Emerging Technologies For The Conversion of Residues PDF

2.
Emerging technologies
for the conversion of residues
2.5.1 Introduction having been expelled from the source rock, migrated
into permeable layers of rock where they were able to
Around the world, there are major reserves of the undergo a series of degrading processes, such as attack
so called non-conventional crude oils, that is to say, by micro-organisms, evaporation or washing out of the
heavy crudes and bitumens that are recoverable light fractions, which resulted in the concentration of
from oil shale and oil sands bitumen, and which the heavier component of the oil. A common
form a strategic reserve to supplement the crudes characteristic of the greater part of heavy oils is their
with which we are familiar and which are presence in fluvial basins relatively close to the
identified as conventional crude oils. Even though surface, as in the case of the Orinoco basin in
there is no universally recognized definition, Venezuela (Orinoco Belt).
normally these fossil sources are classified on the The estimated reserves of heavy crudes and oil
basis of the API gravity and viscosity values at the sand bitumens amount to around 5,000 Gbbl.
reservoir conditions (Table 1). According to this Considering also that the technically recoverable
classification, heavy crudes are defined as oils fraction is in the range 15-20%, it is evident that we
with an API gravity of less than 25°. Among them, are talking about enormous quantities if one considers
those with a viscosity greater than 10,000 mPa·s that the whole of the Middle East has reserves of 2,000
are classified as extra-heavy; in general, their Gbbl, of which 683 is considered to be recoverable
gravity is less than 10°API, which indicates that (IEA, 2004; Perrodon et al., 1998). The greater part of
they have a higher density than water. Bitumens these reserves is concentrated in Canada in the
extractable from bituminous sand, better known by province of Alberta and in Venezuela in the
the term oil sands bitumen, also fall into this above-mentioned Orinoco Belt. A third country which
category, as well as the oil produced through heat is rich in non-conventional oil is Russia, even though
treatment of oil shale. in this case, the data for establishing the quantities of
From a geological point of view, a large part of the these reserves and the types of oils are much more
heavy crudes derive from mature oils which, after uncertain (Table 2).
Table 1. Classification of non-conventional oils
Rheologic
Specific gravity Viscosity
characteristics of oil
(°API) (Pa⭈s)
at reservoir conditions
Heavy crude oils 16-25 Mobile
Extra-heavy crudes ⬍10 ⬎10 Mobile
Bitumens from tar sand 7-12 Non-mobile
Oil shales Impermeability of the source rock
VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 137

HYDROCARBONS FROM NON-CONVENTIONAL AND ALTERNATIVE FOSSIL RESOURCES
Table 2. Main deposits of bitumens (1) and heavy crude oils (2)
Technically
Deposits of bitumens and heavy crudes Reserves (Gbbl) recoverable Depth (m) °API
(Gbbl)
Canada
Athabasca1, Cold Lake1, Peace River1, 1,630 315 0-750 8-20
Lloydminster2
Venezuela2
Orinoco Belt (Cerro Negro, Zuata, etc.), 1,900 272 1,300 8-11
Bachaquero, Boscan
Russia1
450
Siberian platform, Malekess
As far as oil shale is concerned, the worldwide crude, according to which production will peak over
reserves are in the order of 2,600 Gbbl; of these, about the next ten years (Fig. 1), reinforce the idea that it will
2,000 Gbbl are within the territory of the United States be increasingly necessary to make recourse to non-
and, in particular, in the formations called Green River conventional oils, drawing on the reserves of extra-
(Colorado), the Uinta Basin (Utah) and the Washakie heavy crudes and bitumens of Canada, Venezuela and
Basin (Wyoming). Other significant reserves can be Russia and, thereafter (beyond 2030), on oil shale.
found in Brazil, Australia, China, Russia and Estonia These factors are behind a series of industrial
(Dyni, 2004). initiatives which, over the next decades, could bring
The exploitation of these fossil reserves is highly significant amounts of synthetic and/or distilled crudes
strategic inasmuch as it would make it possible to from non-conventional sources onto the market. This is
increase the known reserves without recourse to also due to the progressive reduction in production
investment in new exploration. Moreover, these costs resulting from the development/optimization of
resources help to diversify the sources of supply and, new technologies, both upstream and downstream. In
given their geographical distribution which locates this regard, the most significant case is certainly that of
them predominantly in areas other than the Middle Canada where the efforts in developing ad hoc
East, to eliminate the geopolitical risks which have technologies for exploiting the oil sands bitumen
been a constant factor in the crude oil marketplace. fields, which began in the 1970s, have made it possible
Production of heavy crudes and bitumens very to reduce production costs by more than 50%, making
often involves the use of special technologies this type of activity commercially viable. It is forecast
developed specifically to handle products which are that in 2010, more than 60% of Canadian production
highly viscous or, as in the case of bitumens, dispersed
within sandy mineral groundmasses or, yet again, 125
oil world production (Mbbl/d)
recoverable only through thermal processing of the

organic material contained in sedimentary rocks, as 100
happens with oil shale.
In the last 15-20 years, interest in developing the 75
technologies for exploiting non-conventional oils has
gone through alternating phases, depending on the 50
favourability, or otherwise, of the macro-economic
25
climate for scheduling investments in this sector
(forecasts of the price of crude and of the differential 0
between heavy and light oils). Moreover, expectations 1971 1980 1990 2000 2010 2020 2030
about overcoming various technological obstacles
connected primarily to the compositional existing capacities development of existing reserves
characteristics of these resources often have not been enhanced oil recoveries non-conventional oils
lived up to. development of new discoveries
Nevertheless, the forecasts of the demand for oil
over the next 20-30 years and the pointers which Fig. 1. Medium-term forecasts for worldwide
emerge on the availability of reserves of conventional oil production (IEA, 2004).
138 ENCYCLOPAEDIA OF HYDROCARBONS

EMERGING TECHNOLOGIES FOR THE CONVERSION OF RESIDUES
will come from oil sands bitumen in the form of The methodologies developed to determine their
bitumen itself or synthetic crude oil (SCO), and that characteristics are related to the methods used in
will enable it to increase its oil production from the oilfields to simplify the mixture, operating in such a
current 2.5 Mbbl/d to over 5 Mbbl/d, making it the way as to separate the fractions with the most
fourth biggest producer after Saudi Arabia, Russia and homogeneous chemical-physic characteristics possible
the United States. (Altgelt and Boduszynski, 1993). The primary
operation is distillation which enables the fractions to
be separated based on their volatility. In this regard,
2.5.2 Properties and chemical the heavy oils and bitumens have a distillable
characteristics hydrocarbon content (naphtha and gasoils) which is
of non-conventional oils remarkably lower than that of traditional crudes, such
as for example, Arabian Light (Table 3).
Heavy crude oils and bitumens The different distillation cuts can be further
As far as their compositional characteristics are fractionated, based on criteria of polarity and/or
concerned, as with petroleum, heavy crude oils and molecular weight, by processes with varying degrees
bitumens are made up of highly complex mixtures of of precision according to the complexity of the
hydrocarbons. Their chemical and chemical-physic mixture and depending on the type of information
(molecular weight, H/C ratio, specific gravity, required. In the case of light distillates (naphtha and
volatility, etc.) characteristics vary continuously, from atmospheric gasoils), chromatographic separation is
the simplest paraffin structure (hydrocarbon gases) to used to sub-divide the saturated hydrocarbons from the
the macromolecules made up of scores of carbon aromatic. For the heavier fractions and the distillation
atoms, as well as hetero atoms (sulphur and nitrogen) residues – which, in the case of the products under
and metals. consideration, account for the largest quantity of
Table 3. Principal compositional characteristics of heavy crude oils and bitumens
Arabian Athabasca
Zuata Boscan Maya Cold Lake
Light Bitumen
Source Saudi Arabia Venezuela Venezuela Mexico Canada Canada
API gravity 33.6 8.5 10.5 21.5 10.2 7.4
Distillation yield (% by weight)

Naphtha 20.6 0.0 4.0 12.9 1.5 1.0
Atmospheric gasoil 36.0 14.1 11.6 21.7 14.9 13.0
Vacuum gasoil 23.2 31.0 20.2 22.2 38.8 34.0
Vacuum residue (VR) 20.2 54.9 64.2 42.2 44.8 52.0
Vacuum residue characteristics

TBP cut * 530°C⫹ 500°C⫹ 350°C⫹ 500°C⫹ 340°C⫹ 300°C⫹
API gravity 8.3 2.5 7.2 1.5 7.2 7.8
Sulphur (weight %) 4.0 4.2 6.0 5.2 4.9 4.6
Nitrogen (weight %) 0.25 0.97 0.96 0.81 0.70 0.48
Nickel (ppm) 30 154 119 132 107 70
Vanadium (ppm) 110 697 1,473 866 210 186
C7 Asphaltenes (weight %) 5.3 19.7 18.2 30.3 N/a 12.4
CCR (weight %) 18.0 22.1 18.3 29.3 20.8 13.6
* The mnemonic TBP (True Boiling Point) indicates that the cut has been carried out in accordance with the procedures indicated in the ASTM
standards.

