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Energy Science and Technology
Volume 3
Oil and Natural Gas

Editors
Umesh Chandra Sharma
Ram Prasad
Sri Sivakumar

Executive Editor
J.N. Govil

2015

Studium Press LLC, U.S.A.

Editors: Umesh Chandra Sharma, Ram Prasad & Sri
Sivakumar
Executive Editor: J.N. Govil

Energy Science and Technology

Volume 3
Oil and Natural Gas

2015 Publishers

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304 Energy Sci. & Tech. Vol. 3: Oil and Natural Gas

Upgrading and Hydrotreating of

Heavy Oils and Residua
YANET VILLASANA1*, MIGUEL A. LUIS-LUIS2, FRANKLIN J. MNDEZ1,
HENRY LABRADOR2 AND JOAQUN L. BRITO1*

ABSTRACT
A summary of previous and new technologies for the upgrading of heavy oils
and residua, compiling information on the history of hydrotreating reactions,
catalysts design and a description of the background of widely used
technologies and some new technologies are presented in this chapter. First,
the compositions and characteristics of heavy oils and residua are mentioned.
Then, some definitions regarding hydroprocessing are given to set up
appropriate terminology during the reading of this chapter. Posteriorly, a
critical comparison between conventional and non-conventional hydrotreating
feeds is given based on main problems regarding catalysts deactivation and
yields in middle distillates and/or coke. This section is followed by a
chronological comparison that embraces all technologies since 1956 to 1989,
including processes and patents. Finally, 20 years of different upgrading,
processing and hydrotreating technologies of heavy crude oils and residua
are described in terms of yields in gasoline, middle distillates, residue
conversion and also some technical requirements and details are cited, being
highlighted Venezuelan Technology.
Key words: Heavy oils, Hydroprocessing, Hydrotreating reactions,
Hydrotreating catalysts, Hydrotreating technologies,
Venezuelan technology

1
Centro de Qumica, Instituto Venezolano de Investigaciones Cientficas, Apartado 20632.
Caracas 1020-A, Venezuela.
2
Facultad Experimental de Ciencias y Tecnologa. Universidad de Carabobo. Valencia,
Venezuela.
*Corresponding author: E-mail: ytvillas@gmail.com
Upgrading and Hydrotreating of Heavy Oils and Residua 305

1. INTRODUCTION

As a consequence of the lack of conventional feeds, industrial and academic

efforts have been addressed in order to use widely available heavy crude
oils to meet increasing market demands concerning petroleum derivatives
and also meeting environmental regulations which have become stricter in
the last 20 years. Since hydroprocessing of heavy oil differs from processing
of conventional feeds, some inconveniences are found when conventional
catalysts are used to process non-conventional feeds. Accordingly,
modifications to catalysts properties and catalytic supports are of great
interest since these changes do not imply great modifications to existing
processing units. Below, some modifications and additives that guarantee
an optimum performance of catalysts during these processes are discussed.
Moreover, combination of technologies and processes are widely spread in
industrial configurations where different residue conversion and yields can
be achieved, depending on the feed to be processed and the product quality
required. Before initiating a critical discussion on the technologies, heavy
crudes and residues are described.

2. HEAVY CRUDE OIL AND RESIDUA: COMPOSITION AND

CHARACTERISTICS

A conventional crude oil is known to be a material that can easily be

recovered as a liquid by pumping operations. In contrast, the heavy crude
oils are another kind of crude which are difficult to recover from the
subterraneous reservoir. These latter materials have a higher viscosity
(hence, a lower API gravity) than conventional crude oils and the primary
recovery of this type of feedstock requires thermal stimulation of the
reservoir. Heavy crude oil definition is usually based on API gravity or
viscosity, which is an arbitrary way to define; however, there have been
some attempts to rationalize the definition based on other parameters,
including also density. Consequently, the generic term heavy crude oil or
heavy oil is generally applied to petroleum that has less than 20 in API
gravity. In contrast to conventional oils, heavy crude oils have a darker
colour and they can even be black. On the other hand, residuum is another
type of feed, which is obtained by non-destructive distillation. Usually,
distillation temperature is kept under 350C, due to the fact that the velocity
of the thermal decomposition of petroleum constituents under this condition
is minimal. This type of feed is a viscous black material and can be obtained
through two types of conditions, under atmospheric pressure (leading to
atmospheric residue (AR)) or under reduced pressure (leading to vacuum
residue (VR))[1].

Heavy and conventional crude oil residua have similar compositions, as

for example, low H/C ratio (1.21.4) and high contents of metals (V, Ni),
sulphur and nitrogen[2]. Hence, one of the most important objectives of
306 Energy Sci. & Tech. Vol. 3: Oil and Natural Gas

refining is to convert residua into lighter products through an increment of

the H/C ratio[3]. In spite of some similarities, heavy crude oil and residua
differ in many ways, for example, regarding asphaltenes, S, N and
organometallics compounds contents. However, the composition of residua
is related to the origin of the crude oil. It has been reported that crude oils
from different sources could reach different yields of atmospheric and vacuum
residua. There are several parameters that are relevant to the
hydroprocessing of heavy crude oils including a simple parameter such as
H/C ratio, which exhibits a decreasing trend from light crude oil to heavy
crude oils. A similar behaviour is observed when this parameter is studied
in the same crude oil, starting from lighter fractions until heavier ones and
residua[4]. Further, it is worth to notice that the predominant metals in
crude oil, heavy crude oil and bitumen derived from tar sands are V and Ni.
Metal content may vary from few to several thousand part per million,
being V content generally higher than Ni content[5].

The major problem associated to the heavier fractions of petroleum is

the complexity of the feed and the analysis of its components. Efforts have
been made in order to properly analyse crude oils and their fractions, by
using different methods, leading to an improvement in the understanding
of heavy crude oils[1,6]. In addition to the complex structures present in
crude oil, asphaltenes remain as one group of molecules barely known,
which are common in heavy crude oil. It is believed that asphaltenic fraction
is the most complex, of higher molecular weight, polarity and aromatic
that constitutes the crude oil. However, the microstructure of this fraction
has been studied and in general, it has been reported that it is constituted
by large polyaromatic rings with high molecular weight, which stack one to
another to form asphaltenes aggregates[7,8]. Also, some metalloporphyrins
are associated to asphaltenes molecules through S-S interactions.

In another context, global demand of light products, mostly gasoline and

naphtha, reflects the growth of petrochemical, naval, aviation or automotive
industries. Consequently, the availability of light oils has decreased with
the world population growth; meanwhile the demand of petroleum
derivatives has increased, leading to use heavier feedstocks with severe
problems of handling and processing[9]. In order to meet gradual changes in
petroleum products requirements, in particular, a reduced demand for heavy
fuel oil, advanced technologies are now extremely necessary. A refining
process is required for upgrading the heavy oil properties in the presence of
catalysts and hydrogen at high pressure[10]. The hydrotreating (HDT) process
is emerging as one of the main options for improving the heavier fractions
of crude oil, generating the conversion of undesirable components in products
with higher commercial value. This process can achieve the reduction of
compounds that contain sulphur (hydrodesulphurization, HDS), nitrogen
(hydrodenitrogenation, HDN), oxygen (hydrodeoxygenation, HDO) and
metals such as Ni and V (hydrodemetallization, HDM), which if not removed
affect the efficiency of the refining process and environment[11].
Upgrading and Hydrotreating of Heavy Oils and Residua 307

3. HYDROCONVERSION AND HYDROPROCESSING

Hydroconversion is a term used to describe the processes in which molecules

of petroleum feedstocks are cracked or saturated with hydrogen, diminishing
boiling points ranges and impurities contents in crude oil fractions. In
contrast, hydroprocessing is a wider term that includes hydrocracking, HDT
and hydrorefining[10].

