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2.

Emerging technologies for the conversion of residues

2.5.1 Introduction
Around the world, there are major reserves of the so called non-conventional crude oils, that is to say, heavy crudes and bitumens that are recoverable from oil shale and oil sands bitumen, and which form a strategic reserve to supplement the crudes with which we are familiar and which are identified as conventional crude oils. Even though there is no universally recognized definition, normally these fossil sources are classified on the basis of the API gravity and viscosity values at the reservoir conditions (Table 1). According to this classification, heavy crudes are defined as oils with an API gravity of less than 25. Among them, those with a viscosity greater than 10,000 mPas are classified as extra-heavy; in general, their gravity is less than 10API, which indicates that they have a higher density than water. Bitumens extractable from bituminous sand, better known by the term oil sands bitumen, also fall into this category, as well as the oil produced through heat treatment of oil shale. From a geological point of view, a large part of the heavy crudes derive from mature oils which, after

having been expelled from the source rock, migrated into permeable layers of rock where they were able to undergo a series of degrading processes, such as attack by micro-organisms, evaporation or washing out of the light fractions, which resulted in the concentration of the heavier component of the oil. A common characteristic of the greater part of heavy oils is their presence in fluvial basins relatively close to the surface, as in the case of the Orinoco basin in Venezuela (Orinoco Belt). The estimated reserves of heavy crudes and oil sand bitumens amount to around 5,000 Gbbl. Considering also that the technically recoverable fraction is in the range 15-20%, it is evident that we are talking about enormous quantities if one considers that the whole of the Middle East has reserves of 2,000 Gbbl, of which 683 is considered to be recoverable (IEA, 2004; Perrodon et al., 1998). The greater part of these reserves is concentrated in Canada in the province of Alberta and in Venezuela in the above-mentioned Orinoco Belt. A third country which is rich in non-conventional oil is Russia, even though in this case, the data for establishing the quantities of these reserves and the types of oils are much more uncertain (Table 2).

Table 1. Classification of non-conventional oils Specific gravity (API) Heavy crude oils Extra-heavy crudes Bitumens from tar sand Oil shales 16-25 10 7-12 10 Viscosity (Pa s) Rheologic characteristics of oil at reservoir conditions Mobile Mobile Non-mobile Impermeability of the source rock

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Table 2. Main deposits of bitumens (1) and heavy crude oils (2) Technically recoverable (Gbbl) 315

Deposits of bitumens and heavy crudes

Reserves (Gbbl)

Depth (m)

API

Canada Athabasca1, Cold Lake1, Peace River1, Lloydminster2 Venezuela2 Orinoco Belt (Cerro Negro, Zuata, etc.), Bachaquero, Boscan Russia1 Siberian platform, Malekess

1,630

0-750

8-20

1,900

272

1,300

8-11

450

As far as oil shale is concerned, the worldwide reserves are in the order of 2,600 Gbbl; of these, about 2,000 Gbbl are within the territory of the United States and, in particular, in the formations called Green River (Colorado), the Uinta Basin (Utah) and the Washakie Basin (Wyoming). Other significant reserves can be found in Brazil, Australia, China, Russia and Estonia (Dyni, 2004). The exploitation of these fossil reserves is highly strategic inasmuch as it would make it possible to increase the known reserves without recourse to investment in new exploration. Moreover, these resources help to diversify the sources of supply and, given their geographical distribution which locates them predominantly in areas other than the Middle East, to eliminate the geopolitical risks which have been a constant factor in the crude oil marketplace. Production of heavy crudes and bitumens very often involves the use of special technologies developed specifically to handle products which are highly viscous or, as in the case of bitumens, dispersed within sandy mineral groundmasses or, yet again, recoverable only through thermal processing of the organic material contained in sedimentary rocks, as happens with oil shale. In the last 15-20 years, interest in developing the technologies for exploiting non-conventional oils has gone through alternating phases, depending on the favourability, or otherwise, of the macro-economic climate for scheduling investments in this sector (forecasts of the price of crude and of the differential between heavy and light oils). Moreover, expectations about overcoming various technological obstacles connected primarily to the compositional characteristics of these resources often have not been lived up to. Nevertheless, the forecasts of the demand for oil over the next 20-30 years and the pointers which emerge on the availability of reserves of conventional

crude, according to which production will peak over the next ten years (Fig. 1), reinforce the idea that it will be increasingly necessary to make recourse to nonconventional oils, drawing on the reserves of extraheavy crudes and bitumens of Canada, Venezuela and Russia and, thereafter (beyond 2030), on oil shale. These factors are behind a series of industrial initiatives which, over the next decades, could bring significant amounts of synthetic and/or distilled crudes from non-conventional sources onto the market. This is also due to the progressive reduction in production costs resulting from the development/optimization of new technologies, both upstream and downstream. In this regard, the most significant case is certainly that of Canada where the efforts in developing ad hoc technologies for exploiting the oil sands bitumen fields, which began in the 1970s, have made it possible to reduce production costs by more than 50%, making this type of activity commercially viable. It is forecast that in 2010, more than 60% of Canadian production
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oil world production (Mbbl/d)

100 75 50 25 0 1971

1980

1990

2000

2010

2020

2030

existing capacities enhanced oil recoveries development of new discoveries

development of existing reserves non-conventional oils

Fig. 1. Medium-term forecasts for worldwide

oil production (IEA, 2004).

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will come from oil sands bitumen in the form of bitumen itself or synthetic crude oil (SCO), and that will enable it to increase its oil production from the current 2.5 Mbbl/d to over 5 Mbbl/d, making it the fourth biggest producer after Saudi Arabia, Russia and the United States.

2.5.2 Properties and chemical characteristics of non-conventional oils


Heavy crude oils and bitumens

As far as their compositional characteristics are concerned, as with petroleum, heavy crude oils and bitumens are made up of highly complex mixtures of hydrocarbons. Their chemical and chemical-physic (molecular weight, H/C ratio, specific gravity, volatility, etc.) characteristics vary continuously, from the simplest paraffin structure (hydrocarbon gases) to the macromolecules made up of scores of carbon atoms, as well as hetero atoms (sulphur and nitrogen) and metals.

The methodologies developed to determine their characteristics are related to the methods used in oilfields to simplify the mixture, operating in such a way as to separate the fractions with the most homogeneous chemical-physic characteristics possible (Altgelt and Boduszynski, 1993). The primary operation is distillation which enables the fractions to be separated based on their volatility. In this regard, the heavy oils and bitumens have a distillable hydrocarbon content (naphtha and gasoils) which is remarkably lower than that of traditional crudes, such as for example, Arabian Light (Table 3). The different distillation cuts can be further fractionated, based on criteria of polarity and/or molecular weight, by processes with varying degrees of precision according to the complexity of the mixture and depending on the type of information required. In the case of light distillates (naphtha and atmospheric gasoils), chromatographic separation is used to sub-divide the saturated hydrocarbons from the aromatic. For the heavier fractions and the distillation residues which, in the case of the products under consideration, account for the largest quantity of

Table 3. Principal compositional characteristics of heavy crude oils and bitumens Arabian Light Source API gravity Distillation yield (% by weight) Naphtha Atmospheric gasoil Vacuum gasoil Vacuum residue (VR) 20.6 36.0 23.2 20.2 0.0 14.1 31.0 54.9 4.0 11.6 20.2 64.2 12.9 21.7 22.2 42.2 1.5 14.9 38.8 44.8 1.0 13.0 34.0 52.0 Saudi Arabia 33.6 Zuata Venezuela 8.5 Boscan Venezuela 10.5 Maya Mexico 21.5 Cold Lake Canada 10.2 Athabasca Bitumen Canada 7.4

Vacuum residue characteristics TBP cut * API gravity Sulphur (weight %) Nitrogen (weight %) Nickel (ppm) Vanadium (ppm) C7 Asphaltenes (weight %) CCR (weight %)
* The

530C 8.3 4.0 0.25 30 110 5.3 18.0

500C 2.5 4.2 0.97 154 697 19.7 22.1

350C 7.2 6.0 0.96 119 1,473 18.2 18.3

500C 1.5 5.2 0.81 132 866 30.3 29.3

340C 7.2 4.9 0.70 107 210 N/a 20.8

300C 7.8 4.6 0.48 70 186 12.4 13.6

mnemonic TBP (True Boiling Point) indicates that the cut has been carried out in accordance with the procedures indicated in the ASTM standards.