fractions – the commonly accepted analytical protocol dibenzo- and naphthobenzo- thiophene), but also as
involves the preparation of four classes of compounds aliphatic sulphur in sulphide and disulphide type
called: saturates, aromatics, resins and asphaltenes functional groups. These functionalities are often used
(SARA analysis). Each class can then be analysed to to create links between hydrocarbon clusters.
identify its individual components or to evaluate its Nitrogen, which is contained at levels of 0.5-1% by
most important molecular characteristics, depending weight, tends to concentrate in the heaviest fractions
on the complexity of the mixture and/or the on the distillation curve. This heteroatom is found in
requirements. both basic type (predominantly primary aliphatic and
Compared with traditional crudes, the quantity of aromatic amines and pyridines) and neutral type (in
saturated hydrocarbons contained in heavy crude oils the form of indoles, carbazoles, imides, as well as
and bitumens is considerably lower (Fig. 2). From a porphyrin nitrogen) functional groups.
qualitative point of view, there are major differences Oxygen is present in the crude, in heavy oils and
due to a lower concentration of n-paraffins in favour of bitumens in small amounts, about 1.0-1.5 wt% or less
iso-paraffins and naphthenes with a high degree of and, since it ends up by preference in hydroxylic type
condensation that very often contain sulphur in their groups (phenols, alcohols and carboxylic acids), it
structure. concentrates in the most polarized components of the
The non-aliphatic component is made up of crude such as resins and asphaltenes. Naphthenic acids
aromatic and heteroaromatic hydrocarbons with certainly make up the most researched class of
differing degrees of condensation, different oxygenated compounds, above all because of their
alkyl-substitution and functionalization. Even in this corrosive properties. More rarely, the oxygen can
case, for the same distillation cut, the hydrocarbon appear in the form of ethers or cycloethers, or coupled
structures display a higher degree of condensation with other heteroatoms to form sulphoxides and
compared with what is seen in conventional crudes. amides.
Another characteristic of heavy crudes and As far as metals are concerned, nickel and
bitumens is the fact that they contain significant vanadium are by far the most abundant elements (up to
amounts of heteroatoms (especially sulphur and several hundred ppm), even though some oils can
nitrogen), as well as heavy metals, such as nickel and contain significant quantities of sodium, iron and
vanadium in particular. molybdenum. These metals are contained in
By far, the most common heteroatom is sulphur oil-soluble metallo-organic structures and are
whose concentration can reach values of 6-8% by concentrated in the heaviest parts of the oil, so much
weight. Sulphur is distributed in increasing so that they are found in abundance in asphaltenes. A
percentages in the products with the highest boiling consistent part of the metallo-organic component is
temperature and is present predominantly as the porphyrinic type, but many other structures which
thiophenic sulphur in condensed structures (benzo-, are often difficult to identify broaden the case studies
of the metal-containing compounds present in
asphaltenes.
100%
aromatics Bitumens obtained by extraction from oil sands
bitumen can contain inorganic material, typically clay
and sand which are dispersed within the oily matrix in
granules with linear dimensions in the order of
microns (silt). The amount of the inorganic material
depends on the extraction technology and on the
processes used to separate the organic phase from the
sand; this content is from 0.5 to 1.1% by weight if the
bitumen is produced using traditional mining
conventional processes, whereas it can drop to values of between
crude oils Athabasca, Canada 500 and 1,000 ppm where more modern production
Cold Lake, Canada technologies are used, such as SAGD technology
Lloydminster, Canada (Steam Assisted Gravity Drainage) in particular.
Cherokee, USA
100% 100% resins ⫹ Chemical and chemical-physic characteristics
saturates asphaltenes of asphaltenes
The vacuum residues, i.e. the quantitatively greater
Fig. 2. Distribution of the principal hydrocarbon types fraction of heavy crudes and bitumens, mainly consist
making up heavy crudes and bitumens. of aromatic hydrocarbons condensed to varying

degrees and distributed across a wide range of C5 asphaltene

molecular weights and polarities. They constitute a
compositional continuum even though, as mentioned
C7 asphaltene
earlier, they are generally divided into aromatics,
resins and asphaltenes. The differentiation of these
molecular weight
fractions cannot, however, disregard the operating
parameters used to carry out the separation.
Deasphalting is a typical example which is largely
influenced by the type of precipitating agent used as
well as the operating conditions (Speight, 2004). The
direct consequence is that to be able to carry out a
comparison between different samples, it is essential crude oil
to standardize the analysis conditions, specifying the
precipitating agent used (usually n-pentane or
n-heptane) and supplying details of the method used.
Conceptually, the separation of asphaltenes can be
compared to the fractionating through distillation of polarity
the volatile component of the crude oil. In both cases,
the constituents of the mixture are divided by defining Fig. 3. Representation of the molecular characteristics
a ‘cut point’, such as the boiling temperature of asphaltenes (Long, 1979).
(distillation) or the solubility parameter of the
precipitating agent (deasphalting). The solvent
strength of the hydrocarbons, or better still, its ability asphaltenes from different sources vary considerably
to act as a solvent or anti-solvent in precipitating in their aromaticity, degree and nature of alkyl
asphaltenes, can be correlated to the solubility substitution, as well as the heteroatom content
parameter d defined by Joel Hildebrand and Robert (Cimino et al., 1995).
Scott as: As far as their molecular weight is concerned, the
412 issue is complicated even further because of the
冢
DHV⫺RT
冣
2
d ⫽ 11112 tendency of the asphaltenes to form aggregates, to
V
such an extent that the molecular weight
where DHV is the molar enthalpy of vaporization of measurements made by means of Vapour Pressure
the hydrocarbon concerned, V is its molar volume, and Osmometry (VPO) or Size Exclusion Chromatography
R and T are the universal constant of gases and the (SEC) are significantly affected by the polarity of the
absolute temperature respectively. The solubility solvent used. For this reason, the average molecular
parameter may also be estimated by using the weight values quoted in literature, where you find a
equation: variability ranging from 103-104 units of atomic mass,
1
⫺ 42 have a (relative) significance if considered within a set
d2 ⫽AV 3g
of measurements taken, but can be given little
where A is a constant, g is the surface tension and V is credence as far as the actual molecular dimensions of
the molar volume of the hydrocarbon concerned the sample are concerned.
(Barton, 1991).
A very effective bi-dimensional diagram
illustrating the molecular characteristics of asphaltenes Table 4. Compositional variability of C7 asphaltenes
was suggested by Robert Long (Fig. 3), in which the precipitated from crudes and bitumens
polarity and molecular weight of the hydrocarbons
present in the oil constitute the primary parameters Yield of oil based asphaltenes (% by weight) Up to 30
which, depending on the solvent used, determine the H/C ratio 0.8-1.4
precipitation of specific fractions (Long, 1979). In Sulphur (weight %) 0.5-10.0
addition, this diagram indicates that asphaltenes must
Nitrogen (weight %) 0.6-2.6
be considered to be a class of compounds which, from
a chemical point of view, can be very broad and Oxygen (weight %) 0.3-4.8
diverse. Aromaticity factor 0.45-0.70
As well as the method used during the separation
n (average number of atoms of C per alkylic
phase, the chemical characteristics of the asphaltenes substituent)
4-7
depend on the crude oil origin. As shown in Table 4,

The chemical-structural analysis of asphaltenes can by ‘archipelago’ models, that is, structures made up of
be carried out effectively through techniques of islands of little groups of condensed rings, linked
nuclear magnetic resonance (1H- and 13C-NMR). together by aliphatic chains and sulphide bridges, as
Using these techniques, various average molecular depicted in Fig. 4 (Sheremata et al., 2004).
parameters may be determined, such as aromaticity The resins are compounds that fall between
factor, degree of alkyl substitution, average chain asphaltenes and hydrocarbon components (saturated
length, etc. These are extremely useful for giving an and aromatic); they consist of polar molecules similar
idea of the hydrocarbon skeleton, as well as the to those of asphaltenes, but contain longer lateral
chemical functionality of the molecules present in the aliphatic chains and smaller aromatic rings.
sample. The results of these analyses tend to show the As already stated, because crude oil is a
asphaltenes as macromolecules made up of continuum, it is the separation procedure that
polycondensed aromatic clusters, substituted in determines the difference between asphaltenes and
various ways with alkylic chains which can be fairly resins; resins could be considered to be asphaltenes
long (>C10), and linked together by saturated and with a low molecular weight, just as asphaltenes could
hydrocarbon chains and heteroatoms. The degree of be seen to be resins with a high molecular weight.
condensation of the aromatic units can be high, but From the 1950s onwards, thermo-dynamic models
normally it does not exceed a figure of 5-6 rings have also been proposed in which the asphaltenes
(Speight, 1980). appear as colloidal particles dispersed in the oil due to
As with the other classes of compounds, the the action of the resins which surround them.
asphaltene component of heavy crudes and bitumens is Displaying a comparatively greater polarity than the
also significantly different from that of light crudes. In rest of the oil, the resins are adsorbed onto the surfaces
addition to the high heteroatom and metal content, of the colloidal particles. In accordance with these
asphaltenes have significantly higher molecular models, the asphaltenes are stabilized or ‘peptized’ by
weights, due to the high concentration of sulphur the resins; if a change in conditions of temperature,
which favours the formation of sulphide and pressure or composition leads to the desorption of the
disulphide bridges among the aromatic clusters, a resins from the colloidal particle surfaces, there is a
characteristic which makes these structures very separation (precipitation) of the asphaltenes (Murgich
reactive in relation to thermal cracking and et al., 1996).
hydrogenating reactions (see above). This model, which describes asphaltenes as
From the molecular point of view, the asphaltenes lyophobic colloids, is being increasingly discarded in
contained in bitumens can be represented effectively favour of a description of asphaltenes as lyophilic
H S
S N
CH3
S
H3C CH3 S S
O
N
H3C
S S
N S
O CH3 NH
S
O S
H3C OH O
H3C H
CH3 N S
O
O
A B
Fig. 4. Average molecular structures representing asphaltene molecules from different sources: A, asphaltenes from traditional
crudes; B, asphaltenes from Canadian bitumen (Sheremata et al., 2004).

OH OH
O
O O
OH OH
O O
O O
O O
HO
OH
O OH O
HO S
S HO
O OH
O
HO OH
O
O OH O
O
O HS Cl O
S
O O OH
O HO
O OH
O NH
OH
O OH
Fig. 5. Representation of the molecular structure of kerogen (Lille et al., 2003).
colloids, solvated by the surrounding medium. In this significantly greater than that of coal, with an H/C
model, the separation phase of the asphaltenes is ratio of 1.5-1.6 compared with values of 0.8-0.9 for
linked to a decrease of the medium’s solvent strength, bituminous coals. In a similar way to coal, this organic
and the resins cease to play the key role in the system material is usually divided into groups of macerals
(Cimino et al., 1995). according to their optical (reflection of light) and
morphological characteristics, echoing the nature of
Nature and chemical characteristics of oil shales the biological material which created them. Macerals
Oil shales are sedimentary rocks, generally can be grouped into three primary types called
silicates and carbonates, containing significant telalginite, lamalginite and bituminite which, in turn,
amounts of insoluble organic material which can can be further divided into subgroups.
be recovered through pyrolytic distillation (a
process which is better known as retorting). In the
rocks which cover a site of potential commercial 2.5.3 Chemistry of the conversion
interest, the amount of organic material must be and upgrading processes
greater than 10 gal/t (45 l/t), even though as a
norm, in the richest formations, this value is The purpose of converting and upgrading petroleum
between 30 and 40 gal/t (for Athabasca bitumen it residues, heavy crudes and bitumens is to transform a
is around 22 gal/t). Oil shale deposits can extend substrate consisting of high molecular weight
for hundreds of square kilometres with thicknesses hydrocarbons, which are viscous and rich in toxic
which can reach 700 m, so that the quantity of elements and metals, into products which are lighter
recoverable oil per unit of surface area is greater and more fluid (synthetic crude oil), and are
than the Canadian oil sands by an order of comparable to traditional crudes; or better still, into
magnitude. The productivity of the biggest deposits distillates that can be further upgraded to yield
(for example, Colorado oil shale) can, in fact, gasoline and diesel for motor vehicles. This
reach figures of up to 0.73 bbl of oil per tonne of transformation can be achieved directly through
material extracted (Bunger et al., 2004). thermal or hydrocracking processes, or indirectly
The organic component of oil shale is made up of through transformation of the feedstock (a quantity of
complex hydrocarbon molecules comparable to material for feeding the reactor) into syngas (i.e. a
kerogen (Fig. 5), from which petroleum originates, mixture of CO and H2) through gasification (see Vol.
containing significant quantities of oxygen (5-6% by II, Chapter 7.3), and the subsequent production of
weight) and, to a lesser extent, sulphur and nitrogen. paraffin through Fischer-Tropsch synthesis (see
The hydrogen content of the kerogen itself is Chapter 2.6).

