IP-143.20 The carbon, hydrogen, sulfur,
and nitrogen contents were determined using a CE elemental The results presented in Figure 1 indicate that as the reactor
analyzer, model EA 1110. The 1H and 13C NMR were carried out temperature increases, the products are more purified and
on a Bruker AVANCE300 spectrometer operating at 7.05 T. CDCl3 become lighter, suggesting that they might be processed more
(99.8%) and tetramethylsilane (TMS), both from WILMAD, were easily in the following reactor of an ARDS unit with multiple
used as solvent and as internal standard for the 1H NMR measure-
reactors. However, besides the contaminant levels, the structural
ments. The 13C chemical shift values were referenced to the central
signal of the CDCl3 at 77.7 ppm. For 1H NMR, the sample characteristics of the various fractions of the product oil,
concentration was approximately 15 wt % in 0.5 mL of CDCl3. particularly that of the asphaltene fraction, could play a dominant
The solution was filled into a 5 mm tube, and a drop of TMS was role in the ease of its processibility as well as on catalyst
added. To obtain quantitative 13C NMR spectra, the solution was deactivation in the subsequent reactors in series.16,22 Therefore,
transferred to a 10 mm tube, and the concentration was increased the liquid products collected after hydrotreating of KU-AR at
to about 60 wt %. 1H NMR spectra were acquired with a spectral various temperatures over both types of catalyst were separated
width of 5.5 kHz, a pulse angle of 90° (20 µs), and a delay time of into maltenes and asphaltenes (Table 5). The asphaltenes fraction
3 s. The settings for the quantitative 13C NMR measurements were was subjected to detailed characterization using elemental and
as follows: inverse gated decoupling as pulse program, 25 kHz 13C NMR analysis to examine the nature of changes in its
spectral width, 30° (3 µs) pulse angle, and 60 s delay time.
characteristics.
3.2. Properties of Product Asphaltenes. 3.2.1. Elemental
3. Results and Discussions Analysis. The asphaltene fractions from KU-AR hydrotreating
3.1. Bulk Properties of the Product Oil. Initial studies over both HDM and HDS catalysts were further subjected to
focused on the effect of reaction temperature on the overall elemental analysis to determine C, H, N, and S contents. The
product quality during hydrotreating of KU-AR. The charac- results of H/C, N/C, and S/C molar ratios for the asphaltene
teristics of the product oils obtained from various runs at fractions as a function of temperature are given in Table 6. For
different temperatures for both catalysts are presented in Table both catalysts, the H/C in the asphaltene fractions decreases as
4. The results reveal that an increase in the reactor temperature the temperature increases, with a steeper decrease for the HDM
from 360 °C to 420 °C enhances the removal of various catalyst (Table 6). The S/C and N/C molar ratios in the
hetroatoms present in KU-AR. In the tested range, temperature asphaltene fractions are higher for the HDM catalyst than the
increase has a favorable effect on the purification of the product HDS catalyst at all temperatures. As for the hydroprocessing
from S, N, V, Ni, and CCR. Moreover, the results show for of asphaltenes, the elemental analysis indicates that the HDS
both catalysts that the density of the product oils decreases with catalyst is superior to the HDM catalyst. These results are
increasing temperature, indicating an acceleration of feed consistent with the quality of the product oils obtained from
conversion to lighter products at higher temperature. In terms hydrotreating KU-AR over both catalysts as discussed earlier.
of S, N, V, Ni, and CCR removal, the HDS catalyst shows a 3.2.2. 13C NMR Analysis. The aromaticity and structural
better performance than the HDM catalyst (Figure 1). The characteristics of asphaltenes remaining in the product oil
asphaltene conversion, however, is more efficient over the HDM resulting from hydrotreatment of KU-AR over the two types of
catalyst. This result is expected since the HDM catalyst catalysts were further examined by 13C NMR analysis. The
possesses large pores, which facilitate the diffusion of bulky results presented in Figure 2 show that the aromaticity of the
asphaltene molecules into the catalyst pellet.15,21 The HDS asphaltenic fraction increases with increasing temperature
catalyst, on the other hand, due to its medium pore size and despite an appreciable decline in their concentrations in the
higher hydrogenation activity, is more appropriate to remove product oils. Besides the overall reduction in the amounts of
sulfur, CCR, and to a lesser extent nitrogen. asphaltenes, significant changes in the average chemical struc-
ture of the asphaltenes were also noticed as the temperature
(19) ASTM. Annual Book of ASTM Standards: Petroleum Products, was increased.
Lubricants and Fossil Fuels; American Society for Testing and Materials: Due to a higher hydrogenation activity of the HDS catalyst
Philadelphia, PA, 1996; Vols. 5.01, 5.02, and 5.03.
(20) The Institute of Petroleum. Standard Method for Analysis and compared with the HDM catalyst, the asphaltenes in the products
Testing of Petroleum and Related Products; John Wiley & Sons: New York,
1995; pp 143.1-143.4. (22) Higashi, H.; Takashi, T.; Kai, T. The effect of start-up conditions
(21) Quan, R. J.; Ware, A.; Hang, C. W.; Wei, J. Hydrodemetallation of of hydrotreating catalyst for heavy residue with high asphaltene content.
Petroleum. AdV. Chem. Eng. 1988, 14, 95-257. Catal. SurV. Jpn. 2002, 5, 111-119.
1148 Energy & Fuels, Vol. 20, No. 3, 2006 Marafi et al.