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fractions the commonly accepted analytical protocol involves the preparation of four classes of compounds called: saturates, aromatics, resins and asphaltenes (SARA analysis). Each class can then be analysed to identify its individual components or to evaluate its most important molecular characteristics, depending on the complexity of the mixture and/or the requirements. Compared with traditional crudes, the quantity of saturated hydrocarbons contained in heavy crude oils and bitumens is considerably lower (Fig. 2). From a qualitative point of view, there are major differences due to a lower concentration of n-paraffins in favour of iso-paraffins and naphthenes with a high degree of condensation that very often contain sulphur in their structure. The non-aliphatic component is made up of aromatic and heteroaromatic hydrocarbons with differing degrees of condensation, different alkyl-substitution and functionalization. Even in this case, for the same distillation cut, the hydrocarbon structures display a higher degree of condensation compared with what is seen in conventional crudes. Another characteristic of heavy crudes and bitumens is the fact that they contain significant amounts of heteroatoms (especially sulphur and nitrogen), as well as heavy metals, such as nickel and vanadium in particular. By far, the most common heteroatom is sulphur whose concentration can reach values of 6-8% by weight. Sulphur is distributed in increasing percentages in the products with the highest boiling temperature and is present predominantly as thiophenic sulphur in condensed structures (benzo-,
100% aromatics

conventional crude oils

Athabasca, Canada Cold Lake, Canada Lloydminster, Canada Cherokee, USA

dibenzo- and naphthobenzo- thiophene), but also as aliphatic sulphur in sulphide and disulphide type functional groups. These functionalities are often used to create links between hydrocarbon clusters. Nitrogen, which is contained at levels of 0.5-1% by weight, tends to concentrate in the heaviest fractions on the distillation curve. This heteroatom is found in both basic type (predominantly primary aliphatic and aromatic amines and pyridines) and neutral type (in the form of indoles, carbazoles, imides, as well as porphyrin nitrogen) functional groups. Oxygen is present in the crude, in heavy oils and bitumens in small amounts, about 1.0-1.5 wt% or less and, since it ends up by preference in hydroxylic type groups (phenols, alcohols and carboxylic acids), it concentrates in the most polarized components of the crude such as resins and asphaltenes. Naphthenic acids certainly make up the most researched class of oxygenated compounds, above all because of their corrosive properties. More rarely, the oxygen can appear in the form of ethers or cycloethers, or coupled with other heteroatoms to form sulphoxides and amides. As far as metals are concerned, nickel and vanadium are by far the most abundant elements (up to several hundred ppm), even though some oils can contain significant quantities of sodium, iron and molybdenum. These metals are contained in oil-soluble metallo-organic structures and are concentrated in the heaviest parts of the oil, so much so that they are found in abundance in asphaltenes. A consistent part of the metallo-organic component is the porphyrinic type, but many other structures which are often difficult to identify broaden the case studies of the metal-containing compounds present in asphaltenes. 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 processes, whereas it can drop to values of between 500 and 1,000 ppm where more modern production technologies are used, such as SAGD technology (Steam Assisted Gravity Drainage) in particular.
Chemical and chemical-physic characteristics of asphaltenes

100% saturates

100% resins asphaltenes

Fig. 2. Distribution of the principal hydrocarbon types

making up heavy crudes and bitumens.

The vacuum residues, i.e. the quantitatively greater fraction of heavy crudes and bitumens, mainly consist of aromatic hydrocarbons condensed to varying

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degrees and distributed across a wide range of molecular weights and polarities. They constitute a compositional continuum even though, as mentioned earlier, they are generally divided into aromatics, resins and asphaltenes. The differentiation of these 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 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 the volatile component of the crude oil. In both cases, the constituents of the mixture are divided by defining a cut point, such as the boiling temperature (distillation) or the solubility parameter of the precipitating agent (deasphalting). The solvent strength of the hydrocarbons, or better still, its ability to act as a solvent or anti-solvent in precipitating asphaltenes, can be correlated to the solubility parameter d defined by Joel Hildebrand and Robert Scott as: d DHV 12 111RT V
41 2 2

C5 asphaltene C7 asphaltene

molecular weight

crude oil

polarity
Fig. 3. Representation of the molecular characteristics

of asphaltenes (Long, 1979).

where DHV is the molar enthalpy of vaporization of the hydrocarbon concerned, V is its molar volume, and R and T are the universal constant of gases and the absolute temperature respectively. The solubility parameter may also be estimated by using the equation: d2 AV
41 2 3g

where A is a constant, g is the surface tension and V is the molar volume of the hydrocarbon concerned (Barton, 1991). A very effective bi-dimensional diagram illustrating the molecular characteristics of asphaltenes was suggested by Robert Long (Fig. 3), in which the polarity and molecular weight of the hydrocarbons present in the oil constitute the primary parameters which, depending on the solvent used, determine the precipitation of specific fractions (Long, 1979). In addition, this diagram indicates that asphaltenes must be considered to be a class of compounds which, from a chemical point of view, can be very broad and diverse. As well as the method used during the separation phase, the chemical characteristics of the asphaltenes depend on the crude oil origin. As shown in Table 4,

asphaltenes from different sources vary considerably in their aromaticity, degree and nature of alkyl substitution, as well as the heteroatom content (Cimino et al., 1995). As far as their molecular weight is concerned, the issue is complicated even further because of the tendency of the asphaltenes to form aggregates, to such an extent that the molecular weight measurements made by means of Vapour Pressure Osmometry (VPO) or Size Exclusion Chromatography (SEC) are significantly affected by the polarity of the solvent used. For this reason, the average molecular weight values quoted in literature, where you find a variability ranging from 103-104 units of atomic mass, have a (relative) significance if considered within a set of measurements taken, but can be given little credence as far as the actual molecular dimensions of the sample are concerned.

Table 4. Compositional variability of C7 asphaltenes

precipitated from crudes and bitumens


Yield of oil based asphaltenes (% by weight) H/C ratio Sulphur (weight %) Nitrogen (weight %) Oxygen (weight %) Aromaticity factor n (average number of atoms of C per alkylic substituent) Up to 30 0.8-1.4 0.5-10.0 0.6-2.6 0.3-4.8 0.45-0.70 4-7

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The chemical-structural analysis of asphaltenes can be carried out effectively through techniques of nuclear magnetic resonance (1H- and 13C-NMR). Using these techniques, various average molecular parameters may be determined, such as aromaticity factor, degree of alkyl substitution, average chain length, etc. These are extremely useful for giving an idea of the hydrocarbon skeleton, as well as the chemical functionality of the molecules present in the sample. The results of these analyses tend to show the asphaltenes as macromolecules made up of polycondensed aromatic clusters, substituted in various ways with alkylic chains which can be fairly long (>C10), and linked together by saturated and hydrocarbon chains and heteroatoms. The degree of condensation of the aromatic units can be high, but normally it does not exceed a figure of 5-6 rings (Speight, 1980). As with the other classes of compounds, the asphaltene component of heavy crudes and bitumens is also significantly different from that of light crudes. In addition to the high heteroatom and metal content, asphaltenes have significantly higher molecular weights, due to the high concentration of sulphur which favours the formation of sulphide and disulphide bridges among the aromatic clusters, a characteristic which makes these structures very reactive in relation to thermal cracking and hydrogenating reactions (see above). From the molecular point of view, the asphaltenes contained in bitumens can be represented effectively

by archipelago models, that is, structures made up of islands of little groups of condensed rings, linked together by aliphatic chains and sulphide bridges, as depicted in Fig. 4 (Sheremata et al., 2004). The resins are compounds that fall between asphaltenes and hydrocarbon components (saturated and aromatic); they consist of polar molecules similar to those of asphaltenes, but contain longer lateral aliphatic chains and smaller aromatic rings. As already stated, because crude oil is a continuum, it is the separation procedure that determines the difference between asphaltenes and resins; resins could be considered to be asphaltenes with a low molecular weight, just as asphaltenes could be seen to be resins with a high molecular weight. From the 1950s onwards, thermo-dynamic models have also been proposed in which the asphaltenes appear as colloidal particles dispersed in the oil due to the action of the resins which surround them. Displaying a comparatively greater polarity than the rest of the oil, the resins are adsorbed onto the surfaces of the colloidal particles. In accordance with these models, the asphaltenes are stabilized or peptized by the resins; if a change in conditions of temperature, pressure or composition leads to the desorption of the resins from the colloidal particle surfaces, there is a separation (precipitation) of the asphaltenes (Murgich et al., 1996). This model, which describes asphaltenes as lyophobic colloids, is being increasingly discarded in favour of a description of asphaltenes as lyophilic

S CH3

H N S

H3C N S S O H3C N O OH CH3

CH3

S S

H3C

S S CH3 S H N O S NH

H3C

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).

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

OH O OH O OH S O HO O O O HO OH OH OH S O HS OH OH Cl OH NH OH O O O O O O OH OH

HO

colloids, solvated by the surrounding medium. In this model, the separation phase of the asphaltenes is linked to a decrease of the mediums solvent strength, and the resins cease to play the key role in the system (Cimino et al., 1995).
Nature and chemical characteristics of oil shales

Oil shales are sedimentary rocks, generally silicates and carbonates, containing significant amounts of insoluble organic material which can be recovered through pyrolytic distillation (a process which is better known as retorting). In the rocks which cover a site of potential commercial interest, the amount of organic material must be greater than 10 gal/t (45 l/t), even though as a norm, in the richest formations, this value is between 30 and 40 gal/t (for Athabasca bitumen it is around 22 gal/t). Oil shale deposits can extend for hundreds of square kilometres with thicknesses which can reach 700 m, so that the quantity of recoverable oil per unit of surface area is greater than the Canadian oil sands by an order of magnitude. The productivity of the biggest deposits (for example, Colorado oil shale) can, in fact, reach figures of up to 0.73 bbl of oil per tonne of material extracted (Bunger et al., 2004). The organic component of oil shale is made up of complex hydrocarbon molecules comparable to kerogen (Fig. 5), from which petroleum originates, containing significant quantities of oxygen (5-6% by weight) and, to a lesser extent, sulphur and nitrogen. The hydrogen content of the kerogen itself is

significantly greater than that of coal, with an H/C ratio of 1.5-1.6 compared with values of 0.8-0.9 for bituminous coals. In a similar way to coal, this organic material is usually divided into groups of macerals according to their optical (reflection of light) and morphological characteristics, echoing the nature of the biological material which created them. Macerals can be grouped into three primary types called telalginite, lamalginite and bituminite which, in turn, can be further divided into subgroups.