3.1. Hydrotreating Process

HDT processes are used to remove undesirable components of petroleum
fractions by selective reaction of these components with hydrogen in a
reactor at relatively high temperatures and moderate pressures. Lighter
materials, such as naphtha, are generally hydrotreated to allow subsequent
processing in catalytic reforming units, avoiding catalysts poisoning, while
heavier distillates, from jet fuel to heavy vacuum residue, are submitted to
HDT in order to meet stringent quality specifications of the product or
before being used as feed elsewhere in the refinery. Also, HDT processes
are used to improve the quality of atmospheric residue by diminishing
sulphur, nitrogen and metals levels. It is notable that most of the product
quality specifications are related to environmental regulations, which are
becoming stricter. Hydrotreaters are designed to handle reactions under a
variety of conditions depending on a set of factors such as feed type, desired
cycle length and expected quality of products. Until 1980, HDT processes
were patented and offered by a large number of companies. In the past 25
years, the catalysts have become commodities and the process has been
offered without patent rights[12].

The origin of the HDT processes is related to the research of Sabatier

and Senderens in 1897, regarding hydrogenation of unsaturated
hydrocarbons in vapour phase using a Ni-based catalyst[1315]. In 1904, Ipatieff
extended the range of feasible reactions by introducing high pressures of
hydrogen. At that time, the progress of the automotive industry was expected
to entail a considerable increase in fuel consumption. This led to the
experimental work of Bergius, which began in 1910 in Hannover, Germany,
seeking to produce gasoline by cracking of heavy oil and oil residua, as well
as the conversion of coal to liquid fuels. This researcher found that to
overcome the inferior quality of the unsaturated gasoline thus produced,
the hydrogen mainly removed as methane by cracking during operation
must be replaced by addition of fresh hydrogen. Thus, coke formation was
avoided and gasoline produced was of a rather saturated nature. Bergius
also noted that the S content in oil was largely eliminated as H2S, ferric
oxide being used in the process to remove the S. Actually, ferric oxide and
Fe sulphide formed in the process acted as catalysts, although the activity
was very poor. The first hydrogenation plant of brown coal was custom-
built in 1927 in Leuna-Germany. Development of industrial-scale
308 Energy Sci. & Tech. Vol. 3: Oil and Natural Gas

hydrogenation in Europe, particularly in Germany, was entirely due to

military considerations. Germany used hydrogenation extensively during
the Second World War to produce gasoline. For example, 3.5 million tons
were produced in 1944. The first commercial installation of a hydrorefiner
in the United States was in Standard Oil Company of Louisiana at Baton
Rouge in the 1930s. The plants of the Second World War period were
developed by Humble Oil and Refining Company and Shell Development
Company, even though the countrys dependence on gasoline hydrogenation
was considerably lower. Although hydrogenation had been of great interest
in the oil industry for many years, there was a limited commercial use of
hydrogen-consuming processes, due to the lack of low cost hydrogen sources.
This changed in the early 1950s with the advent of catalytic reforming
hydrogen which was made available as a by-product and resulted in an
extensive and growing interest in processes that would use this hydrogen
to enhance oil reserves. As a result of the enormous growth of HDT, as of
early 2001, there were over 1600 hydrotreaters operating in the world with
a capacity greater than 39 million B/D[12].

3.2. Conventional HDT Catalysts

Nowadays, HDT catalysts are based on Mo supported on ceramic materials,

promoted with Ni or Co. These catalysts are active in their sulphide form,
being pre-sulphided or sulphided in situ. Therefore, CoMo/Al2O3 is the most
widely used for HDS, while catalysts for HDM reaction, generally have
large pores and low metal content. Commonly used supports include
transitional aluminas with high surface areas (~200 m2/g), silica-alumina or
zeolites for hydrocracking. Average pore size is 75 to 300 , although it is
frequent to find wider pore size distributions. Catalytic supports to be used
in HDM may also have macropores, namely a bimodal pore structure.
Micropores can have a significant incidence on reactants diffusion on active
sites, particularly on heavy feed[16].

Several researches have revealed that the catalysts based on Mo sulphide,

consist essentially of a monolayer or cluster of slabs of MoS2 partially
covering the surface of the Al2O3[16]. Layer distribution on the support
depends on Mo loading and sulphuring temperature. Under hydroprocessing
conditions, it can be easily removed sulphur ions from the corners and
edges of MoS2 crystallites and this phenomenon leads to the formation of
coordinatively unsaturated sites and/or vacancies of sulphur ions, which
have Lewis acid character[17] and have been reported as responsible of
catalytic activity. Promoters such as Co or Ni decorate MoS2 crystals at the
edge of the slabs, modifying the electronic environment of MoS2 and
consequently the way in which reactants are absorbed, as is the case for
hydrogen, where homolytic and heterolytic rupture can lead to Mo-H and
S-H species that deliver hydrogen to the hydroprocessing reactions[1821].
Upgrading and Hydrotreating of Heavy Oils and Residua 309

3.3. HDT of Heavy Crude Oil: General Aspects

In spite of some similarities, hydroprocessing of heavy crude oil markedly

differs from light crude oil processing, as a result of the presence of
asphaltenic molecules, with high molecular weight and organometallic
compounds. Accordingly, catalysts must be designed properly in order to
perform hydroprocessing under these conditions. Textural properties should
be optimized in order to handle these molecules. Optimization of such
parameters during preparation of these catalysts leads to an increase in
the costs; hence significant efforts have been made in order to increase the
catalytic performance and deactivation resistance of these materials. An
active hydroprocessing catalyst must be resistant to deactivation by coke
and metal deposits[17].

The HDT catalysts are very versatile and exhibit activity for a wide
number of reactions; being the most important those in which removal of
heteroatoms are involved, such as HDS, HDN and HDM, where
hydrogenolysis of C-heteroatom bond cleavage is implicit. For relatively
light feeds, deactivation of catalysts is minimal and the process can operate
for long periods of time before catalyst replacement. In contrast, when a
heavier feed is used, deactivation becomes severe and this has economic
implications due to reduced times on stream of the catalyst[16].