Processes for conversion into distillates severity of the process increases, the gas yield
The processes for direct conversion of heavy increases, and problems are encountered in relation to
feedstocks into distillates are particularly complex and the stability of the reaction products (see below). The
involve the reduction of the molecular weight of the quality of the distillates is poor, because thermal
feedstock constituents through reactions which break cracking alone is not capable of removing, in any
the bonds of the hydrocarbon molecules (cracking) significant way, the heteroatoms present in the heavy
and increase the H/C ratio; the latter can be achieved feedstocks. Moreover, naphtha and gasoil are rich in
through the removal of carbon (C-rejection process) or olefins and dienes and, hence, must be stabilized
the addition of hydrogen (H-addition process). through hydrotreatment.
The C-rejection processes are thermal processes In the H-addition processes, conversion of the
through which the heavy hydrocarbons in the heavy feedstocks and the distillates is achieved
feedstock are disproportionated, generating distillates through the combined reaction effects of cracking and
with a high H/C ratio and releasing a highly aromatic catalytic hydrogenation of the reactive fragments. In
residue (tar or coke). This is a radicalic type process this way, it is possible to control the propagation of the
and involves the homolytic breaking of the C⫺C and radicalic reactions more effectively, above all, with
the C⫺heteroatom bonds, followed by b-scission regard to the condensation processes of the aromatics
reactions through which, as the reaction progresses, and, hence, to reduce the problem of coke formation
increasingly lighter hydrocarbon fragments are (Fig. 6). Moreover, depending on the reaction
produced, generating distillates and gas. However, the conditions and the type of catalyst used, it is possible
aromatic radicals produced by dealkylation (radical p) to add hydrogen to the products, saturating the
tend to react among themselves, giving rise to highly aromatic structures and facilitating the elimination of
condensed polynuclear structures which become ever the heteroatoms. For this reason, the quality of the
less soluble in the reaction mixture and lead to the distillates and the conversion residue obtained from
formation of mesophase and, hence, coke above a the hydrocracking processes is definitely better than
certain level. The residue’s tendency to form coke is that of distillates obtainable through thermal
linked to the degree of polycondensation of the heavy processes.
aromatic structures and is quantified by the CCR value With regard to the thermodynamics of the process,
(Conradson Carbon Residue), which is measured the aromatic structures’ balance of hydrogenation
according to ASTM (American Society for Testing and reactions is facilitated by a high hydrogen partial
Materials) methodology D 189. pressure, whereas it is hindered by an increase in
The principal types of reaction that operate in these temperature. Therefore, the requirement to operate at
processes are, therefore, the dealkylation of aromatic temperatures in excess of 380°C to promote thermal
structures, the dehydrogenation of naphthenes and cracking makes it necessary to push the hydrogen
condensation. All these reactions are favoured by the partial pressure up to levels exceeding 100-120 bar.
temperature which is generally in excess of 450°C. The ideal catalyst for the upgrading of heavy
From a kinetic point of view, at least as far as feedstocks must facilitate the process of hydrogen
visbreaking is concerned, the production of cracking addition to the products generated in the thermal
products follows an apparent first order kinetics with cracking phase, minimizing the amount of coke
activation energy values of around 230 kJ/mol, which produced. Moreover, it must permit the removal of the
indicates that the reaction speed doubles for each poisons present in the feedstock through
increment in temperature of 14-15°C. hydrogenation of the substrate, or rather it must favour
In general, thermal processes are not very selective the processes of desulphurization
towards the production of distillates since, as the (HDS, Hydrodesulphurization), denitrogenation
Fig. 6. Simplified
representation CH2 R1
H2/
of the process catalyst
of hydroconversion S
of heavy feedstocks.
R R1 CH2 . . R1 H distillates
D
S S R1
mesophase coke

(HDN, Hydrodenitrogenation), demetallization The catalysts used in the slurry processes are often
(HDM, Hydrodemetallization) and reduction of carbon closely associated with carbon material (coke) which
residue from the products (HDCCR, Hydro Conradson is either produced during the reaction or is purposely
Carbon Residue Removal). added. Compared with supported catalysts, on which
The most active catalytic species for these conventional hydrocracking technologies are based,
reactions are certain heavy metal sulphides such as these materials are not very sensitive to the presence
Mo, Ni, Co, W and Rh in particular, often used in of poisons, since they do not display the classic
combinations (Ni/Mo, Co/Mo and Ni/W) and problems resulting from the depositing of coke and
deposited on appropriate porous supports (preferably metals onto the pores of the support. The use of
alumina) or mixed with the feedstock in the form of dispersed catalysts based on metal sulphides from
powder (catalysis in slurry phase). groups V, VI and VIII (in particular Fe, Mo and V) for
The main problem that is encountered when using upgrading residues, heavy crudes, bitumens and coal
supported catalysts to process particularly heavy is well-known and has been fully described in
feedstocks is that of limiting the deactivation of the scientific literature for more than thirty years. The first
catalyst due to the depositing of both the metals and significant works published on this subject make
coke. However, it should be made clear that the reference to Clyde Aldridge and Roby Bearden
deposited coke can be removed through regeneration (Aldridge and Bearden, 1978), and describe the use of
of the catalyst, whereas the activity loss due to the Mo introduced in the form of oil-soluble precursors.
metals is permanent and, hence, the catalyst has to be Subsequently, numerous variations were tried and
replaced. proposed in regard to both the use of various types of
The deactivation due to deposits of coke leads to a precursors and the ex situ synthesis of the catalyst in
loss of activity because the active sites of the catalyst order to improve its specific activity.
are covered by carbonaceous material, primarily from The most active dispersed catalysts, however, are
asphaltenes; in fact, this loss increases with the level still those based on molybdenum and obtained through
of conversion of the feedstock into distillates, that is, the decomposition of oil-soluble precursors such as
when conditions favour the emergence of stability naphthenates, oxalates, xanthates, dithiocarbamates or
problems. The deactivation by coke can be offset by an other metallo-organic derivatives such as Molyvan A
increase in the hydrogen partial pressure. (N,N-dibutyldithiocarbamate of oxothiomolybdenum)
As regards the metals, the deactivation comes which are supplied at the hydrocracking/hydrotreating
about through the obstruction of the porous structure stage together with the feedstock (Delbianco et al.,
and the covering of the active sites by the metals 1995). The in situ decomposition of these precursors
contained in the metallo-porphyrinic structures which in the presence of hydrogen and sulphur generates an
are destroyed during the reaction generating the
corresponding sulphides.
However, the physical characteristics of the support 10 nm
and, in particular, its porosity are as fundamentally
important as those of the active phase in determining
the catalyst’s behaviour. Its high viscosity and the
presence of high molecular weight compounds
(asphaltenes and metallo-organic compounds), which
are characteristic of heavy feedstocks, make access to
the substrate within the catalyst particles difficult; the
diffusion process within the porous structure can be a
problem and can represent the slow stage of the
reaction. If the catalyst does not have a sufficiently
porous structure and the diffusion of the molecules in
the pores is impeded, most of the metals are deposited
on the external surfaces, causing obstruction of the
pores and, therefore, impeding the reaction.
Consequently, in the case of heavy feedstocks,
macroporous materials are used, often as ‘sacrificial
beds’, on which most of the demetallization reactions
are made to take place in order to go ahead with the Fig. 7. Structure of micro-crystalline molybdenite obtained
conversion reactions and upgrading of the feedstock through TEM microscopy (Transmission Electron
using ad hoc catalytic beds. Microscopy; Panariti et al., 2000).

extremely fine powder made up of nano-sized layers sulphur comes about through the formation of H2S
of molybdenum sulphide (molybdenite, MoS2) with a and may or may not be difficult, depending on the
low degree of aggregation (nanocluster) and highly nature of the sulphuretted compound that contains
dispersed within the feedstock. The active catalytic it. In general, the reactivity of the sulphuretted
phase is, therefore, the molybdenite, a well-known species follows a decreasing scale: aromatic S
layered hexagonal structure with molybdenum (condensed thiophenes⬎thiophenes)⬎naphthenic
between two layers of sulphur. The adjacent layers are S⬎paraffinic S (thio-ethers and disulphides).
linked together by the weak dispersion forces (Van der The second heteroatom usually present in heavy
Waals type) in action between the respective sulphur feedstocks is nitrogen, which is removed in the form
atoms. For this reason, the molybdenic structure can of NH3 through hydrogenation of the heteroaromatic
be easily peeled (delaminated) until the elementary structures that contain it. The elimination of nitrogen
foils are obtained which display a very low degree of is more difficult than that of sulphur since the energy
stacking, guaranteeing a high dispersion in the oily of the C⫺N bond is greater than that of the
matrix (Fig. 7). On average, the radius is in the range C⫺S bond (360 kJ/mol against 320 kJ/mol for amine
of 2-4 nm. Microscopic analysis reveals that the and alkylic sulphide, respectively).
molybdenite crystals tend to aggregate into particles As far as metals are concerned, the removal of Ni
with a length in the order of a micron which appear in and V (demetallization reactions) is performed by
the shape of irregular clusters that have an average passing the porphyrinic structures in which they are
diameter of 0.5-2 mm (Panariti et al., 2000). contained through a hydrogenation process. This leads
Its morphological characteristics and the absence to the formation of pyrrhotitic type sulphides, i.e.
of porous supports make molybdenite particularly Ni1⫺xS, V1⫺xS (with x⬍0.1), which are released in the
well-equipped to operate effectively as a reaction mixture or trapped in the porous structure of
hydrogenation catalyst in very severe conditions the supported catalysts used in the process.
because of the presence of high concentrations of The main reactions involved in the residue
poisons, especially heavy metals. The catalytic activity hydrocracking processes are exothermic. The heat
of molybdenite in a hydrogenating environment seems generated depends on the nature of the feedstock being
to be due to both the formation of sulphur vacancies treated and the degree of conversion, as well as the
on the profiles of the nanoclusters due to the effect of level of upgrading achieved by the process. The
the interaction of the hydrogen with MoS2, and the thermal tonality of the different reactions, which occur
formation of –SH groups which evolve into H2S. in the upgrading processes, can be estimated based on
The reactivity of heavy feedstocks to the hydrogen consumption within a determined range
hydrocracking is strongly influenced by the nature of of values, as illustrated in Table 5 (Tominaga and
the substrate which can display differing degrees of Tomaki, 1997).
reactivity, depending on the average molecular
structure and on the concentration and nature of the Stability of petroleum residues
heteroatoms present. From a general point of view, stability expresses the
The most reactive substrates are characterized capacity of a petroleum residue to tolerate dilution with
by the fact that they have average molecular fluxants (cutter stocks) which are predominantly
structures containing relatively small aromatics paraffinic in nature, without giving rise to the
clusters, linked together by alkylic chains or precipitation of asphaltenes. The stability is assessed by
C⫺heteroatom bonds with low bonding energies. determining the P-value, that is, the value of P derived
As regards the hetero-atoms, the elimination of the from the equation: P⫽1⫹Xmin , where Xmin is the value
of the sample’s maximum dilution in cetane (n-C16H34)
where there is no precipitation of asphaltenes,
Table 5. Estimate of reaction heat for the main reactions expressed as ml of cetane per gram of the sample.
involved in the hydrocracking of heavy feedstocks In primary distillation residues (straight run), the
stability is an intrinsic quality of the product and
Type of reaction kJ/(mole H2 consumed) depends on the compositional characteristics of the
Cracking and ring opening 20-45 asphaltenes compared to those of the non asphaltenic
hydrocarbon phase (maltenes). The conversion
Aromatic saturations 55-70
processes, both thermal and catalytic, modify the
Olefin saturations 115-125 chemical nature of these two pseudo-compounds,
Hydrodesulphurization (HDS) 55-75 causing a progressive reduction in stability as the
severity of the treatment grows (linked to the reaction’s
Hydrodenitrogenation (HDN) 60-85
time-temperature combination). The reasons for this