2.5.3 Chemistry of the conversion and upgrading processes


The purpose of converting and upgrading petroleum residues, heavy crudes and bitumens is to transform a substrate consisting of high molecular weight hydrocarbons, which are viscous and rich in toxic elements and metals, into products which are lighter and more fluid (synthetic crude oil), and are comparable to traditional crudes; or better still, into distillates that can be further upgraded to yield gasoline and diesel for motor vehicles. This transformation can be achieved directly through thermal or hydrocracking processes, or indirectly through transformation of the feedstock (a quantity of material for feeding the reactor) into syngas (i.e. a mixture of CO and H2) through gasification (see Vol. II, Chapter 7.3), and the subsequent production of paraffin through Fischer-Tropsch synthesis (see Chapter 2.6).

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Processes for conversion into distillates

The processes for direct conversion of heavy feedstocks into distillates are particularly complex and involve the reduction of the molecular weight of the feedstock constituents through reactions which break the bonds of the hydrocarbon molecules (cracking) and increase the H/C ratio; the latter can be achieved through the removal of carbon (C-rejection process) or the addition of hydrogen (H-addition process). The C-rejection processes are thermal processes through which the heavy hydrocarbons in the feedstock are disproportionated, generating distillates with a high H/C ratio and releasing a highly aromatic residue (tar or coke). This is a radicalic type process and involves the homolytic breaking of the C C and the C heteroatom bonds, followed by b-scission reactions through which, as the reaction progresses, increasingly lighter hydrocarbon fragments are produced, generating distillates and gas. However, the aromatic radicals produced by dealkylation (radical p) tend to react among themselves, giving rise to highly condensed polynuclear structures which become ever less soluble in the reaction mixture and lead to the formation of mesophase and, hence, coke above a certain level. The residues tendency to form coke is linked to the degree of polycondensation of the heavy aromatic structures and is quantified by the CCR value (Conradson Carbon Residue), which is measured according to ASTM (American Society for Testing and Materials) methodology D 189. The principal types of reaction that operate in these processes are, therefore, the dealkylation of aromatic structures, the dehydrogenation of naphthenes and condensation. All these reactions are favoured by the temperature which is generally in excess of 450C. From a kinetic point of view, at least as far as visbreaking is concerned, the production of cracking products follows an apparent first order kinetics with activation energy values of around 230 kJ/mol, which indicates that the reaction speed doubles for each increment in temperature of 14-15C. In general, thermal processes are not very selective towards the production of distillates since, as the
Fig. 6. Simplified

severity of the process increases, the gas yield increases, and problems are encountered in relation to the stability of the reaction products (see below). The quality of the distillates is poor, because thermal cracking alone is not capable of removing, in any significant way, the heteroatoms present in the heavy feedstocks. Moreover, naphtha and gasoil are rich in olefins and dienes and, hence, must be stabilized through hydrotreatment. In the H-addition processes, conversion of the heavy feedstocks and the distillates is achieved through the combined reaction effects of cracking and catalytic hydrogenation of the reactive fragments. In this way, it is possible to control the propagation of the radicalic reactions more effectively, above all, with regard to the condensation processes of the aromatics and, hence, to reduce the problem of coke formation (Fig. 6). Moreover, depending on the reaction conditions and the type of catalyst used, it is possible to add hydrogen to the products, saturating the aromatic structures and facilitating the elimination of the heteroatoms. For this reason, the quality of the distillates and the conversion residue obtained from the hydrocracking processes is definitely better than that of distillates obtainable through thermal processes. With regard to the thermodynamics of the process, the aromatic structures balance of hydrogenation reactions is facilitated by a high hydrogen partial pressure, whereas it is hindered by an increase in temperature. Therefore, the requirement to operate at temperatures in excess of 380C to promote thermal cracking makes it necessary to push the hydrogen partial pressure up to levels exceeding 100-120 bar. The ideal catalyst for the upgrading of heavy feedstocks must facilitate the process of hydrogen addition to the products generated in the thermal cracking phase, minimizing the amount of coke produced. Moreover, it must permit the removal of the poisons present in the feedstock through hydrogenation of the substrate, or rather it must favour the processes of desulphurization (HDS, Hydrodesulphurization), denitrogenation

representation of the process of hydroconversion of heavy feedstocks.

H2/ catalyst R S R1 D CH2

CH2 H S

R1

.
S

R1

distillates

R1 S mesophase coke

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(HDN, Hydrodenitrogenation), demetallization (HDM, Hydrodemetallization) and reduction of carbon residue from the products (HDCCR, Hydro Conradson Carbon Residue Removal). The most active catalytic species for these reactions are certain heavy metal sulphides such as Mo, Ni, Co, W and Rh in particular, often used in combinations (Ni/Mo, Co/Mo and Ni/W) and deposited on appropriate porous supports (preferably alumina) or mixed with the feedstock in the form of powder (catalysis in slurry phase). The main problem that is encountered when using supported catalysts to process particularly heavy feedstocks is that of limiting the deactivation of the catalyst due to the depositing of both the metals and coke. However, it should be made clear that the deposited coke can be removed through regeneration of the catalyst, whereas the activity loss due to the metals is permanent and, hence, the catalyst has to be replaced. The deactivation due to deposits of coke leads to a loss of activity because the active sites of the catalyst are covered by carbonaceous material, primarily from asphaltenes; in fact, this loss increases with the level of conversion of the feedstock into distillates, that is, when conditions favour the emergence of stability problems. The deactivation by coke can be offset by an increase in the hydrogen partial pressure. As regards the metals, the deactivation comes about through the obstruction of the porous structure and the covering of the active sites by the metals contained in the metallo-porphyrinic structures which are destroyed during the reaction generating the corresponding sulphides. However, the physical characteristics of the support and, in particular, its porosity are as fundamentally important as those of the active phase in determining the catalysts 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 conversion reactions and upgrading of the feedstock using ad hoc catalytic beds.

The catalysts used in the slurry processes are often closely associated with carbon material (coke) which is either produced during the reaction or is purposely added. Compared with supported catalysts, on which conventional hydrocracking technologies are based, these materials are not very sensitive to the presence of poisons, since they do not display the classic problems resulting from the depositing of coke and metals onto the pores of the support. The use of dispersed catalysts based on metal sulphides from groups V VI and VIII (in particular Fe, Mo and V) for , upgrading residues, heavy crudes, bitumens and coal is well-known and has been fully described in scientific literature for more than thirty years. The first significant works published on this subject make reference to Clyde Aldridge and Roby Bearden (Aldridge and Bearden, 1978), and describe the use of Mo introduced in the form of oil-soluble precursors. Subsequently, numerous variations were tried and proposed in regard to both the use of various types of precursors and the ex situ synthesis of the catalyst in order to improve its specific activity. The most active dispersed catalysts, however, are still those based on molybdenum and obtained through the decomposition of oil-soluble precursors such as naphthenates, oxalates, xanthates, dithiocarbamates or other metallo-organic derivatives such as Molyvan A (N,N-dibutyldithiocarbamate of oxothiomolybdenum) which are supplied at the hydrocracking/hydrotreating stage together with the feedstock (Delbianco et al., 1995). The in situ decomposition of these precursors in the presence of hydrogen and sulphur generates an

10 nm

Fig. 7. Structure of micro-crystalline molybdenite obtained

through TEM microscopy (Transmission Electron Microscopy; Panariti et al., 2000).

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extremely fine powder made up of nano-sized layers of molybdenum sulphide (molybdenite, MoS2) with a low degree of aggregation (nanocluster) and highly dispersed within the feedstock. The active catalytic phase is, therefore, the molybdenite, a well-known layered hexagonal structure with molybdenum between two layers of sulphur. The adjacent layers are linked together by the weak dispersion forces (Van der Waals type) in action between the respective sulphur atoms. For this reason, the molybdenic structure can be easily peeled (delaminated) until the elementary foils are obtained which display a very low degree of stacking, guaranteeing a high dispersion in the oily matrix (Fig. 7). On average, the radius is in the range of 2-4 nm. Microscopic analysis reveals that the molybdenite crystals tend to aggregate into particles with a length in the order of a micron which appear in the shape of irregular clusters that have an average diameter of 0.5-2 mm (Panariti et al., 2000). Its morphological characteristics and the absence of porous supports make molybdenite particularly well-equipped to operate effectively as a hydrogenation catalyst in very severe conditions because of the presence of high concentrations of poisons, especially heavy metals. The catalytic activity of molybdenite in a hydrogenating environment seems to be due to both the formation of sulphur vacancies on the profiles of the nanoclusters due to the effect of the interaction of the hydrogen with MoS2, and the formation of SH groups which evolve into H2S. The reactivity of heavy feedstocks to hydrocracking is strongly influenced by the nature of the substrate which can display differing degrees of reactivity, depending on the average molecular structure and on the concentration and nature of the heteroatoms present. The most reactive substrates are characterized by the fact that they have average molecular structures containing relatively small aromatics clusters, linked together by alkylic chains or C heteroatom bonds with low bonding energies. As regards the hetero-atoms, the elimination of the