The main problems associated to heavy crude oil processing using

conventional catalysts include the presence of polyaromatics and
heteroatoms, where the cracking of these materials leads to excessive coking
and this process alters catalyst properties, thus reducing intra-particle
diffusion and consequently catalytic activity. Moreover, metalloporphyrins
are present in significant quantities and these are precursors of metal
deposits under hydroprocessing conditions which cause permanent
deactivation. Also, N-containing compounds can poison acid sites and
diminish hydrocracking reacting speed [22] . As mentioned earlier,
hydroprocessing reactions occur in active sites of catalysts; therefore, an
appropriate pore size distribution is required to guarantee the access of the
molecules to the active site. In summary, the loss of active sites is associated
to pore blocking, poisoning, sintering, metal and coke deposits[16]. In order
to overcome these complications, some solutions imply the application of
more severe conditions when heavier feeds are treated[23].

4. BACKGROUND OF TECHNOLOGIES FOR HEAVY CRUDE AND

RESIDUE HDT

Since 1910, with Bergius experiments to produce synthetic gasoline from

heavy feeds, residue and coal, many and diverse technologies have been
developed in order to perform these processes. In Table 1, a summary of
some outstanding technologies is given.
310 Energy Sci. & Tech. Vol. 3: Oil and Natural Gas

Table 1: Summary of old technologies related to hydroprocessing of heavy feeds

Researcher(s) (Year) Process name Description

Beckberger (1956) Hydrocracking A combination of Fluid Coking (see next item)
Sinclair Refining Co. of heavy crude and cracking process to convert crude oil into
oil hydrocarbons with high yields of liquids of low
boiling points. A heavy crude oil is loaded within
a fluidized particle bed of coke in a coking
reaction. Large particles of coke formed are
selectively removed in order to put them in
contact with steam in a separated zone to
generate a mixture of water-gas, which is
returned as fluidizing medium. The top of the
reaction is mixed with activated coke particles
that come out from the generator of water-gas
mixture to form a fluid suspension and the
mixture is cracked in the range of gasoline
products[24].
Pfeiffer et al. (1959) Fluid coking of This process consists in the coking of heavy
Esso Research and heavy hydro- crude oil residue in contact with hot fluidized
Engineering Co. carbons solids[25].
Beuther et al. (1959) Visbreaking This process can be applied to AR and VR and
Gulf Research and to the remnant of the solvent deasphalting
Development Co. process (SDA), where the stream of residue is
heated in a furnace (450500C) and later, the
feed is cracked during a short and specified
residence time, to avoid coking reactions. The
process is carried out under a soaking zone at
moderate temperature and pressure. Cracked
products leave the soaking zone after the
desired conversion is reached and then this
stream is quenched with gasoil to stop the
reaction and prevent coke formation[26].
Kellogg (1960) Cracking of This process is a modification of fluid catalytic
Phillips Refinery heavy crude oils cracking (FCC) and is adapted to heavy
crudes[27].
Colyar and Wisdom H-Oil process It is an ebullating bed process that can operate
(1960) Hydrocarbon under a wide range of conversion levels and is
Research Institute, adapted particularly to heavy vacuum residue
Axen with high metal and Conradson carbon content.
It also preserves product properties during
cycle. Due to the fact that this process is carried
out in a stirring reactor and a fluidized catalyst
it can handle exothermic reactions and solid-
containing feeds[28].
Mosby et al.(1973) Residue The feed is pre-heated by exchange and mixed
Amoco Oil Co. Ultrafining with recycled hydrogen and heated up in a
furnace to the temperature of reactor entrance.
Desulphurization occurs in a multi-bed reactor,
where an intermediate gas cooler avoids
temperature rising and helps maintaining

Table 1: (Contd...)
Upgrading and Hydrotreating of Heavy Oils and Residua 311

Table 1: (Contd...)
Researcher(s) (Year) Process name Description
catalytic activity. The products leaving the
reactor are separated in several steps to
eventually produce fuel gas, naphtha, distillates
and de sulphure d re sidue . Stre ams are
depurated to produce sulphur free fuel oil[29].
Bridge et al. (1975) LSFO (Low Vacuum gasoil (VGO) is used and a process of
Chevron Research Co. sulphur fuel vacuum residuum desulphurization (VRDS) is
and Standard Oil Co. oil) Project applied to obtain products with between 0.1 and
1.2% of sulphur. These products are combined
with the diesel feed to produce fuel oil of low
sulphur content (only 0.5%). Hydrogen comes
from steam reforming[30].
Chen et al. (1981) Delayed coking Delayed coking process in which part of
Mobil Oil Corporation process produced coke is heated by partial combustion
and mixed with a pre-heated feed to reach
coking temperature of the mass present in
pr oce ss drums. This pro ce ss co nducts
essentially to the metal and coal removal while
providing partial conversion to liquid products
(naphtha and diesel)[31].
Crowley et al. (1987) Solvent Feed is mixed with a light paraffinic solvent
Phillips Petroleum Co. deasphalting (propane, butane, pentane or n-heptane) where
(SDA) crude oil is solubilised. Non-soluble part will
precipitate from the mixture as asphaltenic
fraction. The separation gives rise to two
products: A deasphalted oil (DAO), which is rich
in paraffins, and asphaltenes. It is a low cost
process and has flexibility to meet a wide range
of quality DAO[32].
Mc. Daniel et al. (1988) LC-fining Fresh feed is mixed with hydrogen and both
Amoco process react inside an expanded bed of catalyst which
is maintained in turbulence by upflow of liquid
to reach an efficient isothermal operation.
Product quality is constantly maintained at a
high level by occasionally discarding spent and
adding fresh catalyst. The reactor products then
flow through high and low pressure separators,
and finally move to the fractionator. The recycle
hydrogen is separated and purified[33].
Oelderick et al. (1989) HYCON hydro- Operating in a fixed bed reactor, but in the case
Shell Research BV processing with of feeds with high metal content additional
movable beds reactors for HDM are added. In this process
the catalyst and the residue are added in co-
current flow, the fresh catalyst enters the top
of the reactor, while the spent catalyst is
removed from the bottom. The catalyst is
replaced at a rate that ensures that the total
run of the plant has at least one year duration,
which depends on the contaminant level
present in the feed[23].
312 Energy Sci. & Tech. Vol. 3: Oil and Natural Gas

As it can be seen from the summary above, in general, the technologies

are aimed at the conversion of heavy oils and residues into synthetic crude
of higher quality with lower metal content and greater manageability by
modifying their physical and chemical properties. However, coke yields are
very high and as loads become heavier it becomes more difficult to maintain
a conventional catalyst with high catalytic activity during a reasonable run
time. Moreover, the products obtained by using these technologies generally
require downstream treatments to meet the needs of demand. That is why
efforts to improve the scope and performance of both these increasingly
inappropriate technologies as well as the design of new technologies and
processes, have not ceased due to high demand for petroleum products
globally and in particular due to the shortage of so-called conventional oil
(light and medium).

5. NEW TECHNOLOGIES FOR THE HYDROPROCESSING OF

HEAVY CRUDE OIL AND RESIDUE

Refiners have developed innovative business strategies, especially to

modernize existing systems. The technology for converting heavy crudes
and residues has progressed impressively since the 1980s and still gives
excellent progress. Advances in established technologies along with recent
commercial applications, residue fluidized catalytic cracking (RFCC) and
automated residue demetallization, have significantly improved the options
for residue processing. Some requirements have to be overcome in order to
ensure long term strategies for heavy oil processing which could lead to
obtain economic benefits by production of fuel oil, hydrogen and electric
energy from low value feeds. Broadly speaking, there are two groups of
processes in which heavy oil processing technologies can be classified:
thermal and catalytic processes, which are described below.