reduction in stability are due to the fact that during the hydrovisbreaking) which are called Tervahl H and
course of the reaction, the asphaltenes are dealkylated Tervahl C, respectively. The improvement in
and become increasingly aromatic and, hence, performance in terms of HDS activity is, however,
increasingly less soluble in the maltene phase which limited to values of around 20% compared with
tends to become more paraffinic for the same reason. classical visbreaking.
Above a certain conversion level, the asphaltenes Another solution, proposed by PDVSA-Intevep and
precipitate (hence a separation of the liquid-liquid patented in conjunction with Foster-Wheeler/UOP, is a
phase is seen), triggering processes in which process called Aquaconversion. In this instance, the
mesophase is formed and, hence, coke. visbreaking operation is carried out in the presence of
This phenomenon can be observed in all residue water and a catalyst capable of promoting the partial
conversion processes, both thermal and hydrocracking, breakdown of the water to produce hydrogen in situ,
so much so that the stability of the conversion which is used for a partial upgrading of the feedstock,
products actually determines the maximum conversion while the oxygen is used to produce CO2. The process
level obtainable for a given feedstock. For this reason, was developed to pilot plant level and, later, on a
it is not possible to push the conversion beyond demonstration scale using a suitably modified existing
20-30% in visbreaking plants or beyond 40-50% in 18,000 bbl/d visbreaking unit. In the reaction conditions
fixed bed hydrocracking plants. suggested by PDVSA, the cracking reaction can be
managed at a level of severity above that of classic
visbreaking, making it possible to increase the conversion
2.5.4 Carbon rejection yields for the same level of stability of the residue and
technologies improve the quality of the product as well (Table 6).
Then there are thermal cracking processes that
Thermal processes: visbreaking and coking operate at greater severity than visbreaking that aim to
further increase the degree of conversion into distillates
Visbreaking and produce a residue capable of being pumped.
Visbreaking is a very simple technology for the Because the residue is unstable, it cannot be utilized as
treatment of petroleum residues, which is very fuel oil but has to be burned directly in fluid bed
widespread globally. The process involves heating the boilers or gasified. Such is the case of the process
feedstock for just a few minutes to temperatures in called Deep Thermal Conversion developed by Shell.
excess of 450-460°C and at low pressure. In these Other solutions, and in particular, the Eureka
conditions, the high molecular weight hydrocarbon process perfected by Chiyoda Corporation and the
structures that make up the heavy feedstock undergo a HSC process (High-conversion Soaker Cracking)
partial thermal cracking process, resulting in the developed by Toyo Engineering Corporation, operate
production of a limited quantity of distillates, generally in fields of severity which fall between visbreaking
less than 30% by weight, and of a residue with reduced
viscosity. This residue has to be fluxed until the required
viscosity is obtained to produce a fuel oil, using a Table 6. Aquaconversion process performance.
quantity of diluent that is less than that of the feed itself Feedstock treated: extra-heavy crude from the Orinoco
(see Vol. II, Chapter 5.2). The limit on the severity of the Belt (6.5°API)
process is, in fact, linked to the stability of the residue of
which the P-value must be greater than 1.1-1.2. Visbreaking Aquaconversion
The main aim of using visbreaking to upgrade
heavy crudes and bitumens is to make these products Temperature (°C) Base Base ⫹ 5
more fluid, facilitating their transportation via pipeline Conversion (weight %)
without the need to use diluents (naphtha).
Obviously, given the characteristics of the process, Naphtha 2.9 7.5
thermal treatment does not reduce the levels of Distillates 500°C⫺ * 28.2 36.6
pollutants, and for this reason, traditional visbreaking
is of little interest for use in the field of extra heavy Upgrading feedstock
crudes and bitumens. To overcome these limitations, at API gravity of
3.7 5.4
least in part, the Institut Français du Pétrole (IFP) has atmospheric residue
proposed variants of the process that call for the use of P-value 1.2 1.2
hydrogenating atmospheres (hydrovisbreaking) and,
where necessary, metallic additives capable of * Thisis a way of indicating the fraction of distillates that boils
promoting hydrogenation reactions (catalytic below 500°C.

Contrary to what happens with delayed coking, the

Table 7. Comparison of the conversion yields of processes of Fluid Coking and Flexicoking (an
delayed coking and the Eureka processes. Feedstock extension of Fluid Coking) use the coke generated by
treated: vacuum residue with 5.9°API thermal cracking as a reaction medium and as a carrier
of heat. In Flexicoking, the coke is used as a reagent in
Delayed coking Eureka an integrated gasification reactor where it is gasified
Conversion (weight %) with air. In this way, production of pet-coke, the
product of classic coking plants which is of least
Hydrocarbon gases C1-C4 10.4 5.3 value, is eliminated.
Distillates C5-350°C * 39.3 33.6 Both processes were developed by Exxon in the
1950s. The first Fluid Coking plant was set up in 1954
Vacuum gasoil 16.3 28.4
at the Exxon headquarters in Billings and, since then, a
Coke 34.0 0.0 total of 18 units have been constructed. The process
takes place in two fluid bed reactors, connected to
Pitch 0.0 32.7
each other so as to permit circulation of the coke. In
* This is a way of indicating the fraction of distillates that goes from the first reactor vessel, the feedstock is converted by
pentanes to hydrocarbons that boil at 350°C. means of thermal cracking into gas and distillates at a
temperature of 510-560°C in the presence of particles
and coking. In both cases, use is made of steam to of carbonaceous material on which the coke produced
control coke formation. The Eureka process, in by the reaction is deposited. The solid is then removed
particular, is very much like delayed coking in that it from the bottom of the first reactor vessel and sent to
operates with two reactors alternately. The thermal the second one, where it is partially burnt to recover
cracking reaction is carried out in the presence of a heat needed for the process, while the excess amount
recycled oil and high temperature steam to favour is discharged. Alternatively, the residual coke can be
stripping of the distillates. The cracking residue is a gasified with air and steam at a temperature of
fluid pitch at high temperature and, as such, can easily 820-900°C in a third reactor vessel (Flexicoking) to
be recovered from the bottom of the reactor vessel and produce a fuel gas with a low heating value
then cooled and pelletized (Table 7).
Coking Table 8. Product yields and qualities from delayed coking

Delayed coking is the technology most often used
nowadays for upgrading heavy crudes and bitumens. Feedstock Zuata Cold Lake Maya
The process of coking (see Vol. II, Chapter 5.1) TBP cut 510°C⫹ * 565°C⫹ * 565°C⫹ *
involves heating the feedstock in a furnace and then
sending it to reactors known as coking drums, API gravity 2.4 0.4 0.5
operating at high temperatures (around 500°C) and for Sulphur (weight %) 4.4 6.2 5.8
extended reaction times. This process promotes Product yields (weight %)
thermal cracking of the hydrocarbon structures so as to
stimulate the production of gas and distillates from Hydrocarbon gases C1-C4 7.5 8.3 8.2
part of the component with a higher H/C ratio and to Naphtha 10.0 11.0 11.4
leave a carbon residue (coke) in which most of the
Atmospheric gasoil 23.6 20.3 21.1
metals are concentrated (over 90%), and an amount of
sulphur and nitrogen (about 30 and 70%, respectively). Vacuum gasoil 26.1 23.9 25.6
Application of the coking process to heavy Coke 32.8 36.5 33.4
feedstocks becomes relatively simple from a technical
point of view, but it involves the production of huge Distillate characteristics
quantities of coke which is a highly polluting material API gravity 30.3 29.5 28.2
that can be utilized as fuel in power generating Sulphur (weight %) 2.9 4.1 3.8
installations or as feedstock for the production of
hydrogen in gasification plants. The yield of coke can, Coke characteristics
in fact, be directly correlated to the tendency to form Sulphur (weight %) 4.7 6.6 6.2
carbon residues (CCR) in accordance with the
Ni ⫹ V (ppm) 1,976 1,018 2,296
formula: coke (% in weight) = 1.6 · CCR.
Table 8 lists the results of treatment by coking of the * This is a way of indicating the fraction of distillates that boils
vacuum residues from three typical extra heavy crudes. above the temperature indicated.

