Elsevier AMS Code: Sfy ch01-N53084 28-6-2007 9:18 p.m.

Page:1 Trim:165×240 MM TS: Integra, India

Chapter 1

INTRODUCTION

Worldwide trends in crude oil supply have been indicating the declining availability of
conventional crude. This trend has been offset by the increasing production of heavy
crude. For heavy crude, the yield of distillate fractions can be increased by upgrading
distillation residues. A number of thermal processes (e.g., visbreaking, delayed-, fluid-
and flexi-coking) and asphaltenes and metals separation processes (e.g., deasphalting),
the so-called carbon-rejecting processes, have been used on a commercial scale for sev-
eral decades (1,2). Heavy feeds can also be upgraded by hydroprocessing, the so-called
hydrogen addition option (3,4). This requires the presence of hydrogen and an active
catalyst. Compared with thermal processes, hydroprocessing operations are more flexible,
giving higher yields of liquid fractions. However, the costs of high-pressure equipment,
catalysts and H2 required for hydroprocessing have to be offset by the increased yields
and quality of liquid products. The optimum hydroprocessing operation can be achieved
by properly matching the type of reactor and catalyst with the properties of heavy feeds.
Several types of catalytic reactors, i.e., fixed bed, moving bed and ebullated bed reactors,
have been available and used commercially. The efforts to develop entirely new catalytic
phases and reactors with the aim to increase the efficiency of hydroprocessing of heavy
crudes have been made continuously.
In spite of some similarities, the hydroprocessing of heavy feeds differs markedly from
that of light feeds. This results from the presence of high molecular weight asphaltenic
molecules and resins, as well as that of the organometallic compounds in heavy feeds.
In some heavy feeds, a clay-like mineral matter and water-soluble salts in the form of
finely dispersed emulsions can also be present. The difference between hydroprocessing
of heavy feeds and light feeds was clearly indicated in one of the first study dealing
with this issue published by Beuther and Schmid (5) more than four decades ago. More
recently, the topic was reviewed by Oelderik et al. (6) and Beaton and Bertolacini
(7) from the point of view of the Shell and Amoco strategies, respectively. It was
emphasized that the catalyst design for hydroprocessing applications has to take into
consideration the presence of both metals (mostly V and Ni) and heavy species such as
resins and asphaltenes. In this regard, the removal of metals represents a rather complex
set of reactions and events, as was demonstrated in several studies (8–11) focusing
primarily on hydrodemetallization (HDM). A high level of the asphaltenes conversion,
i.e., hydrodeasphaltization (HDAs), has to be maintained simultaneously with that of
HDM (12–14). Therefore, the selection and design of catalysts for hydroprocessing
of heavy feeds is much more challenging than that for light feeds (15,16). Moreover,
the methods used for evaluation of the catalysts have to be carefully chosen to obtain

Font: Times Font Size:10/12 pt Margins:Top:13 mm Gutter:20 mm Text Width:125MM 1 Color COP: Recto page
 Elsevier AMS Code: Sfy ch01-N53084 28-6-2007 9:18 p.m. Page:2 Trim:165×240 MM TS: Integra, India

2 Catalysts for Upgrading Heavy Petroleum Feeds

meaningful results which can be used for catalyst selection (17). Thus, the methods
which have been used traditionally for the evaluation of hydroprocessing catalysts for
the light feeds applications cannot be applied directly to heavy feeds without necessary
modifications.
In designing the suitable catalysts for hydroprocessing of heavy feeds, special atten-
tion has to be paid to the surface properties of catalysts, such as pore size and pore
volume distribution. These parameters have to be selected to ensure that the optimal
combination of porosity and active surface area is achieved. The optimal parameters are
feed dependent suggesting that a combination of the surface properties giving the best
performance for a particular feed may change once the feed is changed. The size and
shape of the catalyst particles are important parameters for ensuring efficient catalyst
utilization, as well as desirable catalyst bed performance. This is much more critical for
fixed bed reactors than for moving and ebullated bed reactors.
An active catalyst for hydroprocessing of heavy feeds has to be resistant to deactivation
by coke and metal deposits. In the case of the latter, the catalyst has to possess a
desirable metal storage capacity. Poisoning of the catalyst by N-bases observed during
the hydroprocessing of light feeds occurs during that of heavy feeds also, although to
a much lesser extent. However, the poisoning by N-compounds increases in the course
of hydroprocessing. For example, when the feed containing asphaltenes and metals is
processed in the fixed bed reactor, the poisoning by N-compounds increases from the
inlet towards the outlet of the fixed bed. In a multistage system, the poisoning by
N-compounds increases towards the last stage of the process.
The duration of a commercial run, before the catalyst replacement is necessary, may be
an indication of the difficulties encountered during the hydroprocessing of heavy feeds.
For example, when a straight run naphtha is used as the feed, the length of hydropro-
cessing run may approach 5 years provided the unwanted events have not occurred. As
a general rule, the units employing fixed bed reactors processing atmospheric gas oils
or vacuum gas oils have typical run lengths of about 2 years. In the case of a high
asphaltenes and metals feed, significant modifications of the process employing fixed
bed reactors would be required to extend the length of the run beyond 1 year. It should
be noted that the structure of catalysts used for hydroprocessing of heavy feeds differs
markedly from those used for light feeds. Thus, a total loss of activity would be observed
within a few weeks onstream, if the catalyst suitable for hydroprocessing of naphtha is
used for hydroprocessing of a heavy feed containing metals and asphaltenes.
Because of the many parameters involved during preparation, the cost of catalysts
used for hydroprocessing of the feeds containing metals and asphaltenes is much greater
than that for the light feeds derived from conventional crudes. Significant efforts have
been made to increase the resistance of catalysts to deactivation, i.e., to prolong their
life onstream. These involved modifications of the currently used Co(Ni)Mo(W)/Al2 O3 -
based catalysts, as well as the development of entirely new types of catalytic phases.
The importance of the conditions applied during catalyst preparation and of the dif-
ferent supports on the catalyst performance has been recognized. New information on
hydroprocessing of heavy feeds published in the literature will be reviewed including
the schemes for regeneration and utilization of spent catalysts. Some problems associ-
ated with the hydroprocessing of heavy feeds can be alleviated by using once-through
low-cost catalysts. Regarding catalyst design and testing, the focus has been on heavy
feeds of petroleum origin. Thus, feeds such as coal-derived liquids, oil shales, bio-crude
have not been considered.