5.1. Thermal Processes

This type of technology have existed since the born of refining industry,
given that the first operators discovered that coke could be formed by enough
heating of crude oil feed. Nevertheless, these technologies are constantly
modified to optimize the yields of high value products.

Historically, thermal processes such as delayed coking and fluid coking

have been taken as a starting point regarding residue conversion due to
their low cost and moderate hydrogen requirements. However, as crude oil
prices have been increasing every year, the option to convert 20 to 35 wt.%
into coke has become less attractive. Moreover, refineries generally do not
have capability to convert heavy products that come out from a coker, being
this fact a limitation to add this technology to the processing line[34]. For
this reason, some modifications were done in order to improve the production
to middle distillates and reduce the presence of metals, sulphur and nitrogen.
Upgrading and Hydrotreating of Heavy Oils and Residua 313

Regarding these modifications, in 1992 Reynolds et al.[34] published a study

in conjunction with Chevron Research and Technology Co. and Stone &
Webster Engineering Corp. (S&W), in which they observed that VR could
be economically improved using desulphurization process of Chevron (VRDS)
and then apply the FCC process of S&W even if all vacuum gasoil is processed
by hydrocracking. The combination of a flexible range of products, high
yield of clean fuels and a proven technology, made this conversion route an
attractive option. During research, they found an improvement in crude oil
quality, regarding API gravity, sulphur and metal content and low yield of
coke.

In 1993, Del Bianco et al.[35] published a work in which a process of

thermal cracking is described. They used crude Belaym VR (Egypt) mixed
with 20% of a hydrogen donor solvent (dihydrophenantren, DHP), working
in a temperature range of 390450C. This process is known as hydrogen-
donor visbreaking and it was investigated for the first time for direct
liquefaction of coal at the end of 1970 by Exxon (Exxon Donor Solvent
Process)[36]. Here, researchers found that DHP addition diminishes coke
production velocity, while middle distillates production increases. The basis
of this process is the thermal cracking of residual crude reaction under
visbreaking conditions in the presence of hydrogen donor compounds, which
provides new reaction paths, so that higher conversion and better control
of condensation reactions are obtained (reduction of coke production).
Hydrogen and catalysts presence is not necessary; consequently it is a low
cost process. Although some works have described the use of this process,
information regarding reaction mechanism and kinetics is limited. Other
aromatic and polar solvents were also studied, for example, phenanthrene,
1-methyl-naphtalene, quinoline and naphthol, resulting in different yields
in coke, distillates and gas. For example, phenanthrene reduces coke
production from 13.5 to 9.8 wt.%, likely due to a solvating control of coke
precursors by this solvent avoiding condensation reaction.

In 1994, Chen et al.[37] proposed a process of mild cracking solvent

deasphalting (MCSD), which combines these two technologies properly, under
supercritical and subcritical conditions, using extraction of solvent as stirring
agent. Two solvents were used, pentane and a mixture of C3-i-C5 (mol%: C3:
5.7; n-C4: 8.3; i-C4: 85.4; i-C5: 0.6), using Gudao and Shengli (China) VR as
feeds. It could be observed when comparing this process with solvent
deasphalting that the yield in DAO was superior, also, while increasing
cracking temperature leads to an increase in the yield of DAO. Also,
demetallization and decarbonization are substantially improved.

5.2. Catalytic Processes

This technology involves catalytic cracking and HDT. In the beginning of
1940s, the catalytic cracking mainly consisted in FCC of gas oil and VGO
314 Energy Sci. & Tech. Vol. 3: Oil and Natural Gas

feeds, aiming to maximize gasoline production. Meanwhile, in

hydroprocessing VGO is considered a residue, traditionally; residue cracking
with low metal content has been referenced as conventional FCC of VGO.
The first round of RFCC started when metal-containing feeds, such as heavy
VGO and deasphalted residue, were sent to units of conventional FCC of
VGO[38]. Feed contamination with metals (V, Ni, Fe and Na) started to play
a role in terms of selectivity (coke and gas) and activity (deactivation by
coke and high temperatures) of the catalysts. This fact motivated to modify
FCC catalysts in order to increase their time on stream. The introduction
of substituted zeolites with rare earth metals revolutionized FCC operations
due to their high activity and selectivity, enabling to introduce FCC designs
with plug flow and lower contact times. Initially, the zeolites were
incorporated in gel type amorphous silica-alumina catalysts in the event of
any manufacturing processes based on synthetic microspheres, or crystallized
in situ as in the classical treatment of the clay-based catalysts. Plank and
Rosinski[39] found desirable that the catalysts be dispersed in a relatively
inactive matrix to avoid over cracking. Elliot and Ostermaier[40] developed
a catalyst with zeolite incorporated in clay-based silica for this purpose.
The zeolite catalyst was commercialized with minimal activity of the non-
zeolitic matrix pointing in the optimum activity and selectivity for coke.
The activity and selectivity of zeolites may be reasonably correlated to
the unit cell size (UCS), which is a measure of the zeolite/alumina ratio in
the zeolite structure. Zeolites which have not been fully replaced by rare
earth metals, called hydrogen Y (HY) or partially substituted (RE-HY)
equilibrate in a lower UCS. These zeolites exhibit a lower tendency toward
hydrogen transfer reactions yielding a higher octane gasoline and a smaller
volume of coke. However, thermal stability of these zeolites is lower than
Y zeolites completely replaced with rare earths (REY). Consequently, zeolites
were developed hydrothermally stabilized and they are called ultrastable
Y. They maintain their structural stability at temperatures above 1000C,
however, are rapidly deactivated by the poisoning of acid sites due to the
metal contaminants such as Ni and V. This protection has become an
important field in the development of catalysts for RFCC[41].
In 1996 Sugioka[42] examined the catalytic activities of noble metals
supported on zeolite USY for HDS of thiophene in order to develop a catalyst
for this reaction based on a highly active zeolite. It was found that the
catalytic activity of the catalysts considerably changed with the noble metal
and their activity followed this order: Pt/USY Rh/USY Pd/USY Ru/
USY. The initial activities of Pt/USY, Rh/USY and Pd/USY were higher
than that of the catalyst Co-Mo/Al2O3. It was also found that Pt/USY exhibited
the highest activity and a relatively long life of all the examined catalysts.
These results indicate that the Pt/USY hydrogenating catalyst has high
capacity and Brnsted acidity, which is necessary for the appropriate
thiophene HDS. Furthermore, it was found that the activities of the
transition metals supported on USY such as Ni, Co, Fe, Mo and their
Upgrading and Hydrotreating of Heavy Oils and Residua 315

mixtures in different atomic ratios were lower than Co-Mo/Al2O3 activity.