100
(4.3-5.3 MJ/Nm3) called flexigas, and made up of
CO, H2, N2, CO2 and heterogas (that is, H2S, NH3, etc.).
Besides the advantage of eliminating the coke
produced, the Flexicoking solution allows for better
contaminants distribution (%)

75
control of the cracking process, contributing to a
higher yield of liquids (Table 9).
Other technologies have been developed on the
same principle as Fluid Coking that differ in the 50
solutions adopted with regards to the reactor or the
type of materials used for transmitting the heat. For
sulphur
example, the LR Coker (Lurgi Ruhrgas) uses a
conversion reactor inside which a type of rotating 25
nitrogen
screw helps to obtain optimum contact between the
feedstock and the heat carrier, allowing the system to metals
operate like a plug-flow reactor. There is one version
of this technology that has been specifically adapted 0
0 20 40 60 80 100
for treating extra heavy feedstocks with a CCR content DAO yield (weight %)
of up to 70% (Satcon process).
Finally, a mention should be made of the process Fig. 8. Comparison of yield vs contaminants content of DAO
known as Rapid Thermal Processing (RTP), currently obtained via deasphaltating.
Table 9. Comparison of product yields and qualities in the development phase in a 1,000 bbl/d
when processing an Arabian Heavy vacuum residue demonstration installation at the Canadian company
(1.8°API and 6.0 weight % of sulphur) Ensyn Group, specifically for the processing of heavy
via coking processes hydrocarbon materials from bitumens to ligneous
biomasses. The process involves a rapid heating of the
Delayed coking Flexicoking feedstock using hot sand at the relatively low
Product yields (weight %) temperature of 500°C in a transported bed reactor onto
which the coke is deposited. In this way, it is possible
Hydrocarbon gases C1-C4 11.1 12.3 to process bitumens from oil sands bitumen, producing
Naphtha 13.4 10.8 stable liquids with conversion yields of up to 80%.
Atmospheric gasoil 17.9 15.9
Extraction processes: solvent deasphalting
Vacuum gasoil 17.2 26.3 The fact that most of the metals present in crudes are
Net Coke 40.4 2.7 concentrated in asphaltenes means that by using Solvent
Deasphaltating (SDA), it is possible to recover
Flexigas
(expressed as
significant amounts of partially demetallized and
32.0 deasphalted oil (DAO) from the residues which can be
fuel oil
equivalent) processed economically in FCC or hydrocracking units.
The main advantages of SDA are low investment and
Distillate characteristics
operational costs, while its principal limitation is that to
API gravity 29.6 23.4 obtain DAO with a low content of pollutants (in
Sulphur (weight %) 3.6 4.1 particular, sulphur, nitrogen, metals and CCR), the yield
must be limited. As a result, significant quantities of
Coke characteristics by-products are generated (asphaltenes) that can be used
Sulphur (weight %) 6.4 as components of low quality fuels or as sources of
carbon for the production of syngas and, therefore,
Metals (ppm) 698
hydrogen in suitable gasification units. The yield and the
Composition of the gases (volume %, dry basis) pollutant content in DAO are, in fact, directly connected,
N2 53 as shown in Fig. 8; therefore, the quality of the product
CH4 2 falls as the yield increases (see also Vol. II, Chapter 7.1).
H2 15 The application of the SDA process in the extra
CO 20 heavy crudes and bitumens upgrading sector has led to
CO2 10
the development of ad hoc technologies in which the

Fig. 9. OPTI
Canada/Nexen premium synthetic crude
Petroleum’s
Long Lake Project hydrocracking
for the exploitation hydrogen
of Canadian bitumens sour synthetic crude
(Zuideveld and
de Graaf, 2003). OrCrude asphaltene gasification power
process process
bitumen
steam
SAGD
Athabasca
oil sands
classic extraction unit is often combined with other heavy crudes, capable of producing distillates and
processes. This is the case with the OrCrude process, naphtha, in particular. In the configuration, which is
developed specifically for the upgrading of Canadian most widely used and known as Fluid Catalytic
bitumens by ORMAT Industries. The process involves: Cracking (FCC), the catalyst is mixed with the
a) the distillation of bitumen (atmospheric and feedstock, then circulated between the riser, the reactor
vacuum); b) the deasphaltating treatment of the vessel and the regenerator.
residue during which the asphaltenes are removed; c) Initially, the feed consisted of gasoil, but
the thermal cracking of the DAO; subsequently, and particularly with the evolution of
d ) the recycling of the cracking products into the catalysts, it has been possible to feed FCCs with a
feedstock to the atmospheric distillation, so as to wide range of hydrocarbons, from naphtha to
recover the distillates and separate the asphaltene atmospheric residue.
component produced by the thermal treatment. In the In general, the size of the hydrocarbon molecules
same way as with coking, the OrCrude process that make up the feedstock to an FCC plant is not
produces distillates and a heavy residue (asphaltenes). compatible with the pores of the zeolitic crystal. First
They are used as feedstock for the gasification plant of all, these molecules have to be reduced in size by a
that produces syngas to generate energy and the steam preliminary cracking that takes place on the external
needed for extraction of the bitumens via SAGD surface (matrix) of the zeolite. This matrix can also
(Steam Assisted Gravity Drainage), as well as the have other functions, such as removal of the metals
hydrogen needed for further upgrading of the present in the feedstock.
products. OPTI Canada and Nexen Petroleum are The feedstock enters the riser where it comes into
moving in this direction; a joint venture between these contact with the regenerated catalyst. This contact
two companies is developing a project (the Long Lake leads to the partial vaporization of the feedstock; the
Project) for the recovery and treatment of 70,000 bbl/d oil/catalyst mixture then flows upwards along the riser.
of bitumen in the province of Alberta, in Canada The cracking reactions take place almost completely
(Fig. 9). Applying the process to this type of feedstock along the riser; being globally endothermic, they cause
will enable a yield of 60,000 bbl/d of synthetic crude a reduction of the temperature. The residence times are
oil at 22°API which may be further treated in between 1 and 4 seconds, during which most of the
desulphurization/hydrocracking units to produce a cracking reactions takes place.
sweet synthetic crude oil with a gravity of 39°API, In some cases, the feedstock is pre-treated to
while the remaining 3,100 t/d of asphaltenes will reduce the content of metals and asphaltenes by means
become the feedstock for the gasification unit. of extraction with solvents, deasphaltating with
propane, or treatment with hydrogen.
Catalytic processes: catalytic cracking A high content of asphaltenes and/or aromatics in
The technology of catalytic cracking, conceived in the feedstock favours the formation and deposit of
1936 with the first industrial fixed bed installation, is coke on the catalyst, thus reducing its activity.
characterized by the fact that it uses acidic catalysts Over the years, the process has undergone
based on zeolite to assist the reactions for cracking significant improvements, as regards both the flow

sheet of the process and the catalysts, making it poisons can actually cause a rapid deactivation of the
possible to improve the selectivity towards the catalyst and an increased pressure drop in the reaction
production of naphtha to be used in the gasoline pool circuit with a subsequent reduction in the cycle length.
and increasing its flexibility as far as feedstocks with To overcome these difficulties, appropriate
high contents of pollutants are concerned. At a catalytic systems can be used which make it possible
technical level, improvements have been made in the to minimize the problems associated with the high
system for distributing the feed in the riser and lifting content of contaminants in the feedstock and/or to
the catalyst, in the internal arrangements of the modify the technology, so as to prevent the
reactor-regenerator system, and in the addition of an accumulation of coke and/or to enable the replacement
external heat exchanger, through which part of the of part of the catalyst during operation of the plant.
catalyst circulates to remove part of the heat produced The hydroconversion plants that use supported
by the combustion of the coke deposited on the spent catalysts can be divided into two categories, based on
catalyst. the technology used: those with fixed bed reactors and
There have also been new developments in the those with expanded (or ebullated) bed reactors.
configuration of catalytic cracking, for example, in the The plant layout, where fixed bed reactors are
one perfected by UOP in conjunction with BAR-CO used, generally consists of three or more reactors in
Industries, which features a very low contact time series and a fractionating section where the reactor
(MSCC MilliSecond Catalytic Cracking). effluents are separated by atmospheric and vacuum
The reduced contact time minimizes the formation distillation. The liquid feedstock must be filtered
of gas and coke; this solution makes it possible to feed before being mixed with the hydrogen and sent to the
the plant with feedstocks (residues) with a higher reactors in order to eliminate the particles of solids
content of carbon residue. New catalysts have also present and prevent them from being deposited onto
been formulated which are more resistant to poisons the catalytic beds. The flow through the reactors is of
(nitrogen and metals such as nickel and vanadium). the downward type (from the top towards the bottom).
To maintain a satisfactory level of catalyst activity The liquid feedstock and the hydrogen are heated
circulating within the plant, provision is made for a up in two separate furnaces until they have reached the
greater quantity of fresh catalyst to be fed in with a required reaction temperature.
corresponding withdrawal of spent catalyst. The fresh One particular innovation developed by Chevron
catalyst make-up will also compensate for the loss of for fixed bed technology consists of adding an
catalyst fines which are not trapped by the cyclones. Onstream Catalyst Replacement system (OCR) which
Moreover, additives (passivators) have been developed makes it possible to replace part of the catalyst even
to reduce the deactivation effect of the catalyst caused while the plant is kept in operation. This configuration
by the presence of metals. The second improvement consists of the addition of a reactor upstream of the
made by UOP goes under the name of X DESIGN. A normal reaction train that has an upward flow (from
vessel is added between the reactor and the regenerator the bottom to the top) and special internals that allow
in which the spent and the regenerated catalyst are the removal of the spent catalyst and the addition of
mixed at a temperature below that of the regenerated fresh catalyst from the top of the reactor. Handling of
catalyst. The overall result is a reduction in the thermal the catalyst is made possible by a special system.
reactions in the riser. Its extreme sensitivity to high concentrations of
To sum up, the improvements enable the catalytic poisons makes fixed bed technology particularly
cracking process to be used for the conversion of suitable for treating the atmospheric residues from
relatively heavy feedstocks, even though fairly strong conventional crudes, but not suitable for feedstocks
constraints persist regarding the feedstock’s content of produced from non-conventional oils.
metals and carbon residues that limit its use for the In a similar way to fixed bed hydrocracking, the
treatment of non-conventional oils. flow scheme with ebullated bed reactors is also
generally made up of two or three reactors in series
with a fractionating section where the reactor effluents
2.5.5 Hydrogen addition are separated by atmospheric and vacuum distillation.
technologies: hydrocracking Also in this arrangement, the liquid feedstock and
the hydrogen are heated up separately to the reaction
Technologies with supported catalysts temperature, and the flow through the reactors is of the
As mentioned, the application of hydrocracking upward type. The liquid flow, which will allow the
technologies to the upgrading of non-conventional oils catalyst to be expanded (ebullated), is ensured by a
can be strongly affected by the presence of metals and pump that re-circulates part of the liquid collected in
carbon residue in the feedstock to be treated. These the upper portion of the reactor. The recycle pump can

feedstock and from a mixture of Mexican crudes with

Table 10. Product yields and qualities from ebullated bed a more than 60% Maya content.
Mexican Technologies with catalysis in dispersed phase