Figure 1. Performance of HDM and HDS catalysts in S, N, V, Ni, CCR, and asphaltenes removal; normalized contaminant level in product oils
(KU-AR feed ) 100%).

Table 5. Yield Comparison between HDM and HDS Catalysts

temperature
fraction unit 360 °C 380 °C 400 °C 420 °C
HDM Catalyst
maltenes wt % 97.80 98.32 98.79 99.46
asphaltenes wt % 2.2 1.68 1.21 0.54
HDS Catalyst
maltenes wt % 97.07 97.61 98.25 98.68
asphaltenes wt % 2.93 2.41 1.75 1.32

Table 6. H/C, N/C, and S/C Atomic Ratios in Asphaltenes Fraction

in the Product Oil Obtained from Hydrotreating of KU-AR over
HDM and HDS Catalysts as a Function of Reaction Temperature
temperature
ratio 360 °C 380 °C 400 °C 420 °C
HDM Catalyst
H/C 1.11 1.09 0.85 0.82
N/C 0.01 0.01 0.01 0.01
S/C 0.04 0.04 0.03 0.02
HDS Catalyst
Figure 2. Asphaltene aromaticity and content of asphaltanes in the
H/C 1.22 1.15 1.20 1.19
N/C 0.01 0.01 0.01 0.01 product oils from hydrotreating of KU-AR over an HDM and an HDS
S/C 0.03 0.03 0.02 0.01 catalyst vs reactor temperature.