sulphur comes about through the formation of H2S and may or may not be difficult, depending on the nature of the sulphuretted compound that contains it. In general, the reactivity of the sulphuretted species follows a decreasing scale: aromatic S (condensed thiophenes thiophenes) naphthenic S paraffinic S (thio-ethers and disulphides). The second heteroatom usually present in heavy feedstocks is nitrogen, which is removed in the form of NH3 through hydrogenation of the heteroaromatic structures that contain it. The elimination of nitrogen is more difficult than that of sulphur since the energy of the C N bond is greater than that of the C S bond (360 kJ/mol against 320 kJ/mol for amine and alkylic sulphide, respectively). As far as metals are concerned, the removal of Ni and V (demetallization reactions) is performed by passing the porphyrinic structures in which they are contained through a hydrogenation process. This leads to the formation of pyrrhotitic type sulphides, i.e. Ni1 xS, V1 xS (with x 0.1), which are released in the reaction mixture or trapped in the porous structure of the supported catalysts used in the process. The main reactions involved in the residue hydrocracking processes are exothermic. The heat generated depends on the nature of the feedstock being treated and the degree of conversion, as well as the level of upgrading achieved by the process. The thermal tonality of the different reactions, which occur in the upgrading processes, can be estimated based on the hydrogen consumption within a determined range of values, as illustrated in Table 5 (Tominaga and Tomaki, 1997).
Stability of petroleum residues

Table 5. Estimate of reaction heat for the main reactions

involved in the hydrocracking of heavy feedstocks


Type of reaction Cracking and ring opening Aromatic saturations Olefin saturations Hydrodesulphurization (HDS) Hydrodenitrogenation (HDN) kJ/(mole H2 consumed) 20-45 55-70 115-125 55-75 60-85

From a general point of view, stability expresses the capacity of a petroleum residue to tolerate dilution with fluxants (cutter stocks) which are predominantly paraffinic in nature, without giving rise to the precipitation of asphaltenes. The stability is assessed by determining the P-value, that is, the value of P derived from the equation: P 1 Xmin , where Xmin is the value of the samples maximum dilution in cetane (n-C16H34) where there is no precipitation of asphaltenes, expressed as ml of cetane per gram of the sample. In primary distillation residues (straight run), the stability is an intrinsic quality of the product and depends on the compositional characteristics of the asphaltenes compared to those of the non asphaltenic hydrocarbon phase (maltenes). The conversion processes, both thermal and catalytic, modify the chemical nature of these two pseudo-compounds, causing a progressive reduction in stability as the severity of the treatment grows (linked to the reactions time-temperature combination). The reasons for this

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reduction in stability are due to the fact that during the course of the reaction, the asphaltenes are dealkylated and become increasingly aromatic and, hence, increasingly less soluble in the maltene phase which tends to become more paraffinic for the same reason. Above a certain conversion level, the asphaltenes precipitate (hence a separation of the liquid-liquid phase is seen), triggering processes in which mesophase is formed and, hence, coke. This phenomenon can be observed in all residue conversion processes, both thermal and hydrocracking, so much so that the stability of the conversion products actually determines the maximum conversion level obtainable for a given feedstock. For this reason, it is not possible to push the conversion beyond 20-30% in visbreaking plants or beyond 40-50% in fixed bed hydrocracking plants.

2.5.4 Carbon rejection technologies


Thermal processes: visbreaking and coking
Visbreaking

Visbreaking is a very simple technology for the treatment of petroleum residues, which is very widespread globally. The process involves heating the feedstock for just a few minutes to temperatures in excess of 450-460C and at low pressure. In these conditions, the high molecular weight hydrocarbon structures that make up the heavy feedstock undergo a partial thermal cracking process, resulting in the production of a limited quantity of distillates, generally 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 quantity of diluent that is less than that of the feed itself (see Vol. II, Chapter 5.2). The limit on the severity of the process is, in fact, linked to the stability of the residue of which the P-value must be greater than 1.1-1.2. The main aim of using visbreaking to upgrade heavy crudes and bitumens is to make these products more fluid, facilitating their transportation via pipeline without the need to use diluents (naphtha). Obviously, given the characteristics of the process, thermal treatment does not reduce the levels of pollutants, and for this reason, traditional visbreaking is of little interest for use in the field of extra heavy crudes and bitumens. To overcome these limitations, at least in part, the Institut Franais du Ptrole (IFP) has proposed variants of the process that call for the use of hydrogenating atmospheres (hydrovisbreaking) and, where necessary, metallic additives capable of promoting hydrogenation reactions (catalytic

hydrovisbreaking) which are called Tervahl H and Tervahl C, respectively. The improvement in performance in terms of HDS activity is, however, limited to values of around 20% compared with classical visbreaking. Another solution, proposed by PDVSA-Intevep and patented in conjunction with Foster-Wheeler/UOP, is a process called Aquaconversion. In this instance, the visbreaking operation is carried out in the presence of water and a catalyst capable of promoting the partial breakdown of the water to produce hydrogen in situ, which is used for a partial upgrading of the feedstock, while the oxygen is used to produce CO2. The process was developed to pilot plant level and, later, on a demonstration scale using a suitably modified existing 18,000 bbl/d visbreaking unit. In the reaction conditions 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 yields for the same level of stability of the residue and improve the quality of the product as well (Table 6). Then there are thermal cracking processes that operate at greater severity than visbreaking that aim to further increase the degree of conversion into distillates and produce a residue capable of being pumped. Because the residue is unstable, it cannot be utilized as fuel oil but has to be burned directly in fluid bed boilers or gasified. Such is the case of the process called Deep Thermal Conversion developed by Shell. Other solutions, and in particular, the Eureka process perfected by Chiyoda Corporation and the HSC process (High-conversion Soaker Cracking) developed by Toyo Engineering Corporation, operate in fields of severity which fall between visbreaking

Table 6. Aquaconversion process performance. Feedstock treated: extra-heavy crude from the Orinoco Belt (6.5API) Visbreaking Aquaconversion Temperature (C) Conversion (weight %) Naphtha Distillates 500C
*

Base

Base

2.9 28.2

7.5 36.6

Upgrading feedstock API gravity of atmospheric residue P-value


* This

3.7 1.2

5.4 1.2

is a way of indicating the fraction of distillates that boils below 500C.

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Table 7. Comparison of the conversion yields of

delayed coking and the Eureka processes. Feedstock treated: vacuum residue with 5.9API
Delayed coking Conversion (weight %) Hydrocarbon gases C1-C4 Distillates C5-350C Vacuum gasoil Coke Pitch
*

Eureka

10.4 39.3 16.3 34.0 0.0

5.3 33.6 28.4 0.0 32.7

* This is a way of indicating the fraction of distillates that goes from pentanes to hydrocarbons that boil at 350C.

and coking. In both cases, use is made of steam to control coke formation. The Eureka process, in particular, is very much like delayed coking in that it operates with two reactors alternately. The thermal cracking reaction is carried out in the presence of a recycled oil and high temperature steam to favour stripping of the distillates. The cracking residue is a fluid pitch at high temperature and, as such, can easily be recovered from the bottom of the reactor vessel and then cooled and pelletized (Table 7).
Coking

Contrary to what happens with delayed coking, the processes of Fluid Coking and Flexicoking (an extension of Fluid Coking) use the coke generated by thermal cracking as a reaction medium and as a carrier of heat. In Flexicoking, the coke is used as a reagent in an integrated gasification reactor where it is gasified with air. In this way, production of pet-coke, the product of classic coking plants which is of least value, is eliminated. Both processes were developed by Exxon in the 1950s. The first Fluid Coking plant was set up in 1954 at the Exxon headquarters in Billings and, since then, a total of 18 units have been constructed. The process takes place in two fluid bed reactors, connected to each other so as to permit circulation of the coke. In the first reactor vessel, the feedstock is converted by means of thermal cracking into gas and distillates at a temperature of 510-560C in the presence of particles of carbonaceous material on which the coke produced by the reaction is deposited. The solid is then removed from the bottom of the first reactor vessel and sent to the second one, where it is partially burnt to recover heat needed for the process, while the excess amount is discharged. Alternatively, the residual coke can be gasified with air and steam at a temperature of 820-900C in a third reactor vessel (Flexicoking) to produce a fuel gas with a low heating value

Table 8. Product yields and qualities from delayed coking Feedstock TBP cut API gravity Sulphur (weight %) Product yields (weight %) Hydrocarbon gases C1-C4 Naphtha Atmospheric gasoil Vacuum gasoil Coke 7.5 10.0 23.6 26.1 32.8 8.3 11.0 20.3 23.9 36.5 8.2 11.4 21.1 25.6 33.4 Zuata Cold Lake Maya 510C 2.4 4.4
*

Delayed coking is the technology most often used nowadays for upgrading heavy crudes and bitumens. The process of coking (see Vol. II, Chapter 5.1) involves heating the feedstock in a furnace and then sending it to reactors known as coking drums, operating at high temperatures (around 500C) and for extended reaction times. This process promotes thermal cracking of the hydrocarbon structures so as to stimulate the production of gas and distillates from part of the component with a higher H/C ratio and to leave a carbon residue (coke) in which most of the metals are concentrated (over 90%), and an amount of sulphur and nitrogen (about 30 and 70%, respectively). Application of the coking process to heavy feedstocks becomes relatively simple from a technical point of view, but it involves the production of huge quantities of coke which is a highly polluting material that can be utilized as fuel in power generating installations or as feedstock for the production of hydrogen in gasification plants. The yield of coke can, in fact, be directly correlated to the tendency to form carbon residues (CCR) in accordance with the formula: coke (% in weight) = 1.6 CCR. Table 8 lists the results of treatment by coking of the vacuum residues from three typical extra heavy crudes.