Feedstock Athabasca
blend (slurry)
TBP cut 540°C+ * 538°C+ * These hydrotreatment technologies use
non-supported hydrogenation catalysts finely
API gravity 1.9 1.5 dispersed in the substrate to be hydrogenated. These
Sulphur (weight %) 5.89 4.7 catalysts consist of transition metals sulphide and
therefore have no acidic actions, as a result of which,
Product yields (weight %) the conversion (cracking) remains purely thermal.
Hydrocarbon gases C1-C4 8.6 8.6 The development of hydrogenation technologies
with dispersed catalysts in the field of upgrading
Naphtha 5.6 5.6 heavy hydrocarbon feedstocks can be traced back to
Atmospheric gasoil 14.2 14.2 Friedrich Bergius who, in the 1930s, developed
processes for the hydrogenation of heavy crudes and
the direct liquefaction of coal in which the catalysts
Vacuum residue 43.2 43.2 consisted of a mixture of Fe, Al and Ti oxides (see
Chapter 2.4). Subsequently, many other catalysts based
Distillate characteristics
on Fe, Mo and, in general, metals of the VIII group
API gravity 29.1 29.3 have been proposed and used, even though
microcrystalline molybdenite generated from
Sulphur (weight %) 0.20 0.16
oil-soluble precursors remains by far the most efficient
Vacuum residue characteristics catalyst. As mentioned earlier, these catalysts are not
very sensitive to poisons and, therefore, do not present
API gravity 5.9 6.0
problems of deactivation through the deposition of
Sulphur (weight %) 1.6 1.3 coke and metals on the pores of the support. That
makes them of particular interest when processing
Metals (ppm) 290 393
feedstocks which have very high concentrations of
* This
is a way of indicating the fraction of distillates that boils metals, sulphur, nitrogen and asphaltenes.
above the temperature indicated. The main limitation of dispersed catalysts is
undoubtedly the difficulty of recovering them from the
be installed directly on the bottom head of the reactor unconverted residue. Consequently, the cheapest
or even outside the reactor. catalysts have almost always been preferred
Part of the catalyst contained in the reactors is (particularly those based on Fe), or solutions that use
replaced on a daily basis in order to keep the activity more active materials, but in low concentrations, to
constant. avoid the separation phase and recovery from the
There are two different technologies available on unconverted product. In both cases, the level of
the market: the first, that keeps its original name upgrading of the products is medium-low. This
H-Oil, was originally developed by HRI and then problem has strongly influenced the development at an
purchased by Axens, while the second, called industrial level of all the technological solutions based
LC-Fining, was developed by ABB Lummus Global. on the use of catalysts in dispersed phase, which are
Subsequently, ABB Lummus Global made a strategic classified according to the nature of the catalyst, the
alliance with ChevronTexaco to develop and market configuration of the reactor, the method of recovery
the technology. and recycling of the catalyst, etc. Some of these
Unlike fixed bed technology, ebullated bed solutions have reached the point of demonstration in
technology is suitable for treating feedstocks with a pilot or pre-industrial plants, but until now, no real
high content of contaminants and, as such, is used to plants have been set up at an industrial level (SFA
process vacuum residues even from particularly heavy Pacific Inc., 2003).
feedstocks. Furthermore, this solution displays a high
degree of flexibility for feedstocks coming from VEBA CombiCracking process (VCC)
different crudes, provides almost constant yields and This process has resulted from the German
product quality, and has high operational flexibility. industry’s decades of experience in the field of
Table 10 shows product yields and qualities obtainable high pressure hydrogenation of heavy
by processing vacuum residues from a Canadian hydrocarbons feedstock and coal. The heart of the

process is a slurry reactor where cracking and 43% and vacuum gas oil (VGO) 36%. The distilled
hydrogenation reactions take place in liquid phase products, however, have to be reprocessed, whereas the
(LPH, Liquid Phase Hydrogenation) at high residue is incinerated to recover the catalyst.
temperature (450-490°C) and pressure (over 250 The process, initially developed by Intevep using
bar), and in the presence of a catalyst/additive two sizes of pilot plant of 0.3 and 3 bbl/d, was later
based on iron/coal that limits the formation of coke developed on a larger scale (150 bbl/d plant) using the
and favours metal removal. This unit is integrated VEBA Oel facilities in the Bottrop refinery where,
with a fixed bed reactor operating in gas phase from 1986 to 1988, several trial campaigns were
(GPH, Gas Phase Hydrogenation) for further conducted for over 7,000 hours using Morichal crude.
hydrogenation of the products. In the most recent version, called HDHPlus, the
The VCC technology was developed to the point of catalyst also contains Mo incorporated on coke used as
a demonstration plant of 4,000 bbl/d at Ruhr Oel’s a support, so as to improve the degree of dispersion
Bottrop refinery. This unit operated for several years and to make it easier to separate it from the heavy
(1988-1993) processing different feedstocks (residues, residue (pitch) after the reaction.
heavy crudes, coal and plastic residues) and was then Later, in the period 1992-1997, a survey was
dismantled in February 2000. At the moment, no carried out to set up an industrial plant of 15,000 bbl/d
further developments of the technology are capacity at the Venezuelan Cardon refinery to process
anticipated, also because of issues related to the the heavy crude from the Orinoco Belt.
incorporation of VEBA Oel by BP.
Canmet process
HDH and HDHPlus processes The process was initially studied by NCUT (the
The HDH process (Hydrocracking-Distillation- National Center for Upgrading Technology) in the
Hydrotreating) was developed by Intevep-PDVSA in 1970s and was later developed by Petro-Canada and
the 1980s and its scheme follows a similar pattern to SNC-Lavalin. The hydrocracking reactor is an empty
the VEBA CombiCracking process. Compared with vessel in which the feedstock is processed in the
the latter, HDH works at relatively less severe presence of an Fe sulphide based catalyst deposited on
conditions, that is, at a temperature of 420-480°C, 130 particles of coal. Because the desulphuration activity
bar pressure, space velocity (WHSV, Weight Hourly of Fe is very low, Mo can be added at a level of tens of
Space Velocity) of 0.4-0.8 h-1, and using an Fe ppm in the form of naphthenate.
sulphate as the catalyst. The reaction products are fractionated and sent to
The performances reported indicate maximum the hydrotreatment unit (Unifining and Unicracking),
conversion into distillates of around 95% broken down while the unconverted residue (5-10% of the
as follows: naphtha 21%, atmospheric gas oil (AGO) feedstock) can be burnt or gasified.
The performances recorded in the treatment of
Canadian bitumen for different degrees of conversion
Table 11. Canmet process performance. Feedstock under the typical reaction conditions of the
treated: Cold Lake vacuum residue hydrocracking unit, that is temperature of 400-490°C,
pressure up to 140 bar and LHSV ( Liquid Hourly
Conversion 525°C⫹ * (weight %) 84.2 93.5 Space Velocity) in the range of 0.5-2 h⫺1, are shown in
Table 11.
Product yields (weight %)
In 1986, a demonstration unit with a capacity of
Hydrocarbon gases C1-C4 9.3 11.5 5,000 bbl/d was set up at the Montreal refinery which
is still working.
Naphtha 15.8 19.8
Atmospheric gasoil 29.1 33.5 Microcat-RC process
The process, originally called M-Coke, was
developed by Exxon during the 1980s and 1990s up to
Upgrading feedstock the present configuration which consists of:
% HDS 62 70
• A hydrocracking stage in the presence of
molybdenum based micronic catalysts supported
% HDN 31 41 on coal particles in dispersed phase (slurry); the
Hydrogen consumption (weight %) 1.6 2.5
reaction is carried out in a reactor that operates
within a temperature range of 440-470°C, at a
* This
is a way of indicating the fraction of distillates that boils hydrogen pressure that can reach 170 bar, with
above 525°C. LHSV in a range from 0.5 to 2 h⫺1.

Fig. 10. Flow sheet recycle wash water

for (HC)3 technology gas lean amine
⫺370°C
(Lott and Lee, 2002).
fuel gas
hot separator
feed
SCO
hydrotreater
mixed feed
vacuum
tower
reactor
⫹370°C
H2S rich amine
conditioning
recycle
precursor gas sour water
catalyst
recycle
make-up recycle
H2 gas residue
• The separation of the reaction products through levels (of the fraction that boils above 500°C) into gas,
flash and vacuum distillation to obtain a distillate light distillates and heavy distillates can be obtained
with a high yield of the fraction that boils below up to 95%.
560°C and to produce a residue in which the The process was developed at a pilot plant level of
catalyst and all the metals contained in the 1 bbl/d (Fig. 10). During 2002, a patent agreement was
feedstock are concentrated (this residue can be reached between ARC and Hydrocarbon Research, a
burnt or gasified). company controlled by Headwaters, to develop and
• The hydrotreatment of the distilled fraction in a market the (HC)3 technology.
fixed bed reactor for the finishing of the products
that are subsequently fractionated into naphtha, Eni Slurry Technology (EST) Process
atmospheric gasoil and vacuum gasoil. The Eni Slurry Technology (EST) process was
This process can reach conversions of up to 95% developed recently by Snamprogetti and
with a typical product distribution of naphtha 10-15%, EniTecnologie, both companies of the Eni Group
AGO 45-55% and VGO 30-40%. It was tested at a pilot (Montanari et al., 2003). Unlike the technologies
plant level of 8 bbl/d at the beginning of the 1990s, but available today, EST operates in such a way as to
there have been no further developments of the permit the almost complete conversion of heavy
technology even though ExxonMobil remains active in petroleum feedstocks into distillates and avoid the
the field, at least judging by the patents being filed. production of fuel oil and coke.
(HC)3 process distillates

The process called (HC)3 (High DAO
Conversion/Hydrocracking/Homogeneous Catalyst)
was developed at the end of the 1980s by the Alberta
Oil Sands Technology & Research Authority
fractionator
reactor
(AOSTRA) and the Alberta Research Council (ARC).

SDA
The upgrading reaction is carried out in the

presence of a catalyst defined as ‘colloidal’, formed in
situ starting with oil-soluble precursors such as iron
pentacarbonyl or molybdenum 2-ethylhexanoate and, if
necessary, by an aromatic diluent to prevent asphaltene
precipitation. The conversion product is fractionated feedstock
under vacuum and the residue can be recycled. asphaltene recycle and catalyst purge
The operating conditions of the hydrocracking unit hydrogen
call for a reference temperature of around 450°C and a Fig. 11. Flow sheet for EST technology
pressure of 140 bar. Also for this process, conversion (Montanari et al., 2003).