These results indicate that hydrogenating ability of these components and
mixtures thereof are insufficient. Moreover, on analysis by X-ray diffraction
(XRD) of the reduced catalysts no signals of Pt and Rh were found, but large
peaks of Ru and small peaks of Pd were observed. From these results, it
can be said that Ru showed the lower dispersion among the noble metal
supported on USY and metal dispersion is assumed to be follow this order:
Pt/USY = Rh/USY Pd/USY Ru/USY, which is in agreement with that
found in the initial activity and stability of the catalysts mentioned above.
Therefore, it is very important to prepare catalysts with noble metal/USY
with high dispersion of noble metal in order to maintain a high and stable
activity for HDS. Additionally, since Pt/USY was the most active for HDS of
thiophene but activity gradually decreased over time, tests were made with
mixtures of Pt, Pd and Rh in order to enhance catalyst stability. We found
that the combination of Pt with Pd/USY was successful and the Pt-Pd/USY
catalyst was more active and more stable than Co-Mo/Al2O3 and Pt/USY for
this reaction. This fact can be attributed to the increased Pt hydrogenating
capacity when combined with Pd. However, it was not clear from the XRD
analysis of the reduced catalyst if Pt-Pd/USY form alloys of Pt and Pd on
USY.

As mentioned above, catalytic cracking technology was characterized by

the use of zeolite-based acidic catalysts to assist heavy oil cracking reactions,
being able to produce distillates and naphtha. In general, the size of the
hydrocarbon molecules that constitutes the feed of an FCC process is not
compatible with the pores of the zeolite crystals. First, these molecules
must be reduced in size by a preliminary cracking that occurs on the external
surface of the zeolite, which may have other features such as metal removal
capacity. In this sense, Ng in 1997[43] presented the combination of SDA and
FCC, using several solvents (n-heptane, n-pentane, n-butane and propane)
to carry out a deasphalted process and cracking was done using a commercial
catalyst (DA-440) which has a medium activity, metal tolerance and is
composed by a REY zeolite, which possess an active matrix able to handle
residue cracking. Studied feeds include vacuum towers bottoms (VTB) from
unconventional oil sands of Athabasca and Lloydminster heavy oil and it
was found that while the solvent was lighter, the DAO yield was lower but
with better quality. The DAO yield also decreases with lower solvent/VTB
relationships, higher temperatures or pressures with a slight change in the
composition. Increasing system temperature has a similar effect to that
which is obtained by reducing the molecular weight of the solvent with
respect to the performance and recovery of DAO components VTB, except
that the solvent effect becomes stronger. Furthermore, it was established
that at constant severity, yields of products can be correlated to asphaltenes
content or total hydrocarbon content (saturates and aromatics). As oil content
increases, the yield of liquefied petroleum gas (LPG), distillates (gasoline,
low cycle oil-LCO and heavy cycle oil-HCO) increases as yields of undesirable
316 Energy Sci. & Tech. Vol. 3: Oil and Natural Gas

products (dry gas and coke) decrease with a decrease of the total conversion.
Furthermore, it has been found that about 50% of the total hydrocarbons
and 20% of the DAO resins can be converted into gasoline. For a given oil
content, Lloydminster DAO yields 25% more fuel than the DAO from
Athabasca. Although poor quality DAO associated to the use of a heavier
solvent provides a lower gasoline mileage based on FCC feed, produces
substantially more fuel based on VTB due to the higher yield of DAO in the
deasphalting process. In summary, under certain assumptions, DAOs
produced from VTBs of Athabasca and Lloydminster heavy oils or using
propane or n-butane as a solvent can be accepted as feeds for residue
cracking. Obtained DAOs using other higher molecular weight solvents
must be diluted with cleaner feeds as diesel or have to be hydrotreated to
reduce impurity levels and thus produce an acceptable FCC feed.
Notably, over the years the catalytic cracking process has been
significantly improved in terms of process and catalyst, enabling to enhance
selectivity towards the production of naphtha to be used in the gasoline
pool and increase their flexibility to handle feeds with high contents of
contaminants[44]. However, some limitations persist regarding carbon and
metal contents. In this sense, Rana et al.[45] in 2008 worked on the synthesis
of a USY zeolite mixed with an Al2O3 of high surface area, with moderate
acidity and meso-and macro-porosity, to support a catalyst based on CoMo
for hydroprocessing of Maya heavy crude oil under moderate pressure
conditions. The combination of zeolite USY and Al2O3 can produce bimodal
type of pore distribution in the catalyst which can contribute to a better
combination of HDS and HDM performances and selectivity to asphaltenes
cracking on acidic catalyst. According to the catalytic test, the catalysts
obtained were more active for the hydrogenolysis (in reactions as HDM,
HDS and HDN) than for hydr ogenation (in reactions such as
Hydrodeasphalting-HDA), which is due to the CoMoS phase. In general, a
hydrogenation catalyst is undesirable for the first reactor in a series of
HDT reactors, because this type of reactions can increase paraffinic
hydrocarbons content, which favours the precipitation of asphaltenes.
Furthermore, the direct hydrogenation of asphaltenes has a role on
weakening of asphaltenes complex molecules and expose metals (Ni and V)
and nitrogen at the catalytic sites[45].
Moreover, other supports have been proved in heavy crude oil processing,
as it was reported by Trejo et al.[46] for the preparation of mixed supports of
type MgO-Al2O 3. In this regard, MgO nanocrystals were uniformly
distributed in the matrix of the CoMo/MgO-Al2O3 catalyst. This catalyst
prepared with chelating agent (1,2-cyclohexanediamine-N, N, N,N-
tetraacetic acid) showed improved thiophene HDS when using calcinations
before activity test. This calcination may contribute to the interaction of
the chelating agent with the MgO in the preparation of the catalyst, which
facilitates the sulphidation due to the weak interaction between Mo and
support, making them more active. It is also important to note that Raman
Upgrading and Hydrotreating of Heavy Oils and Residua 317