565C 0.4 6.2

565C 0.5 5.8

Distillate characteristics API gravity Sulphur (weight %) Coke characteristics Sulphur (weight %) Ni V (ppm) 4.7 1,976 6.6 1,018 6.2 2,296 30.3 2.9 29.5 4.1 28.2 3.8

* This is a way of indicating the fraction of distillates that boils above the temperature indicated.

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(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 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 solutions adopted with regards to the reactor or the type of materials used for transmitting the heat. For example, the LR Coker (Lurgi Ruhrgas) uses a conversion reactor inside which a type of rotating screw helps to obtain optimum contact between the feedstock and the heat carrier, allowing the system to operate like a plug-flow reactor. There is one version of this technology that has been specifically adapted for treating extra heavy feedstocks with a CCR content of up to 70% (Satcon process). Finally, a mention should be made of the process known as Rapid Thermal Processing (RTP), currently

100

contaminants distribution (%)

75

50

sulphur
25

nitrogen metals
0 0 20 40 60 80 100

DAO yield (weight %)


Fig. 8. Comparison of yield vs contaminants content of DAO

obtained via deasphaltating.

Table 9. Comparison of product yields and qualities when processing an Arabian Heavy vacuum residue (1.8API and 6.0 weight % of sulphur) via coking processes Delayed coking Flexicoking Product yields (weight %) Hydrocarbon gases C1-C4 Naphtha Atmospheric gasoil Vacuum gasoil Net Coke Flexigas (expressed as fuel oil equivalent) Distillate characteristics API gravity Sulphur (weight %) Coke characteristics Sulphur (weight %) Metals (ppm) 6.4 698 29.6 3.6 23.4 4.1 11.1 13.4 17.9 17.2 40.4 12.3 10.8 15.9 26.3 2.7

in the development phase in a 1,000 bbl/d demonstration installation at the Canadian company Ensyn Group, specifically for the processing of heavy hydrocarbon materials from bitumens to ligneous biomasses. The process involves a rapid heating of the feedstock using hot sand at the relatively low temperature of 500C in a transported bed reactor onto which the coke is deposited. In this way, it is possible to process bitumens from oil sands bitumen, producing stable liquids with conversion yields of up to 80%.
Extraction processes: solvent deasphalting

32.0

Composition of the gases (volume %, dry basis) N2 CH4 H2 CO CO2 53 2 15 20 10

The fact that most of the metals present in crudes are concentrated in asphaltenes means that by using Solvent Deasphaltating (SDA), it is possible to recover significant amounts of partially demetallized and deasphalted oil (DAO) from the residues which can be processed economically in FCC or hydrocracking units. The main advantages of SDA are low investment and operational costs, while its principal limitation is that to obtain DAO with a low content of pollutants (in particular, sulphur, nitrogen, metals and CCR), the yield must be limited. As a result, significant quantities of by-products are generated (asphaltenes) that can be used as components of low quality fuels or as sources of carbon for the production of syngas and, therefore, hydrogen in suitable gasification units. The yield and the pollutant content in DAO are, in fact, directly connected, as shown in Fig. 8; therefore, the quality of the product falls as the yield increases (see also Vol. II, Chapter 7.1). The application of the SDA process in the extra heavy crudes and bitumens upgrading sector has led to the development of ad hoc technologies in which the

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Fig. 9. OPTI

Canada/Nexen Petroleums Long Lake Project for the exploitation of Canadian bitumens (Zuideveld and de Graaf, 2003).

premium synthetic crude hydrocracking sour synthetic crude OrCrude process bitumen SAGD Athabasca oil sands steam asphaltene gasification process power hydrogen

classic extraction unit is often combined with other processes. This is the case with the OrCrude process, developed specifically for the upgrading of Canadian bitumens by ORMAT Industries. The process involves: a) the distillation of bitumen (atmospheric and vacuum); b) the deasphaltating treatment of the residue during which the asphaltenes are removed; c) the thermal cracking of the DAO; d ) the recycling of the cracking products into the feedstock to the atmospheric distillation, so as to recover the distillates and separate the asphaltene component produced by the thermal treatment. In the same way as with coking, the OrCrude process produces distillates and a heavy residue (asphaltenes). They are used as feedstock for the gasification plant that produces syngas to generate energy and the steam needed for extraction of the bitumens via SAGD (Steam Assisted Gravity Drainage), as well as the hydrogen needed for further upgrading of the products. OPTI Canada and Nexen Petroleum are moving in this direction; a joint venture between these two companies is developing a project (the Long Lake Project) for the recovery and treatment of 70,000 bbl/d of bitumen in the province of Alberta, in Canada (Fig. 9). Applying the process to this type of feedstock will enable a yield of 60,000 bbl/d of synthetic crude oil at 22API which may be further treated in desulphurization/hydrocracking units to produce a sweet synthetic crude oil with a gravity of 39API, while the remaining 3,100 t/d of asphaltenes will become the feedstock for the gasification unit.
Catalytic processes: catalytic cracking

The technology of catalytic cracking, conceived in 1936 with the first industrial fixed bed installation, is characterized by the fact that it uses acidic catalysts based on zeolite to assist the reactions for cracking

heavy crudes, capable of producing distillates and naphtha, in particular. In the configuration, which is most widely used and known as Fluid Catalytic Cracking (FCC), the catalyst is mixed with the feedstock, then circulated between the riser, the reactor vessel and the regenerator. Initially, the feed consisted of gasoil, but subsequently, and particularly with the evolution of catalysts, it has been possible to feed FCCs with a wide range of hydrocarbons, from naphtha to atmospheric residue. In general, the size of the hydrocarbon molecules that make up the feedstock to an FCC plant is not compatible with the pores of the zeolitic crystal. First of all, these molecules have to be reduced in size by a preliminary cracking that takes place on the external surface (matrix) of the zeolite. This matrix can also have other functions, such as removal of the metals present in the feedstock. The feedstock enters the riser where it comes into contact with the regenerated catalyst. This contact leads to the partial vaporization of the feedstock; the oil/catalyst mixture then flows upwards along the riser. The cracking reactions take place almost completely along the riser; being globally endothermic, they cause a reduction of the temperature. The residence times are between 1 and 4 seconds, during which most of the cracking reactions takes place. In some cases, the feedstock is pre-treated to reduce the content of metals and asphaltenes by means of extraction with solvents, deasphaltating with propane, or treatment with hydrogen. A high content of asphaltenes and/or aromatics in the feedstock favours the formation and deposit of coke on the catalyst, thus reducing its activity. Over the years, the process has undergone significant improvements, as regards both the flow

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sheet of the process and the catalysts, making it possible to improve the selectivity towards the production of naphtha to be used in the gasoline pool and increasing its flexibility as far as feedstocks with high contents of pollutants are concerned. At a technical level, improvements have been made in the system for distributing the feed in the riser and lifting the catalyst, in the internal arrangements of the reactor-regenerator system, and in the addition of an external heat exchanger, through which part of the catalyst circulates to remove part of the heat produced by the combustion of the coke deposited on the spent catalyst. There have also been new developments in the configuration of catalytic cracking, for example, in the one perfected by UOP in conjunction with BAR-CO Industries, which features a very low contact time (MSCC MilliSecond Catalytic Cracking). The reduced contact time minimizes the formation of gas and coke; this solution makes it possible to feed the plant with feedstocks (residues) with a higher content of carbon residue. New catalysts have also been formulated which are more resistant to poisons (nitrogen and metals such as nickel and vanadium). To maintain a satisfactory level of catalyst activity circulating within the plant, provision is made for a greater quantity of fresh catalyst to be fed in with a corresponding withdrawal of spent catalyst. The fresh catalyst make-up will also compensate for the loss of catalyst fines which are not trapped by the cyclones. Moreover, additives (passivators) have been developed to reduce the deactivation effect of the catalyst caused by the presence of metals. The second improvement made by UOP goes under the name of X DESIGN. A vessel is added between the reactor and the regenerator in which the spent and the regenerated catalyst are mixed at a temperature below that of the regenerated catalyst. The overall result is a reduction in the thermal reactions in the riser. To sum up, the improvements enable the catalytic cracking process to be used for the conversion of relatively heavy feedstocks, even though fairly strong constraints persist regarding the feedstocks content of metals and carbon residues that limit its use for the treatment of non-conventional oils.