Table 12. EST process performances
Feedstock Zuata Maya Athabasca Bitumen

TBP cut 530°C⫹ * 500°C⫹ * 300°C⫹ *
API gravity 2.5 1.5 7.9
Sulphur (weight %) 4.2 5.2 4.6
Product yields (weight %)
Hydrocarbon gases C1-C4 15.1 9.9 12.9
Naphtha 14.0 3.9 4.1
Atmospheric gasoil 39.1 26.9 39.1
Vacuum gasoil 23.3 34.9 32.1
DAO 8.5 24.4 11.8
Products Upgrading
% HDS 86 84 83
% HDN 59 52 47
% HDM ⬎99 ⬎99 ⬎99
% removal of CCR 98 96 95
* This is a way of indicating the fraction of distillates that boils above the temperature indicated.
The heart of the process consists of a hydrotreating The process proved extremely flexible in treating
(HT) reactor in which the heavy crude feedstock different types of heavy feedstocks, such as vacuum
undergoes a hydrogenation treatment in relatively mild residues from conventional crudes (Ural and Arabian
conditions (410-420°C and 160 bar), limiting the Heavy), heavy crudes (Maya) and extra heavy crudes
conversion per pass to distillates, but ensuring a (from Orinoco), as well as bitumens from oil sands
satisfactory margin of stability for the unconverted (Athabasca). In all cases, the technical validity of the
residue. The hydrotreatment is carried out in the process was confirmed, especially regarding the
presence of several thousand ppm of a molybdenum catalyst life, the recyclability of the asphaltenes and
based catalyst finely dispersed in the liquid mass so as the minimum amount of purge stream needed to
to promote the upgrading reactions (metal removal, prevent the accumulation in the plant of the metals
desulphuration, denitrogenation and reduction of the contained in the feedstock. The EST process enables
carbon residue). The hydrotreated products leaving the an almost complete conversion of the feedstock
HT unit are sent to a fractionating section to recover (⬎95%) and guarantees an excellent level of
the distillates. The unconverted residue from the upgrading of the products (Table 12). The technology
bottom of the fractionating column is then sent to a is in an advanced phase of development in a
solvent deasphaltating section (SDA) to recover the commercial demonstration plant of 1,200 bbl/d inside
deasphalted and demetallized oil (DAO), while the the battery limits of an Eni refinery.
asphaltene stream that contains all of the catalyst is
recycled to the HT section to be reprocessed together Other processes
with additional fresh feedstock (Fig. 11). After a In addition to the processes discussed above, there
number of recyclings, a stationary steady-state are other industrial initiatives that broaden the range of
condition is reached that makes it possible to obtain technologies potentially available, even though at the
almost total conversion levels, overcoming the moment, they are in the early stages of development.
traditional limitations of the classical conversion Among these, there is the Hydrogen Transfer
processes, i.e. the loss of stability of the reaction Cracking process, developed by Toyo Engineering
products and, consequently, the deposition of coke. Corporation (Japan) in the early 1990s. It is based on
The technical validity of the EST process was the use of iron catalysts on active coals that act so as to
demonstrated through an experimental activity adsorb and desorb the radicals produced by the
conducted at a pilot plant level of 0.3 bbl/d capacity. cracking, thus preventing the formation of coke. The

process operates at relatively low pressures (70-100 formulation seems particularly suitable for facilitating
bar) but, nevertheless, makes it possible to obtain good nitrogen removal. The process also foresees recycling
levels of upgrading even when processing very heavy of the catalyst from the bottom of the distillation
feedstocks, such as vacuum residues from Arabian column. The operating conditions reported by Chevron
Heavy and Maya or the extra heavy Cerro Negro. The cover a very wide range of conditions: temperature
performances reported indicate maximum conversions 400-480°C, pressure 95-130 bar and concentration of
of between 85 and 90%, with good levels of upgrading the catalyst which can go up to 10,000 ppm from 500
(HDM and HDS around 95 and 80%, respectively). ppm. Development of the CASH process is currently
Toyo recently reached an agreement with the Instituto at the stage of a small pilot plant (0.1 bbl/d).
Mexicano del Petróleo (a company affiliated to Finally, the technology called GNO-V, proposed by
PEMEX) to build a demonstration unit at Tula. Genoil, is also in the development stage at a pilot plant
Another process proposed by Nikko Consulting level. The hydrogenation process operates with
and Engineering Corporation is the Succeed Process catalysts in slurry phase at 400°C and 130 bar, and
that operates in two stages: hydrocracking of the makes it possible to upgrade Canadian bitumen,
feedstock with catalysts in slurry phase using a raising the specific gravity from 7 to 28°API, with
dispersed catalyst based on transition metals to obtain yields in volume above 100% and reductions of
a conversion of 60-65%; coking of the part that has sulphur from 5 to 0.2%. In recent years, Genoil has
not reacted so as to reach a total conversion of 85%. finalized agreements with Syneco Energy (a Canadian
The Japanese company is planning to build a company owning reserves of non-conventional oils
demonstration unit of 5,000 bbl/d. and coal) and ConocoPhillips to carry out
The CASH process (Chevron’s Activated Slurry demonstration tests on a 6 bbl/d pilot unit, the
Hydrocracking), proposed by ChevronTexaco, is the construction of which was started in January 2003 at
result of a long period of research activity carried out Two Hills (Alberta, Canada).
in the 1980s and recently restarted. CASH is based on
the use of a dispersed catalyst based on molybdenum
in the presence of nickel as a promoter. This catalytic 2.5.6 Technologies for the
exploitation of oil shale
The first utilization of oil shale goes back to
seventeenth century, when, in Sweden, this rock was
roasted to extract sulphates for use as dyestuff. The
first exploitation for energy usage, however, is dated at
about the middle of the Nineteenth century with the
starting up of mines and the first processing plants in
Pennsylvania which were developed in the following
century (Fig. 12).
In recent decades, the exploitation of oil shale has
been concentrated in just a few countries, reaching a
peak of 45 million t/a worked in 1980; assuming a yield
in oil of 10%, that equates to an annual production of
about 4 million t. In the two following decades, this
figure fell significantly, to the extent that in 2002 the
worldwide production of oil from shale (therefore
called shale oil) was less than 600,000 t. The country in
which, by far, the greatest consumption of oil shale was
recorded is Estonia, where even today, a good part of
their energy needs are met from this source; in this
case, however, the oily mineral is used almost
exclusively as fuel in fossil-fuelled power stations.
The traditional technologies for the exploitation of
oil shale involve three principal phases: the recovery
of the mineral in mines; its thermal treatment for the
Fig. 12. Shale oil retorting furnace production of gas and crude oil; hydrotreatment
with a capacity of 200-330 t/d built in the United States (upgrading) of the liquids up to the production of
in the 1940s (USBM). distillates for the fuel market.

Recovery of the oil from the rock in which it is methane and heavier hydrocarbons, and can be used
contained passes through a treatment of pyrolysis for the production of hydrogen needed for the
carried out at high temperature for which different upgrading processes or as fuel gas.
solutions have been developed over the years (Johnson The mineral residue, generally waste material, has to
et al., 2004). be transported back to the mine or dumped in a rubbish
The process, known as retorting, starts at 200°C, tip. In some cases, depending on the nature of the
finishing at higher temperatures (500-600°C), and is feedstock and the method of pyrolysis, the mineral
carried out in reactor vessels called retorts. residue may still contain a considerable quantity of
The main objective in the design of a retort is to organic material and can, therefore, be burned to supply
heat at low cost by using as little energy as possible. heat for the process. Similar to what takes place in
There are different types of retorts distinguished by coking furnaces, the pyrolysis reaction, in fact, produces
the way the heat is applied to the crushed oil shale: a sort of disproportionation of the hydrocarbon matrix,
retorts heated indirectly by gas; retorts heated directly producing a liquid enriched with hydrogen and a carbon
by gas by internal and external combustion; retorts residue (coke) that remains in the mineral.
heated directly by solids (Matar, 1982). The product generated from the retorting of oil
In the first type of retort, the heating comes from shale is a dark, viscous liquid with a high content of
outside and the heat is applied through a wall, heteroatoms and unsaturated compounds produced
generally of cast iron. Because of its limited capacity during the pyrolysis. Compared with heavy crudes or
and the low thermal efficiency of the method, this type bitumen, the liquids from oil shale display a high
of retort has not been developed further. The second concentration of hydrocarbon structures with a high
type uses hot gases that pass directly through the oil H/C ratio, owing to the fact that the initial kerogen
shale, usually in a vertical furnace (Union B Process contains a high percentage of paraffin structures.
developed by Unocal). The gases can be generated The distribution of the distillates in shale oils is
through the combustion of a portion of the linked to the retorting technology used but, in general,
hydrocarbons produced within the retort (internal it is similar to that of the products from the coking of
combustion) or by partial gasification with air and petroleum residues.
steam at 800-850°C of the carbon residue that remains As regards the heteroatom content, shale oils are
on the mineral after the pyrolysis treatment (SGR characterized by the fact that, in addition to sulphur,
technology, Stream Gas Recirculation). This is a low they contain significant quantities of oxygen and
cost method, but its yield in hydrocarbons is nitrogen. The pyrolysis liquids can include several tens
correspondingly low. In the third type of retort, of ppm of metals and, amongst these, iron in
preheated solid carriers, for example ceramic balls 0.5 particular, but also traces of nickel, vanadium and
inch (1,27 cm) in diameter, are mixed with the oil arsenic; the last element can create serious
shale and provide the heat necessary for the pyrolysis. contamination problems for the hydrogenation
The first process carried out using this solution, catalysts. In fact, the upgrading of shale oils to
known as TOSCO (The Oil Shale Corporation) II, was produce fuels has its roots in the classic technologies
developed at the end of the 1960s by a consortium of developed in the field of petroleum refining and, in
several companies. It uses a rotating reactor operating particular, hydrotreatments.
at 500°C that is fed continuously with the mineral, and An alternative solution to convert the oil shale into
involves a rather complex system of circulation of the liquids is known as in situ conversion. This type of
carrier, but offers advantages in terms of the oil yield. technology was initially put forward in the USA around
A conceptually similar technology was later the 1960s by several mining companies, among them in
developed by UMA Engineering (Alberta Taciuk particular, Occidental Oil Shale. The idea was to inject
Process, ATP), and is currently considered the air and steam into the deposit, causing partial
reference technology for this type of application. In combustion of the organic material (in situ combustion)
this process, the mineral is first pyrolyzed in a rotating and, therefore, the heating up of the formation, reaching
oven in order to produce oil (500°C) and is then sent temperatures of 700-800°C (Braun et al., 1984). In this
to a second combustion furnace where the organic way, the pyrolysis process is carried out directly in the
material which has not reacted is burnt (750°C), deposit, from which the conversion products can then
before being partially returned into circulation so as to be recovered using appropriate production wells. With
recover the heat needed for the retorting. the aim of optimizing the technology, several solutions
The gas produced during the retorting consists have been proposed that relate, above all, to the deposit
mainly of carbon monoxide and carbon dioxide, as a exploitation methods, i.e. the layout of the injector and
result of the release of most of the oxygen present in producer wells, but the different trials have always
the initial kerogen, hydrogen, hydrogen sulphide, experienced serious difficulties in controlling the

combustion front and, hence, in guaranteeing a industrial exploitation of non-conventional oils.