spectroscopy results confirmed that the chelating agent prevents the

formation of Co3O4 and CoMoO4; instead it promotes interaction of Mo with
MgO-Al2O3 support leading to the formation of MgMoO4 species, which are
easily converted into MoS2. By submitting Maya heavy crude to HDT with
Al2O3 supported catalysts with different contents of MgO, it was found that
the catalyst containing 10 wt.% MgO is more selective to hydrogenolysis
reactions than for hydrogenation, because despite of having larger pores
(which would favour the HDA), hydrogenolysis function is further enhanced
by the basic nature of the support. Additionally, a higher content of MgO
leads to a more stable catalysts and this is associated to a larger pore
diameter. It is known that catalysts with wide pores are recommended
when large molecules are present, such as porphyrin complexes containing
metals, at the expense of reducing the specific surface area and consequently
reduce the activity of HDS process[47]. Therefore, preferred catalysts are
bimodal catalysts, since the HDS occurs effectively in smaller pores while
the HDM is performed in larger pores, as it was discussed in section 3.2. In
contrast to this contribution, where HDT of heavy oil with a catalyst support
of basic nature was studied, Leyva et al.[48] worked with Al2O3-SiO2 acidic
supports synthesized by the method of homogeneous precipitation, varying
the SiO2 content (31, 56, 78 wt.%) and therefore varying the acidity of the
support. They tested the catalytic activity of NiMo supported on the matrix
in the hydroconversion of Maya crude, finding that the catalyst with 31wt.%
of SiO2 on Al2O3 had the highest activity in HDS, HDM and HDN, but the
trend is reversed in the case of HDA, which may be due to two effects, the
acidity or average pore diameter. However, compromising the two properties
favours HDA because the effective diffusion of asphaltenes molecules occurs
in the macropores and acidity promotes the cracking of the molecules. In
order to elucidate which of the properties affects more the HDT reactions,
selectivity plots were used. Those plots permitted to infer that activity
variation is due to a combined effect of the two properties. HDM activity
showed a roughly similar trend to HDA, while the activity in HDS indicates
very different results for the two catalysts. The explanation behind the
selectivity towards HDA and HDM reactions is the nature and size of the
molecules and the similar role of the acidic sites for both functions. It appears
that these results indicate that large pores and optimum dispersion of the
active phase so as to complete the processing of heavy loads are needed,
but the acidity of the catalysts is a secondary parameter for design of the
catalyst and depends on the selectivity towards the desired product,
accordingly, it cannot be said that there is an optimum combination of
parameters for acidity, dispersion and pore diameter, that provides the
best activity in all cases, because it affects the properties of the catalyst of
each reaction in a different way. After the study of the catalytic activity was
completed, the authors examined the properties and characteristics of the
spent catalyst, finding considerable variation in the textural properties with
respect to the fresh catalyst, as well as variations in the content of metals
and coal deposited in both catalysts, which concluded that the deposition of
318 Energy Sci. & Tech. Vol. 3: Oil and Natural Gas

sulphides of V and Ni depended primarily on the diameter of the pores,

wherein the catalyst with a larger pore diameter contained a greater amount
of deposited species, which were proportionally distributed along the radius
of the extrudate, while for the catalyst with a smaller pore deposition
occurred primarily on the external surface of the extrudate.

On the other hand, besides support modifications, changes in the

precursor of the active phase have also been made, such as the work
published by Soogund et al.[49] where oxidic MoV based precursors were
synthesized with mixed metals heteropolyanions (HPA) as a starting
material, for which solutions containing substituted Keggin HPA, where
the Mo and V were introduced into the same structure. It was observed
that these catalysts display improved catalytic hydrogenation of toluene
and cyclohexane isomerization compared with the conventional catalyst in
a model reference feed containing dimethyldisulphide (5.9 wt.%) and toluene
(20 wt.%) in cyclohexane (74.1 wt.%), which is due to the good dispersion of
both metals. Hydrogenation activity of the catalyst increases with V loading
and is much higher than the reference catalyst. The same trend is observed
for the isomerization and this may be due to the acidity provided by V,
which favours isomerization reactions. In general, the use of MoV catalysts
provides a synergistic effect, which increases with the content of V compared
to reference catalyst without V. However, while performing tests using VR
from Safaniya crude, they observed that the HDS is very little affected by
the presence of V in the catalyst and this result was in agreement with that
obtained in 1990 by Loos et al.[50] for unsupported catalysts.

Dejonghe et al.[51] showed that in the presence of V, Ni-Mo-S phase was

gradually replaced by V-Mo-S phase which was much less active. In contrast,
Takeuchi et al.[52] reported that the V incorporated in phase V-Mo-S could
be more active in the HDM and HDA than V sulphides during HDT of heavy
oil. Similarly, Sasaki et al.[53] reported that they could have a catalytic activity
comparable with CoMo for residue HDM. NiV sulphide catalyst was also
suggested by Betancourt et al.[54], therefore, it is highly likely that a novel
active site is formed between the V and Mo that may be responsible for the
high activity catalyst in HDM and HDA. In summary, the use of substituted
Keggin HPA as precursors, where Mo and V are in the same structure as
the starting material seems to be favourable for the preparation of new
catalysts of HDM.

Recently, Ti-HMS (Hexagonal Mesoporous Sieves) materials were

synthesized and used as catalyst supports for NiPMo (12-molybdophosphoric
acid promoted with Ni). The effect of Ti ions in the immobilization of 12-
molybdophosphoric acid on mesoporous materials was studied. In this work
developed by Boahene et al.[55] double modification of HMS silica surface
was made by combining grafting with H3PMo12O40 (HPMo) and modification
of Ti4+ ion structure. The authors found that the synthesis of NiPMo/Ti -
HMS catalyst from the corresponding HPA leads to obtaining better
Upgrading and Hydrotreating of Heavy Oils and Residua 319

performances in HDS and HDN of a sample of coker light gas oil (CLGO)
than their counterparts prepared from ammonium salts of Mo, which are
used traditionally. The reason for the high activity of the formulations of
NiPMo/Ti- HMS seems to be related to the specific structure of the Keggin
type precursor, where small units of Mo oxide form aggregates of defined
sizes, since catalysts synthesized with this methodology generate lower
metal supports interactions, which helps the formation of NiMoS phase
(type II), whose activity has been reported for HDT reactions.
Moreover, Mndez et al.[56] reported the use of Keggin heteropolyacids
(H3PM12O40, M=Mo or W) as active phase source for a series of tungsten
and molybdenum catalysts supported on MCM-41. These materials were
tested for thiophene HDS, which helped to demonstrate the importance of
supporting heteropolyacids to increase the catalytic activity, also obtaining
a correlation between surface acidity and calcination temperature with the
activity and stability of these catalysts in the HDS reaction.
Catalysts acidity impact on activity in HDN, HDS, HDM and HDA residue
was recently studied by Marques et al.[57], where bimodal and multimodal
Al2O3 supported catalysts NiMoP were used. Supports were doped with
different additives: F, SiO2 and zeolites. It was found from the results of
simulated distillation that the catalysts with acidity improved by F may be
selective towards heavy fractions such as asphaltenes, since no additional
performance was observed in light fractions (Hydrocracking (HDC) of
compounds: 370C+~ 5 wt.%) or even in converting residue (HDC of
compounds 540C+ ~ 15 wt.%) in comparison to reference catalyst, which
confirms that an increase in acidity may increase performance in HDT
reactions. The generated Brnsted acid sites increased HDT activity and
asphaltenes conversion through a bifunctional type of reaction mechanism,
where no additional coke deposition was observed on the catalyst. In order,
to explain the effect of acidity on the performances in HDT, authors proposed
two hypotheses: Increased activities in HDT may be an indirect effect of
acidity, since acidity increases the adsorption of asphaltenes on the acid
sites, thereby increasing their availability to the neighbouring hydrogenation

reactions through the breaking of C-C bond by E scission of carbenium ions.

sites; or it may be a direct effect of acidity due to acid hydrocracking

In summary, compared to thermal processes, hydroprocessing operations

are more flexible, resulting in high yields of liquid fractions. An optimal
operation can be achieved by adjusting reactor type and catalysts with the
properties of the heavy feedstock[17].

5.2.1. Technologies based on slurry phase catalysts

HDT technologies with a fluidized bed developed in the 1960s are similar to
the slurry type reactor technology[58,59]. The advantages of slurry type
reactors include a simple and low-capital construction required, good
320 Energy Sci. & Tech. Vol. 3: Oil and Natural Gas

temperature control, high capacity, low pressure loss reducing compression

costs considerably, capacity of removal and addition of fresh catalyst in run,
less required amount of catalyst compared to the fixed bed reactor because
of the greater efficiency of the catalyst in this type of reactor.