Font: Times Font Size:10/12 pt Margins:Top:13 mm Gutter:20 mm Text Width:125MM 1 Color COP: Recto page
 Elsevier AMS Code: Sfy ch01-N53084 28-6-2007 9:18 p.m. Page:3 Trim:165×240 MM TS: Integra, India

Introduction 3

Catalytic dewaxing is a process operating under conditions approaching those

employed during conventional hydroprocessing. However, the structure of dewaxing
catalysts may differ markedly from that of the typical hydroprocessing catalysts. During
catalytic dewaxing, heavy feeds such as vacuum gas oil (VGO) and deasphalted oil
(DAO) are upgraded to obtain diesel oil and the lube base stock. The latter is used for
preparation of lubricants. The primary objective of dewaxing is the enhancement of the
cold flow properties of the products. In the case of the lube base stock, improvement
in viscosity index may be achieved by converting aromatic structures to naphthenic
compounds. The latter possess a higher viscosity index. Also, the long chain paraf-
fins which would affect the pour point and freezing point of lube oils and diesel oil
have to be removed. For this purpose, catalytic hydroisomerization of n-paraffins to
iso-paraffins is the method of choice. The details of catalytic dewaxing of VGO and
DAO are given in the Chapter 11 with the aim of identifying the difference between
the structure of the dewaxing catalysts and that of the conventional hydroprocessing
catalysts.
The methods for unconventional hydroprocessing are in various stages of development.
The focus, in this case, has been on the catalysts in either dissolved or micronized form.
In these forms, catalysts can be readily slurried with heavy feeds. The catalyst precursors
can also be dissolved in an oil and water. These solutions can then be blended with
a heavy feed. When added to the heavy feed, catalytically active phase is formed in
situ from the dissolved precursor. A nearly molecular size of the catalytically active
phase ensures almost complete catalyst utilization in the slurry bed reactor, typically
used for such catalysts. These catalysts are dominated by transition metals, particularly
those which are part of the conventional catalysts. Unconventional methods such as
bio-upgrading are still in the early stages of development, in spite of the decades of
research. Although the account of these processes in this book is rather cursory, sufficient
information is provided to assess the viability of the emerging hydroprocessing methods
in relation to those used commercially. Moreover, references made to numerous articles
and reviews published during the last decade may assist in identifying the source of
necessary information for those interested in the field.
Among the non-hydroprocessing methods for upgrading heavy feeds, fluid catalytic
cracking (FCC) process has been receiving most of the attention. Attempts have been
made to use this process for upgrading heavy feeds containing asphaltenes and metals.
However, significant modifications of the process configurations, as well as entirely dif-
ferent catalytic phases compared with the traditionally used FCC catalysts, are required.
Although some progress has been made, it is unlikely that the upgrading of heavy
feeds with metals content approaching 50 ppm of V + Ni, using significantly modi-
fied FCC process, i.e., residue FCC (RFCC) process, can be achieved without diffi-
culties. For comparison with the conventional and unconventional hydroprocessing, a
chapter on FCC/RFCC (Chapter 13) is added to indicate a significant difference in
the ability of these methods to process heavy feeds. Thus, a high flexibility of the
hydroprocessing method is indicated by the fact that heavy feeds differing widely in
the content of asphaltenes and metals can be processed contrary to that for RFCC.
This suggests that it may be inaccurate to refer to the latter as the method for residues
upgrading.
Upgrading of heavy feeds using thermal processes (e.g., coking) and separation pro-
cesses (deasphalting) is discussed in the last chapters. At least a cursory account of these

Font: Times Font Size:10/12 pt Margins:Top:13 mm Gutter:20 mm Text Width:125MM 1 Color COP: Recto page
 Elsevier AMS Code: Sfy ch01-N53084 28-6-2007 9:18 p.m. Page:4 Trim:165×240 MM TS: Integra, India

4 Catalysts for Upgrading Heavy Petroleum Feeds

processes was deemed necessary to aid the reader in identifying the non-catalytic options
for upgrading heavy petroleum feeds, as well as to determine the limits beyond which
catalytic upgrading becomes unattractive compared with the carbon rejection option.
Moreover, some heavy feeds under consideration in this book, i.e., heavy gas oil (HGO)
and DAO, were obtained using non-catalytic upgrading processes such as coking and
deasphalting, respectively.

Font: Times Font Size:10/12 pt Margins:Top:13 mm Gutter:20 mm Text Width:125MM 1 Color COP: Recto page