2.5.5 Hydrogen addition technologies: hydrocracking


Technologies with supported catalysts

As mentioned, the application of hydrocracking technologies to the upgrading of non-conventional oils can be strongly affected by the presence of metals and carbon residue in the feedstock to be treated. These

poisons can actually cause a rapid deactivation of the catalyst and an increased pressure drop in the reaction circuit with a subsequent reduction in the cycle length. To overcome these difficulties, appropriate catalytic systems can be used which make it possible to minimize the problems associated with the high content of contaminants in the feedstock and/or to modify the technology, so as to prevent the accumulation of coke and/or to enable the replacement of part of the catalyst during operation of the plant. The hydroconversion plants that use supported catalysts can be divided into two categories, based on the technology used: those with fixed bed reactors and those with expanded (or ebullated) bed reactors. The plant layout, where fixed bed reactors are used, generally consists of three or more reactors in series and a fractionating section where the reactor effluents are separated by atmospheric and vacuum distillation. The liquid feedstock must be filtered before being mixed with the hydrogen and sent to the reactors in order to eliminate the particles of solids present and prevent them from being deposited onto the catalytic beds. The flow through the reactors is of the downward type (from the top towards the bottom). The liquid feedstock and the hydrogen are heated up in two separate furnaces until they have reached the required reaction temperature. One particular innovation developed by Chevron for fixed bed technology consists of adding an Onstream Catalyst Replacement system (OCR) which makes it possible to replace part of the catalyst even while the plant is kept in operation. This configuration consists of the addition of a reactor upstream of the normal reaction train that has an upward flow (from the bottom to the top) and special internals that allow the removal of the spent catalyst and the addition of fresh catalyst from the top of the reactor. Handling of the catalyst is made possible by a special system. Its extreme sensitivity to high concentrations of poisons makes fixed bed technology particularly suitable for treating the atmospheric residues from conventional crudes, but not suitable for feedstocks produced from non-conventional oils. In a similar way to fixed bed hydrocracking, the 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 are separated by atmospheric and vacuum distillation. Also in this arrangement, the liquid feedstock and the hydrogen are heated up separately to the reaction temperature, and the flow through the reactors is of the upward type. The liquid flow, which will allow the catalyst to be expanded (ebullated), is ensured by a pump that re-circulates part of the liquid collected in the upper portion of the reactor. The recycle pump can

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Table 10. Product yields and qualities from ebullated bed Mexican blend 538C+ * 1.5 4.7

feedstock and from a mixture of Mexican crudes with a more than 60% Maya content.
Technologies with catalysis in dispersed phase (slurry)

Feedstock TBP cut API gravity Sulphur (weight %)

Athabasca 540C+ * 1.9 5.89

Product yields (weight %) Hydrocarbon gases C1-C4 Naphtha Atmospheric gasoil Vacuum gasoil Vacuum residue Distillate characteristics API gravity Sulphur (weight %) 29.1 0.20 29.3 0.16 8.6 5.6 14.2 28.4 43.2 8.6 5.6 14.2 28.4 43.2

Vacuum residue characteristics API gravity Sulphur (weight %) Metals (ppm)


* This

5.9 1.6 290

6.0 1.3 393

is a way of indicating the fraction of distillates that boils above the temperature indicated.

be installed directly on the bottom head of the reactor or even outside the reactor. Part of the catalyst contained in the reactors is replaced on a daily basis in order to keep the activity constant. There are two different technologies available on the market: the first, that keeps its original name H-Oil, was originally developed by HRI and then purchased by Axens, while the second, called LC-Fining, was developed by ABB Lummus Global. Subsequently, ABB Lummus Global made a strategic alliance with ChevronTexaco to develop and market the technology. Unlike fixed bed technology, ebullated bed technology is suitable for treating feedstocks with a high content of contaminants and, as such, is used to process vacuum residues even from particularly heavy feedstocks. Furthermore, this solution displays a high degree of flexibility for feedstocks coming from different crudes, provides almost constant yields and product quality, and has high operational flexibility. Table 10 shows product yields and qualities obtainable by processing vacuum residues from a Canadian

These hydrotreatment technologies use non-supported hydrogenation catalysts finely dispersed in the substrate to be hydrogenated. These catalysts consist of transition metals sulphide and therefore have no acidic actions, as a result of which, the conversion (cracking) remains purely thermal. The development of hydrogenation technologies with dispersed catalysts in the field of upgrading heavy hydrocarbon feedstocks can be traced back to Friedrich Bergius who, in the 1930s, developed processes for the hydrogenation of heavy crudes and the direct liquefaction of coal in which the catalysts consisted of a mixture of Fe, Al and Ti oxides (see Chapter 2.4). Subsequently, many other catalysts based on Fe, Mo and, in general, metals of the VIII group have been proposed and used, even though microcrystalline molybdenite generated from oil-soluble precursors remains by far the most efficient catalyst. As mentioned earlier, these catalysts are not very sensitive to poisons and, therefore, do not present problems of deactivation through the deposition of coke and metals on the pores of the support. That makes them of particular interest when processing feedstocks which have very high concentrations of metals, sulphur, nitrogen and asphaltenes. The main limitation of dispersed catalysts is undoubtedly the difficulty of recovering them from the unconverted residue. Consequently, the cheapest catalysts have almost always been preferred (particularly those based on Fe), or solutions that use more active materials, but in low concentrations, to avoid the separation phase and recovery from the unconverted product. In both cases, the level of upgrading of the products is medium-low. This problem has strongly influenced the development at an industrial level of all the technological solutions based on the use of catalysts in dispersed phase, which are classified according to the nature of the catalyst, the configuration of the reactor, the method of recovery and recycling of the catalyst, etc. Some of these solutions have reached the point of demonstration in pilot or pre-industrial plants, but until now, no real plants have been set up at an industrial level (SFA Pacific Inc., 2003).
VEBA CombiCracking process (VCC)

This process has resulted from the German industrys decades of experience in the field of high pressure hydrogenation of heavy hydrocarbons feedstock and coal. The heart of the

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process is a slurry reactor where cracking and hydrogenation reactions take place in liquid phase (LPH, Liquid Phase Hydrogenation) at high temperature (450-490C) and pressure (over 250 bar), and in the presence of a catalyst/additive based on iron/coal that limits the formation of coke and favours metal removal. This unit is integrated with a fixed bed reactor operating in gas phase (GPH, Gas Phase Hydrogenation) for further hydrogenation of the products. The VCC technology was developed to the point of a demonstration plant of 4,000 bbl/d at Ruhr Oels Bottrop refinery. This unit operated for several years (1988-1993) processing different feedstocks (residues, heavy crudes, coal and plastic residues) and was then dismantled in February 2000. At the moment, no further developments of the technology are anticipated, also because of issues related to the incorporation of VEBA Oel by BP.
HDH and HDHPlus processes

43% and vacuum gas oil (VGO) 36%. The distilled products, however, have to be reprocessed, whereas the residue is incinerated to recover the catalyst. The process, initially developed by Intevep using two sizes of pilot plant of 0.3 and 3 bbl/d, was later developed on a larger scale (150 bbl/d plant) using the VEBA Oel facilities in the Bottrop refinery where, from 1986 to 1988, several trial campaigns were conducted for over 7,000 hours using Morichal crude. In the most recent version, called HDHPlus, the catalyst also contains Mo incorporated on coke used as a support, so as to improve the degree of dispersion and to make it easier to separate it from the heavy residue (pitch) after the reaction. Later, in the period 1992-1997, a survey was carried out to set up an industrial plant of 15,000 bbl/d capacity at the Venezuelan Cardon refinery to process the heavy crude from the Orinoco Belt.
Canmet process

The HDH process (Hydrocracking-DistillationHydrotreating) was developed by Intevep-PDVSA in the 1980s and its scheme follows a similar pattern to the VEBA CombiCracking process. Compared with the latter, HDH works at relatively less severe conditions, that is, at a temperature of 420-480C, 130 bar pressure, space velocity (WHSV Weight Hourly , Space Velocity) of 0.4-0.8 h-1, and using an Fe sulphate as the catalyst. The performances reported indicate maximum conversion into distillates of around 95% broken down as follows: naphtha 21%, atmospheric gas oil (AGO)

Table 11. Canmet process performance. Feedstock

treated: Cold Lake vacuum residue


Conversion 525C
*

(weight %)

84.2

93.5

Product yields (weight %) Hydrocarbon gases C1-C4 Naphtha Atmospheric gasoil Vacuum gasoil Upgrading feedstock % HDS % HDN Hydrogen consumption (weight %)
* This

9.3 15.8 29.1 30.0

11.5 19.8 33.5 28.7

The process was initially studied by NCUT (the National Center for Upgrading Technology) in the 1970s and was later developed by Petro-Canada and SNC-Lavalin. The hydrocracking reactor is an empty vessel in which the feedstock is processed in the presence of an Fe sulphide based catalyst deposited on particles of coal. Because the desulphuration activity of Fe is very low, Mo can be added at a level of tens of ppm in the form of naphthenate. The reaction products are fractionated and sent to the hydrotreatment unit (Unifining and Unicracking), while the unconverted residue (5-10% of the feedstock) can be burnt or gasified. The performances recorded in the treatment of Canadian bitumen for different degrees of conversion under the typical reaction conditions of the hydrocracking unit, that is temperature of 400-490C, pressure up to 140 bar and LHSV ( Liquid Hourly Space Velocity) in the range of 0.5-2 h 1, are shown in Table 11. In 1986, a demonstration unit with a capacity of 5,000 bbl/d was set up at the Montreal refinery which is still working.
Microcat-RC process

62 31 1.6

70 41 2.5

is a way of indicating the fraction of distillates that boils above 525C.