HDT technologies in a dispersed phase (slurry type) use unsupported

hydrogenation catalysts finely dispersed in the substrate to be hydrogenated.
This catalyst consists of transition metal sulphides and therefore lacking
acidic functions, as a result of which cracking remains purely thermal.
Such catalysts are resistant to multiple poisons and therefore no serious
problems of deactivation, especially for the deposition of coke and metal
due to the absence of the support, which makes them interesting when
feeds having high concentrations of metals S, N and asphaltenes are
processed. Catalyst recovery from unconverted residue is the main limitation
of these processes. Consequently, low cost catalysts are almost always
preferred, being Fe-based catalyst the most common. This problem has
strongly influenced the development up to an industrial level of technological
solutions based on the use of catalysts in dispersed phase, which are classified
according to the nature of the catalyst, the reactor configuration, the method
of recovery and recycling catalyst, etc.[44].

Among the technologies that use slurry catalysts, the VEBA

CombiCracking (VCC) process is a high-pressure hydrogenation of heavy
hydrocarbon feedstocks and coal. A slurry reactor, where cracking and
hydrogenation reactions occur in liquid phase and in the presence of a
catalyst/additive based on Fe/carbon, limiting coke formation and promoting
metal removal, constitutes the main unit of this process. This unit is
integrated with a fixed bed reactor operating in the gas phase for subsequent
hydrogenation of the products. It can reach very high residue conversion
rates ( 95%, 524C+) and liquid yields above 100 vol.% obtaining high value
distillates. One of the main advantages of the VCC process is its independence
from the quality of the feed on a high mode conversion processing[60].

Another process technology based on the use of catalysts in dispersed

phase is the Canmet process, which was studied for the first time by the
National Centre for Upgrading Technology (NCUT), a Canadian center, in
the 1970s and was later developed by Petro-Canada and SCN-Lavalin. This
process is a high conversion, high demetallization and hydrocracking of
residues, where an additive is used to inhibit coke formation and achieve
high conversion of hydrocarbons in lighter products. This emerging
technology proved to be promising due in large part to the relatively high
conversion (90%) of the fraction 525C+, the simplicity, the absence of
expensive catalysts, demetallization capacity and other characteristics. The
feed is processed in the presence of Fe sulphide-based catalysts supported
on carbon particles. Mo can be added to a level of tens of ppm in the form of
naphthenate to increase HDS activity[44]. Reaction products are fractionated
Upgrading and Hydrotreating of Heavy Oils and Residua 321

and sent to a HDT unit, where the unconverted residue (510% of the load)
can be burned or gasified. Obtained reactor products contain undesirable
components such as diolefins, N and S; however, these products are better
than the products of a coker. Consequently, a downstream HDT is a
prerequisite for some of these fractions which can be achieved in
conventional plants with commercially available catalysts[61].

The Microcat-RC process, which was originally called M-Coke, developed

by Exxon during the 1980s and 1990s to the present, is a process that includes
the following steps: First, a hydrocracking step in the presence of a catalyst
based on Mo of micrometric dimension supported on carbon particles in the
dispersed phase. Then, flash distillation and vacuum distillation is applied
in order to obtain a distillate with a high yield of the fraction which boils
below 560C and a residue in which are accumulated the metal and catalyst
loading. This residue can be burned or gasified. Finally, a HDT reaction for
the refinement of the products, which are then divided into naphtha,
atmospheric Oil (AGO: Atmospheric gas oil) and VGO. This process can
achieve conversions up to 95%, with a typical distribution of 1015% naphtha
products, AGO 4555% and 3040% VGO.

The EST (Eni Slurry Technology) process developed by Snamproguetti

and Eni technologies, both companies of the Eni Group[62], in contrast with
the technologies available today, operates in a way that allows the almost
complete conversion of loads of heavy oil distillates, avoiding coke production.
The heart of the process is a HDT reactor in which the load of heavy oil is
subjected to hydrogenation treatment under relatively mild conditions (410
420C and 160 bar), limiting the conversion by passing to distillates, but
ensuring satisfactory stability margin of unconverted residue. The HDT is
carried out in the presence of several thousand ppm of a Mo-based catalyst
dispersed in the bulk of liquid in order to promote upgrading reactions
(metal removal, desulphurization, denitrogenation and carbon residue
reduction). The hydrotreated products coming out of this section are sent
to the fractionation section to recover distillates. The unconverted residue
from the bottom of the fractionating column is then sent to a section of
SDA to recover a DAO, while stream asphaltenes containing all of the catalyst
is recycled to the section HDT for reprocessing along with fresh feed. After
a given number of cycles a steady state condition makes it possible to obtain
nearly total conversion level, beyond the traditional limitations of classical
conversion processes, such as loss of stability of the reaction products
production and consequently coke formation[44]. The process proved to be
extremely flexible to treat different types of heavy loads, such as VR of
conventional crudes (Arabian crude), heavy crude oil (Maya from Mexico)
and extra heavy crude (Orinoco Oil Belt from Venezuela) and bitumen from
oil sands (Athabasca from Canada). Good performances regarding catalyst
life, the ability to recycle the asphaltenes and the minimum amount of
322 Energy Sci. & Tech. Vol. 3: Oil and Natural Gas

purge required to prevent accumulation of metals contained in the feed

have given merits to this technology during heavy oil processing. The EST
process allows almost complete conversion of the load ( 95%) and ensures
an excellent level of improvement in the products quality.

Another slurry process is the so-called slurry HC3 (High conversion,

hydrocracking, Homogeneous Catalyst) process developed by the Authority
for Research and Technology of the Alberta Tar Sands and the Alberta
Research Council (ARC). Here, the upgrading reaction is conducted in the
presence of a catalyst defined as colloidal, formed in situ from hydrocarbon
soluble precursors such as pentacarbonyl Fe and 2-ethylhexanoate of Mo
and if necessary an aromatic diluent is used to prevent asphaltenes
precipitation. Conversion products are fractionated in vacuum and the
residue may be re-circulated. Also for this process, conversion levels (the
fraction that boils above 500C) in gas, light and heavy distillates can reach
95%. The process was developed on a pilot level 1 bbl/d plant. In 2002, a
patented agreement between ARC and Hydrocarbon Research, a company
controlled by Headwaters Inc., to develop and commercialize this technology
was given[44,63]. In addition to the processes discussed above, there are other
industrial initiatives that expand the range of potentially available
technologies. These technologies include the cracking process Hydrogen
Transfer, developed by Japans Toyo Engineering Corporation in the early
90s, which is based on the use of a catalyst supported on activated carbon
Fe acting on the adsorption and desorption of radicals produced by cracking,
thereby preventing the formation of coke. The process operates at relatively
low pressures (70100 bar), but, however, makes it possible to achieve good
levels of upgrading even with very heavy feeds, such as the Arab oil VGO,
Maya heavy crude oil or Carabobo extra heavy crude oil. Reported
performances indicate a maximum conversion of 85 to 90%, with good levels
of upgrading (HDM and HDS of 95 and 80%, respectively)[44].