temperature in the “HDM asphaltenes” than in the “HDS

hydrotreated over the HDS catalyst possess about 10% less
aromatic carbon than the asphaltenes in the “HDM products”
(Figure 3a). As for the types of aromatic carbon in the
asphaltenes, the following observations have been made: (i)
the “HDM asphaltenes” contain more tertiary and quaternary
aromatic carbons than the “HDS asphaltenes” (Figure 3b) and
(ii) the tertiary aromatic carbon increases faster with increasing
asphaltenes” (Figure 3c).
The degree of condensation, defined as the ratio between
carbon in bridgehead positions of condensed aromatic rings and
total aromatic carbon, increases progressively with increasing
temperature (Figure 4). At low temperatures; the “HDS asphal-
tenes” are more condensed than the “HDM asphaltenes”. As
the reactor temperature rises, the degree of condensation in the
ARDS Process for Residual Oil Upgrading
Figure 3. Distribution of (a) aromatic carbon, (b) tertiary aromatic
carbon, and (c) quaternary aromatic carbon in the asphaltenes remaining
in the product oils vs reactor temperature: comparison between the
HDM and HDS processes.
Figure 4. Degree of condensation in the asphaltenes vs reactor
temperature: comparison between the HDM and HDS processes.
“HDM asphaltenes” increases at a faster rate than in the “HDS
asphaltenes”. Because of the lower hydrogenation activity of
the unpromoted HDM catalyst, thermal cracking and condensa-
tion may occur predominantly at higher temperature; while in
the presence of the HDS catalyst, progressive asphaltene
condensation may be prevented at the same temperatures.
The degree of alkyl substitution of aromatic rings, defined
as ratio of alkyl-substituted carbon to peripheral carbon in
aromatic rings, stays lower in the “HDM asphaltenes” than in
“HDS asphaltenes” through the whole temperature range (Figure
5). This points to differences in the ability of hydrothermal
cleavage of side chains from aromatic rings by both catalysts.
In catalytic hydroprocessing, highly condensed aromatic
asphaltenes are the least reactive feed constituents, and they
have a high propensity to form coke that could foul the
catalyst.18,23,24 High operating severity in the first reactor of the
ARDS unit in the presence of an unpromoted Mo/A2O3 catalyst
with relatively low hydrogenation activity appears to have
resulted in the formation of coke precursors in the product,
Energy & Fuels, Vol. 20, No. 3, 2006 1149
Figure 5. Degree of alkyl substitution of aromatic rings in the
asphaltenes remaining in the product oils vs reactor temperature:
comparison between the HDM and HDS processes.
which in turn can lead to rapid deactivation of the catalyst in
the next reactor in series. Thus, mild temperatures in the first
rector in series and high hydrogen pressure and an active
hydrogenation catalyst in the reactors following the “HDM
reactor” can improve hydrogenation of the asphaltenes and
suppress conversion of coke precursors to coke on the catalysts.
The results obtained from this study have demonstrated that
the quality of the residual asphaltenes in the product oil plays
a key role in predicting catalyst deactivation and fuel oil stability.
The results obtained from this study will be useful for catalyst
selection and for optimization of the operating conditions in
the ARDS process.
4. Conclusions
In the present study, the effect of operating severity on the
quality of liquid products obtained during catalytic hydrotreating
of Kuwait atmospheric residue (KU-AR) was investigated. Two
types of industrial hydrotreating catalysts, namely, Mo/Al2O3
(HDM) and Ni-Mo/Al2O3 (HDS) catalysts, were used in the
study. The results indicated that the quality of the liquid products
formed during catalytic hydrotreating of petroleum residues
depends strongly on the operating severity and catalyst type
used in the process. The product oil became more purified by
the removal of the undesirable contaminants (S, N, V, and Ni)
with increasing temperature. The asphaltenes and resins present
in the residual oil were converted to saturates and resins during
the hydrotreating process. However, the polynuclear aromatic
rings in the asphaltenes remaining in the product oil became
more condensed and less alkyl substituted with increasing
operating temperature regardless of the types of catalysts used.
The catalyst’s hydrogenation activity also played a dominant
role in determining the nature of the asphaltenes in the product
oil. The aromaticity and degree of condensation in the product
asphaltenes were higher when a MO/Al2O3 catalyst with low
hydrogenation activity was used for hydrotreating compared to
that for a NiMo/Al2O3 catalyst with high hydrogenation function.
Acknowledgment. This work is a joint project between the
Japan Cooperation Center Petroleum, JCCP (funded by the Ministry
of Economic, Trade and Industry, METI), Japan, and the Kuwait
Institute for Scientific Research, KISR, Kuwait. It bears the KISR
Project No. PF010C.
EF050395D
(23) Seki, H.; Yoshimito, M. Deactivation of HDS catalyst in two-stage
RDS process. II. Effect of crude oil and deactivation mechanism. Fuel
Process. Technol. 2001, 69, 229-238.
(24) Absi-Halabi, M.; Stanislaus, A.; Trimm, D. L. Coke formation on
catalysts during the hydroprocessing of heavy oil. Appl. Catal. 1991, 72,
193-215.