reasonable level of productivity of the oil. A different As far as extra heavy crudes are concerned, in
approach is currently being evaluated that provides for Venezuela four projects for exploitation of the crudes
the boring of a series of vertical wells into the oil shale from the Orinoco Belt have been carried out for a total
deposit, which are then heated either electrically, or by of 634,000 bbl/d, with production of 573,000 bbl/d of
means of superheated steam, or using the hot gases synthetic crude with API gravities varying from 16 to
produced by partial combustion of the organic material. 32. Negotiations are taking place with the Venezuelan
In this way, the formation is brought up to a temperature state oil company (PDVSA) for an increase in
in the order of some hundreds of degrees Celsius and production to about 2 million barrels a day by
kept in this condition for several years. The high 2010-2012. Table 14 shows the most significant data
temperature accelerates the natural process of relating to these projects.
degradation of the kerogen into oil (at about 300°C, the In Canada, in the province of Alberta, about 1.1
degradation kinetics of kerogen increase significantly; million bbl/d of oil sands are treated annually to
Lewan et al., 1979) that can then be extracted like produce, in part, synthetic crudes and, in part, diluted
traditional crude from a production well. The bitumen with a diluent (consisting generally of
conversion yields are lower than that which could be naphtha) in order to reduce its viscosity to enable it to
obtained with traditional retorting (about 20% in weight be pumpable to allow transportation. An updated list
compared to the organic material), but the quality of the of the main industrial projects is shown in Table 15.
oil produced is decidedly superior, as shown in Table 13 Finally, as far as oil shale is concerned, at an
and, above all, the environmental problems linked to international level, there are several research and
recovery of the mineral and disposal of the processing development initiatives aimed at experimenting
residues are significantly reduced. solutions for its exploitation, particularly in Canada,
Australia, China, Russia and Israel, but applications at
an industrial or demonstration level are still very limited.
2.5.7 Main development projects Amongst these, a project worthy of note is the one
being run by two Australian companies, Southern
At present, there are numerous projects (started or at Pacific Petroleum NL and Central Pacific Minerals
an advanced stage of development) relative to the NL who, in 1995, signed an agreement with the
Table 13. Comparison of product yields and qualities when processing American oil shale
by means of different processes
Traditional retorting TOSCO process Union Oil process Shell ICP process
Oil characteristics
API gravity 19.8 21.2 18.6 38
H/C 1.63 1.64 1.70 1.84
Sulphur (weight %) 0.7 0.9 0.9 0.5
Nitrogen (weight %) 2.1 1.9 2.0 1.0
Oxygen (weight %) 1.6 0.8 0.9 0.5
Bromine number* 33 49 n/a n/a
Ni ⫹ V (ppm) 10 9 5 2
Fe (ppm) 108 100 55 9
Distillate distribution (volume %) **
C5-230°C 11 23 5 45
230-343°C 25 21 25 39
343-554°C 54 56 70 16
554°C⫹ 10 – – –
* The bromine number is a parameter that quantifies the olefin content in a hydrocarbon cut.
** The distillates are divided into groups starting with pentanes through to hydrocarbons which boil at the temperatures indicated.

Table 14. Projects for the exploitation of extra heavy Venezuelan crudes
Petrozuata Cerro Negro Sincor Hamaca

Operator Petrozuata ExxonMobil Sincor Petrolera Ameriven
ExxonMobil 41.7 Total 47 ConocoPhillips 40
ConocoPhillips 50.1
Percentage participation PDVSA 41.7 PDVSA 38 PDVSA 30
PDVSA 49.9
BP 16.6 Statoil 15 ChevronTexaco 30
Reserves (gbbl) 1.4 1.4 2.3 2.2
Total CAPEX (billions of dollars) 3.9 2.0 4.6 4.5
Upgrader CAPEX
1.5 0.7 2.5 2.0
(billions of dollars)
Production of heavy oil
120,000 120,000 204,000 190,000
into upgrader (bbl/d)
Syncrude production
108,000 105,000 180,000 180,000
out of upgrader (bbl/d)
Syncrude density (°API) 20-26 16 32 26
Delayed coking Delayed coking
Delayed coking Delayed coking
Upgrader technology Hydrocracking Hydrocracking
Naphtha hydrotreating Naphtha hydrotreating
Hydrotreating Hydrotreating
Table 15. Main Canadian projects for the industrial exploitation of non-conventional oils
Cost
Company Project Capacity (bbl/d) Status Start-up
(millions of dollars)
Shell Canada, Chevron Canada
Muskeg River 155,000 5,700 Operative 2003
and Western Oil Sands
Syncrude Canada Aurora 140,000 5,000 Under construction 2005
Suncor Energy Inc. Firebag 105,000 2,100 Under construction 2007
Petro-Canada Meadow Creek 80,000 800 Proposed 2007
Nexen Petroleum & OPTI
Long Lake 30,000 2,600 Proposed 2007
Canada
Imperial Oil Nabiye 30,000 1,000 Proposed 2006
TrueNorth Energy
Fort Hills 95,000 3,500 On hold ?
& UTS Energy
Japan Canada Oil Sands Preliminary proposal
Hangingstone 35,000 250 2007
Ltd. filed
Husky Energy Inc. Tucker Lake 30,000 350 Proposed 2006
EnCana Corp. Christina Lake 70,000 900 Pilot 2007
Devon Canada Corp. Jackfish 35,000 400 Preparing proposal 2007
Preliminary proposal
Syneco Energy Northern Lights 80,000 3,500 2007
filed
ConocoPhillips Canada,
Surmont 100,000 1,000 Proposed 2006
TotalFina & Devon Energy
Canadian Natural Resources
Horizon 232,000 8,000 Proposed 2011
Ltd.
Deer Creek Energy
Joslyn Creek 40,000 450 Preparing proposal 2008
& Enerplus Resources Fund
Black Rock Ventures Hilda Lake 20,000 260 Proposed 2005

Canadian company, Suncor Energy, aimed at Dyni J.R. (2004) Oil shale. World energy council, in: Survey
exploiting the Australian deposit known as Stuart. The of energy resources 2004, Amsterdam, Elsevier.
first phase of this project was completed in 1999 with IEA (International Energy Agency) (2004) World energy outlook
2004, Paris, Organization for Economic Cooperation and
the creation of an industrial complex for the treatment
Development/IEA.
of 6,000 t/d of mineral, from which 4,500 bbl/d of a Johnson H.R. et al. (2004) Strategic significance of America’s
light oil (42°API) with a sulphur content of 0.4 oil shale resource, 2v.: Volume II: Oil shale resources,
weight % and a nitrogen content of 1 weight % is technology and economics, US DOE Office of naval
produced. The processing technology used for petroleum and oil shale reserves.
extraction of the oil is the previously mentioned Lewan M.D. et al. (1979) Generation of oil-like pyrolysates
Alberta Taciuk Processor (ATP). from organic rich shales, «Science», 203, 897-899.
In Estonia, there are currently three retorting Lille Ü. et al. (2003) Molecular model of Estonian kukersite
kerogen evaluated by 13C MAS NMR spectra, «Fuel», 82,
installations in operation that produce 8,000 bbl/d of 799-804.
liquid. Looking to the future, the private chemical Long R.B. (1979) The concept of asphaltenes, in: Proceedings
company, Viru Keemia Grupp (VKG), has plans for of the 178th meeting of the American Chemical Society,
the setting up of a 4 million bbl/a plant for distillates Washington (D.C.), 10-11 September, 891-900.
(naphtha and diesel) whose profitability would be Lott R., Lee L.K. (2002) Upgrading of heavy crude oils and
increased by the possibility of extracting oxygenated residues with (HC)3TM hydrocracking technologies,
Lawrenceville (NJ), Hydrocarbon Technology Inc.
derivatives for the chemical industry (in particular,
Matar S. (1982) Synfuels. Hydrocarbon of the future, Tulsa
phenols and cresols) from the pyrolysis oil. (OK), PennWell.
Finally, it should be remembered that in Brazil, one Montanari R. et al. (2003) Production of ULS fuels from
of the biggest retorting plants is already in operation heavy feedstocks, «Petroleum Technology Quarterly»,
using gas combustion (Petrosix), through which 3,870 Winter, 61-67.
bbl of liquid are produced daily. Murgich J. et al. (1996) Molecular recognition and molecular
As far as the in situ conversion process is mechanics of micelles of some asphaltenes and resins,
«Energy & Fuels», 10, 68-76.
concerned, in the last fifteen years, several studies and
Panariti N. et al. (2000) Petroleum residue upgrading with
tests have been carried out in the field to optimize the dispersed catalysts. I: Catalyst activity and selectivity,
technology. Particularly worthy of note is the work that «Applied Catalysis A. General», 204, 203-213.
is being carried out by Shell on the development of the Perrodon A. et al. (1998) The world’s non-conventional oil
technology referred to as ICP (In situ Conversion & gas, «Petroleum Economist», March.
Process), which is in an advanced experimentation SFA Pacific Inc. (2003) Upgrading heavy crude oils and
phase in the Piceance Creek basin in Colorado, while a residues to transportation fuels. Technology, economics,
new project has been announced in Jilin province in and outlook. Phase 7, Multisponsored reports, Petroleum
processing program, SFA Pacific Inc., 4, 39-48.
North East China.
Sheremata J.M. et al. (2004) Quantitative molecular
representation and sequential optimization of Athabasca
asphaltenes, «Energy and Fuels», 18, 1377-1384.
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processing, «CHEMTECH», November, 35-43. San Donato Milanese, Milano, Italy

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2.

Table 1. Classification of non-conventional oils

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recoverable only through thermal processing of the

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Table 3. Principal compositional characteristics of heavy crude oils and bitumens

Distillation yield (% by weight)

Vacuum residue characteristics

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degrees and distributed across a wide range of C5 asphaltene

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Fig. 5. Representation of the molecular structure of kerogen (Lille et al., 2003).

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Contrary to what happens with delayed coking, the

Coking Table 8. Product yields and qualities from delayed coking

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contaminants distribution (%)

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feedstock and from a mixture of Mexican crudes with

Mexican Technologies with catalysis in dispersed phase

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Fig. 10. Flow sheet recycle wash water

(HC)3 process distillates

(AOSTRA) and the Alberta Research Council (ARC).

The upgrading reaction is carried out in the

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Table 12. EST process performances

Feedstock Zuata Maya Athabasca Bitumen

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combustion front and, hence, in guaranteeing a industrial exploitation of non-conventional oils.

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Petrozuata Cerro Negro Sincor Hamaca

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