The process, originally called M-Coke, was developed by Exxon during the 1980s and 1990s up to the present configuration which consists of: A hydrocracking stage in the presence of molybdenum based micronic catalysts supported on coal particles in dispersed phase (slurry); the reaction is carried out in a reactor that operates within a temperature range of 440-470C, at a hydrogen pressure that can reach 170 bar, with LHSV in a range from 0.5 to 2 h 1.

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Fig. 10. Flow sheet for (HC)3 technology (Lott and Lee, 2002).

370C

recycle wash water gas lean amine

feed

hot separator

fuel gas SCO

370C conditioning

reactor

mixed feed hydrotreater

vacuum tower

H2S rich amine sour water

recycle gas catalyst precursor recycle

make-up H2

recycle gas

residue

The separation of the reaction products through flash and vacuum distillation to obtain a distillate with a high yield of the fraction that boils below 560C and to produce a residue in which the catalyst and all the metals contained in the feedstock are concentrated (this residue can be burnt or gasified). The hydrotreatment of the distilled fraction in a fixed bed reactor for the finishing of the products that are subsequently fractionated into naphtha, atmospheric gasoil and vacuum gasoil. This process can reach conversions of up to 95% with a typical product distribution of naphtha 10-15%, AGO 45-55% and VGO 30-40%. It was tested at a pilot plant level of 8 bbl/d at the beginning of the 1990s, but there have been no further developments of the technology even though ExxonMobil remains active in the field, at least judging by the patents being filed.
(HC)3 process

levels (of the fraction that boils above 500C) into gas, light distillates and heavy distillates can be obtained up to 95%. The process was developed at a pilot plant level of 1 bbl/d (Fig. 10). During 2002, a patent agreement was reached between ARC and Hydrocarbon Research, a company controlled by Headwaters, to develop and market the (HC)3 technology.
Eni Slurry Technology (EST) Process

The Eni Slurry Technology (EST) process was developed recently by Snamprogetti and EniTecnologie, both companies of the Eni Group (Montanari et al., 2003). Unlike the technologies available today, EST operates in such a way as to permit the almost complete conversion of heavy petroleum feedstocks into distillates and avoid the production of fuel oil and coke.
distillates

The process called (HC)3 (High Conversion/Hydrocracking/Homogeneous Catalyst) was developed at the end of the 1980s by the Alberta Oil Sands Technology & Research Authority (AOSTRA) and the Alberta Research Council (ARC). 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 under vacuum and the residue can be recycled. The operating conditions of the hydrocracking unit call for a reference temperature of around 450C and a pressure of 140 bar. Also for this process, conversion

DAO

fractionator

reactor

feedstock hydrogen asphaltene recycle and catalyst purge

Fig. 11. Flow sheet for EST technology (Montanari et al., 2003).

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SDA

EMERGING TECHNOLOGIES FOR THE CONVERSION OF RESIDUES

Table 12. EST process performances Feedstock TBP cut API gravity Sulphur (weight %) Product yields (weight %) Hydrocarbon gases C1-C4 Naphtha Atmospheric gasoil Vacuum gasoil DAO Products Upgrading % HDS % HDN % HDM % removal of CCR
* This

Zuata 530C 2.5 4.2


*

Maya 500C 1.5 5.2


*

Athabasca Bitumen 300C 7.9 4.6


*

15.1 14.0 39.1 23.3 8.5

9.9 3.9 26.9 34.9 24.4

12.9 4.1 39.1 32.1 11.8

86 59 99 98

84 52 99 96

83 47 99 95

is a way of indicating the fraction of distillates that boils above the temperature indicated.

The heart of the process consists of a hydrotreating (HT) reactor in which the heavy crude feedstock undergoes a hydrogenation treatment in relatively mild conditions (410-420C and 160 bar), limiting the conversion per pass to distillates, but ensuring a satisfactory margin of stability for the unconverted residue. The hydrotreatment is carried out in the presence of several thousand ppm of a molybdenum based catalyst finely dispersed in the liquid mass so as to promote the upgrading reactions (metal removal, desulphuration, denitrogenation and reduction of the carbon residue). The hydrotreated products leaving the HT unit are sent to a fractionating section to recover the distillates. The unconverted residue from the bottom of the fractionating column is then sent to a solvent deasphaltating section (SDA) to recover the deasphalted and demetallized oil (DAO), while the asphaltene stream that contains all of the catalyst is recycled to the HT section to be reprocessed together with additional fresh feedstock (Fig. 11). After a number of recyclings, a stationary steady-state condition is reached that makes it possible to obtain almost total conversion levels, overcoming the traditional limitations of the classical conversion processes, i.e. the loss of stability of the reaction products and, consequently, the deposition of coke. The technical validity of the EST process was demonstrated through an experimental activity conducted at a pilot plant level of 0.3 bbl/d capacity.

The process proved extremely flexible in treating different types of heavy feedstocks, such as vacuum residues from conventional crudes (Ural and Arabian Heavy), heavy crudes (Maya) and extra heavy crudes (from Orinoco), as well as bitumens from oil sands (Athabasca). In all cases, the technical validity of the process was confirmed, especially regarding the catalyst life, the recyclability of the asphaltenes and the minimum amount of purge stream needed to prevent the accumulation in the plant of the metals contained in the feedstock. The EST process enables an almost complete conversion of the feedstock ( 95%) and guarantees an excellent level of upgrading of the products (Table 12). The technology is in an advanced phase of development in a commercial demonstration plant of 1,200 bbl/d inside the battery limits of an Eni refinery.
Other processes

In addition to the processes discussed above, there are other industrial initiatives that broaden the range of technologies potentially available, even though at the moment, they are in the early stages of development. Among these, there is the Hydrogen Transfer Cracking process, developed by Toyo Engineering Corporation (Japan) in the early 1990s. It is based on the use of iron catalysts on active coals that act so as to adsorb and desorb the radicals produced by the cracking, thus preventing the formation of coke. The

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process operates at relatively low pressures (70-100 bar) but, nevertheless, makes it possible to obtain good levels of upgrading even when processing very heavy feedstocks, such as vacuum residues from Arabian Heavy and Maya or the extra heavy Cerro Negro. The performances reported indicate maximum conversions of between 85 and 90%, with good levels of upgrading (HDM and HDS around 95 and 80%, respectively). Toyo recently reached an agreement with the Instituto Mexicano del Petrleo (a company affiliated to PEMEX) to build a demonstration unit at Tula. Another process proposed by Nikko Consulting and Engineering Corporation is the Succeed Process that operates in two stages: hydrocracking of the feedstock with catalysts in slurry phase using a dispersed catalyst based on transition metals to obtain a conversion of 60-65%; coking of the part that has not reacted so as to reach a total conversion of 85%. The Japanese company is planning to build a demonstration unit of 5,000 bbl/d. The CASH process (Chevrons Activated Slurry Hydrocracking), proposed by ChevronTexaco, is the result of a long period of research activity carried out 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

formulation seems particularly suitable for facilitating nitrogen removal. The process also foresees recycling of the catalyst from the bottom of the distillation column. The operating conditions reported by Chevron cover a very wide range of conditions: temperature 400-480C, pressure 95-130 bar and concentration of the catalyst which can go up to 10,000 ppm from 500 ppm. Development of the CASH process is currently at the stage of a small pilot plant (0.1 bbl/d). Finally, the technology called GNO-V proposed by , Genoil, is also in the development stage at a pilot plant level. The hydrogenation process operates with catalysts in slurry phase at 400C and 130 bar, and makes it possible to upgrade Canadian bitumen, raising the specific gravity from 7 to 28API, with yields in volume above 100% and reductions of sulphur from 5 to 0.2%. In recent years, Genoil has finalized agreements with Syneco Energy (a Canadian company owning reserves of non-conventional oils and coal) and ConocoPhillips to carry out demonstration tests on a 6 bbl/d pilot unit, the construction of which was started in January 2003 at Two Hills (Alberta, Canada).

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 production of gas and crude oil; hydrotreatment (upgrading) of the liquids up to the production of distillates for the fuel market.

Fig. 12. Shale oil retorting furnace with a capacity of 200-330 t/d built in the United States in the 1940s (USBM).