Another process proposed by Nikko Consulting and Engineering

Corporation operates in two stages: hydrocracking loads using a slurry-
type catalyst based on transition metals for 6065% conversion and then
coking of the non-reacting part in order to achieve a total conversion of
85%. On the other hand, there is a process called CASH (Chevrons Activated
Slurry Hydrocracking) proposed by Chevron Texaco, which is the result of
a long period of research, based on the use of a dispersed Mo catalyst promoted
with Ni. This formulation appears to be adequate to facilitate the removal
of Ni. The process also provides for the recycling of the catalyst from the
bottom of the distillation column. Finally, GNO-V technology, proposed by
Genoil, involves a hydrogenation process operating with a catalyst in slurry
phase at 400C and 130 bar pressure and upgrading Canadian bitumen enables
increasing the specific gravity of 7 to 28 API with volumetric yields above
100% and sulphur reductions from 5 to 0.2%.
Upgrading and Hydrotreating of Heavy Oils and Residua 323

5.3. Venezuelan Technologies

Petrleos de Venezuela S.A. (PDVSA)[64] is the Venezuelan state company

in charge of exploration, production, refining, transportation and marketing
of hydrocarbons. PDVSA INTEVEP, Inc. is the technology arm, a subsidiary
whose strategic direction of research is to generate comprehensive
technological solutions, with special emphasis on the activities of exploration,
production, refining and industrialization.

INTEVEP has earned international recognition for the development of

the following technology products and services:

5.3.1. ISAL

ISAL is a hydroconversion technology to produce gasoline of low sulphur

content without loss of octane rating. This process generates gas with <30
wppm of S from FCC gasoline with S 20005000 wppm. Further, it has a
combination of catalyst and process for HDS, also performing octane recovery
via hydrocracking. Since 2003, a unit of 32,500 B/D began operation in
CITGO Lemont Refinery[64].

5.3.2. HDHPLUS

HDHPLUS is a treatment for conversion and recovery of heavy and extra-

heavy Orinoco Belt crude oil. HDHPLUS/SHP, residue hydroconversion
technology has conversion levels located in the range 8592 wt.%. It is the
result of 20 years of research and development with a high liquid yield
(above 90 wt.%). It has a novel catalytic system that allows high conversions
with very low metal injection rate. Mo-based catalyst contains incorporated
coke, which is used as a support in order to improve the degree of dispersion
and to facilitate removal of the residue after the reaction. This technology
is also able to treat refractory feeds with high content of contaminants as
they have moderate HDS and HDN activities besides HDM of the entire
feed. Finally, note that HDHPLUS significantly minimizes solid and
refinery products and additionally is completely environmentally friendly[64].

5.3.3. DHDVTM

It is a technology to produce diesel with ultralow S content (less than 15

ppm) and at the same time to meet cetane number specifications, both
American and European (40 and 51, respectively). It can be applied to virgin
or cracked feeds operating under moderate pressure (less than 1300 psi)
and standard temperature (320375C) using 30 to 50% less catalyst volume
than conventional technology. This technology has also been evaluated for
the HDT of VGO to prepare FCC feeds. DHDVTM can be used in the
324 Energy Sci. & Tech. Vol. 3: Oil and Natural Gas

hydroprocessing of streams mixture (petroleum-diesel-VGO), as well as for

treating these streams separately[64].

5.3.4. Aqua ConversionTM

It is a residue upgrading technology where greater decrease in viscosity is

achieved without causing any deterioration of the quality of oil; this has
some positive effects on transportation making these feedstocks
transportable with consequent savings in diluents[64]. This is a process of
residue hydrogenation and mild cracking which is achieved through the
transfer of hydrogen from water which is activated by a single catalyst to
the residual oil being thermally cracked. It is considered a catalytic
visbreaking, which operates in the presence of steam. However, an
improvement in the stability is obtained in comparison to the products
obtained in conventional visbreaking processes, although similar conditions
of pressure and temperature are used. The addition of H2 in this process is
much less than that required when a deep hydroconversion process under
a high H2 partial pressure is employed. Still, it is sufficient to saturate the
free radicals formed by the thermal process, which normally lead to
polymerization reactions forming large asphaltenes and thus causing
stability problems. With this H2 addition, a higher level of conversion can
be achieved, thus enabling improvement in the API gravity and viscosity
and also helps maintaining product stability[65].

5.3.5. INT-MECS

It is a process for upgrading heavy and extra heavy crude, based on

deasphalting through a liquid-liquid extraction with the use of low molecular
weight solvents (e.g., C3H6) under low severity operation conditions. The
benefits provided by this technology embraces the improvement of physico-
chemical properties of heavy and extra heavy crude in their API gravity
(1620API) and reduction in the content of S and metals. Also, upgraded oil
can be incorporated into another crude oil production line, such as Merey
crude production line. Additionally, the proliferation of new waste pits and
the treatment of already existing pits are removed[66].

6. CONCLUSIONS

Today, as a consequence of the high demand on petroleum derivatives, the

near future will be inevitably dominated by heavy oil refining. In this sense,
upgrading of this type of feedstock is a major goal in oil producing countries.
The upgrading can be achieved through carbon rejection or hydrogen
addition technologies. The use of enormous amounts of catalysts during
HDT of heavy feeds, have made the carbon rejection route (thermal cracking,
Upgrading and Hydrotreating of Heavy Oils and Residua 325

hydrocracking and direct coking) the preferred option as it reduces processing

costs. However, recent advances in technology for the upgrading of heavy
crudes and residues are focused on the production of transport fuels with
high quality from crude fractions of low H/C or high boiling point.

The understanding of the role of conventional catalysts during

hydroprocessing of heavy feeds has motivated the development of catalysts
with high deactivation resistance and selectivity to convert heavier fractions
of petroleum. Fluorine, phosphorus, zeolites, SiO2 among others, have been
used to modify the chemical and physical properties of both the supports
and the active phase, providing improved selectivity and cracking activity.
Moreover, textural properties have also been taken into account since large
pores are required to handle large molecules found in these heavy loads,
such as asphaltenes and porphyrins which are the precursors of coke and
metals deposits on the support. However, a compromise regarding textural
properties between HDS and HDM functionalities of the catalysts must be
guaranteed by using bimodal and multimodal catalysts. Macroporous
catalysts avoid poisoning and/or fouling caused by blocking the active pore
mouth either by deposition of metals or coke. In any case, the use of a
guard-bed type reactor is highly desirable to retain organometallic
compounds that are difficult to process. In addition, high conversions were
found when using catalysts in dispersed phase (slurry), but it has an
inconvenience in the recovery of the catalyst to be reused from the products
and unreacted feed, forcing them to be inexpensive materials with high
catalytic activity. Unfortunately, there is no ideal recipe to handle and
processing heavy crude oils for all refineries in the world, since these feeds
vary as also do the parameters to be achieved in order to meet the needs of
the market that is being addressed and the environmental standards.
Everything will depend on the configuration of the refinery, the crude oil
prices and products, local needs and market trends, which will be defined
according to the needs and technical and financial capacity of the refinery.

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