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Recovery of the oil from the rock in which it is contained passes through a treatment of pyrolysis carried out at high temperature for which different solutions have been developed over the years (Johnson et al., 2004). The process, known as retorting, starts at 200C, finishing at higher temperatures (500-600C), and is carried out in reactor vessels called retorts. The main objective in the design of a retort is to heat at low cost by using as little energy as possible. There are different types of retorts distinguished by the way the heat is applied to the crushed oil shale: retorts heated indirectly by gas; retorts heated directly by gas by internal and external combustion; retorts heated directly by solids (Matar, 1982). In the first type of retort, the heating comes from outside and the heat is applied through a wall, generally of cast iron. Because of its limited capacity and the low thermal efficiency of the method, this type of retort has not been developed further. The second type uses hot gases that pass directly through the oil shale, usually in a vertical furnace (Union B Process developed by Unocal). The gases can be generated through the combustion of a portion of the hydrocarbons produced within the retort (internal combustion) or by partial gasification with air and steam at 800-850C of the carbon residue that remains on the mineral after the pyrolysis treatment (SGR technology, Stream Gas Recirculation). This is a low cost method, but its yield in hydrocarbons is correspondingly low. In the third type of retort, preheated solid carriers, for example ceramic balls 0.5 inch (1,27 cm) in diameter, are mixed with the oil shale and provide the heat necessary for the pyrolysis. The first process carried out using this solution, known as TOSCO (The Oil Shale Corporation) II, was developed at the end of the 1960s by a consortium of several companies. It uses a rotating reactor operating at 500C that is fed continuously with the mineral, and involves a rather complex system of circulation of the carrier, but offers advantages in terms of the oil yield. A conceptually similar technology was later developed by UMA Engineering (Alberta Taciuk Process, ATP), and is currently considered the reference technology for this type of application. In this process, the mineral is first pyrolyzed in a rotating oven in order to produce oil (500C) and is then sent to a second combustion furnace where the organic material which has not reacted is burnt (750C), before being partially returned into circulation so as to recover the heat needed for the retorting. The gas produced during the retorting consists mainly of carbon monoxide and carbon dioxide, as a result of the release of most of the oxygen present in the initial kerogen, hydrogen, hydrogen sulphide,

methane and heavier hydrocarbons, and can be used for the production of hydrogen needed for the upgrading processes or as fuel gas. The mineral residue, generally waste material, has to be transported back to the mine or dumped in a rubbish tip. In some cases, depending on the nature of the feedstock and the method of pyrolysis, the mineral residue may still contain a considerable quantity of organic material and can, therefore, be burned to supply heat for the process. Similar to what takes place in coking furnaces, the pyrolysis reaction, in fact, produces a sort of disproportionation of the hydrocarbon matrix, producing a liquid enriched with hydrogen and a carbon residue (coke) that remains in the mineral. The product generated from the retorting of oil shale is a dark, viscous liquid with a high content of heteroatoms and unsaturated compounds produced during the pyrolysis. Compared with heavy crudes or bitumen, the liquids from oil shale display a high concentration of hydrocarbon structures with a high H/C ratio, owing to the fact that the initial kerogen contains a high percentage of paraffin structures. The distribution of the distillates in shale oils is linked to the retorting technology used but, in general, it is similar to that of the products from the coking of petroleum residues. As regards the heteroatom content, shale oils are characterized by the fact that, in addition to sulphur, they contain significant quantities of oxygen and nitrogen. The pyrolysis liquids can include several tens of ppm of metals and, amongst these, iron in particular, but also traces of nickel, vanadium and arsenic; the last element can create serious contamination problems for the hydrogenation catalysts. In fact, the upgrading of shale oils to produce fuels has its roots in the classic technologies developed in the field of petroleum refining and, in particular, hydrotreatments. An alternative solution to convert the oil shale into liquids is known as in situ conversion. This type of technology was initially put forward in the USA around the 1960s by several mining companies, among them in particular, Occidental Oil Shale. The idea was to inject air and steam into the deposit, causing partial combustion of the organic material (in situ combustion) and, therefore, the heating up of the formation, reaching temperatures of 700-800C (Braun et al., 1984). In this way, the pyrolysis process is carried out directly in the deposit, from which the conversion products can then be recovered using appropriate production wells. With the aim of optimizing the technology, several solutions have been proposed that relate, above all, to the deposit exploitation methods, i.e. the layout of the injector and producer wells, but the different trials have always experienced serious difficulties in controlling the

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combustion front and, hence, in guaranteeing a reasonable level of productivity of the oil. A different approach is currently being evaluated that provides for the boring of a series of vertical wells into the oil shale deposit, which are then heated either electrically, or by means of superheated steam, or using the hot gases produced by partial combustion of the organic material. In this way, the formation is brought up to a temperature in the order of some hundreds of degrees Celsius and kept in this condition for several years. The high temperature accelerates the natural process of degradation of the kerogen into oil (at about 300C, the degradation kinetics of kerogen increase significantly; Lewan et al., 1979) that can then be extracted like traditional crude from a production well. The conversion yields are lower than that which could be obtained with traditional retorting (about 20% in weight compared to the organic material), but the quality of the oil produced is decidedly superior, as shown in Table 13 and, above all, the environmental problems linked to recovery of the mineral and disposal of the processing residues are significantly reduced.

2.5.7 Main development projects


At present, there are numerous projects (started or at an advanced stage of development) relative to the

industrial exploitation of non-conventional oils. As far as extra heavy crudes are concerned, in Venezuela four projects for exploitation of the crudes from the Orinoco Belt have been carried out for a total of 634,000 bbl/d, with production of 573,000 bbl/d of synthetic crude with API gravities varying from 16 to 32. Negotiations are taking place with the Venezuelan state oil company (PDVSA) for an increase in production to about 2 million barrels a day by 2010-2012. Table 14 shows the most significant data relating to these projects. In Canada, in the province of Alberta, about 1.1 million bbl/d of oil sands are treated annually to produce, in part, synthetic crudes and, in part, diluted bitumen with a diluent (consisting generally of naphtha) in order to reduce its viscosity to enable it to be pumpable to allow transportation. An updated list of the main industrial projects is shown in Table 15. Finally, as far as oil shale is concerned, at an international level, there are several research and development initiatives aimed at experimenting solutions for its exploitation, particularly in Canada, Australia, China, Russia and Israel, but applications at an industrial or demonstration level are still very limited. Amongst these, a project worthy of note is the one being run by two Australian companies, Southern Pacific Petroleum NL and Central Pacific Minerals 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 Oil characteristics API gravity H/C Sulphur (weight %) Nitrogen (weight %) Oxygen (weight %) Bromine Ni number* 19.8 1.63 0.7 2.1 1.6 33 10 108
**

TOSCO process

Union Oil process

Shell ICP process

21.2 1.64 0.9 1.9 0.8 49 9 100

18.6 1.70 0.9 2.0 0.9 n/a 5 55

38 1.84 0.5 1.0 0.5 n/a 2 9

V (ppm)

Fe (ppm) Distillate distribution (volume %) C5-230C 230-343C 343-554C 554C


* **

11 25 54 10

23 21 56

5 25 70

45 39 16

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.

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Table 14. Projects for the exploitation of extra heavy Venezuelan crudes Petrozuata Operator Percentage participation Reserves (gbbl) Total CAPEX (billions of dollars) Upgrader CAPEX (billions of dollars) Production of heavy oil into upgrader (bbl/d) Syncrude production out of upgrader (bbl/d) Syncrude density (API) Upgrader technology Petrozuata ConocoPhillips 50.1 PDVSA 49.9 1.4 3.9 1.5 120,000 108,000 20-26 Cerro Negro ExxonMobil ExxonMobil PDVSA BP 1.4 2.0 0.7 120,000 105,000 16 41.7 41.7 16.6 Sincor Sincor Total PDVSA Statoil 2.3 4.6 2.5 204,000 180,000 32 Delayed coking Hydrocracking Hydrotreating 47 38 15 Hamaca Petrolera Ameriven ConocoPhillips 40 PDVSA 30 ChevronTexaco 30 2.2 4.5 2.0 190,000 180,000 26 Delayed coking Hydrocracking Hydrotreating

Delayed coking Delayed coking Naphtha hydrotreating Naphtha hydrotreating

Table 15. Main Canadian projects for the industrial exploitation of non-conventional oils Company Shell Canada, Chevron Canada and Western Oil Sands Syncrude Canada Suncor Energy Inc. Petro-Canada Nexen Petroleum & OPTI Canada Imperial Oil TrueNorth Energy & UTS Energy Japan Canada Oil Sands Ltd. Husky Energy Inc. EnCana Corp. Devon Canada Corp. Syneco Energy ConocoPhillips Canada, TotalFina & Devon Energy Canadian Natural Resources Ltd. Deer Creek Energy & Enerplus Resources Fund Black Rock Ventures Project Muskeg River Aurora Firebag Meadow Creek Long Lake Nabiye Fort Hills Hangingstone Tucker Lake Christina Lake Jackfish Northern Lights Surmont Horizon Joslyn Creek Hilda Lake Capacity (bbl/d) 155,000 140,000 105,000 80,000 30,000 30,000 95,000 35,000 30,000 70,000 35,000 80,000 100,000 232,000 40,000 20,000 Cost (millions of dollars) 5,700 5,000 2,100 800 2,600 1,000 3,500 250 350 900 400 3,500 1,000 8,000 450 260 Status Operative Under construction Under construction Proposed Proposed Proposed On hold Preliminary proposal filed Proposed Pilot Preparing proposal Preliminary proposal filed Proposed Proposed Preparing proposal Proposed Start-up 2003 2005 2007 2007 2007 2006 ? 2007 2006 2007 2007 2007 2006 2011 2008 2005

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Canadian company, Suncor Energy, aimed at exploiting the Australian deposit known as Stuart. The first phase of this project was completed in 1999 with the creation of an industrial complex for the treatment of 6,000 t/d of mineral, from which 4,500 bbl/d of a light oil (42API) with a sulphur content of 0.4 weight % and a nitrogen content of 1 weight % is produced. The processing technology used for extraction of the oil is the previously mentioned Alberta Taciuk Processor (ATP). In Estonia, there are currently three retorting installations in operation that produce 8,000 bbl/d of liquid. Looking to the future, the private chemical company, Viru Keemia Grupp (VKG), has plans for the setting up of a 4 million bbl/a plant for distillates (naphtha and diesel) whose profitability would be increased by the possibility of extracting oxygenated derivatives for the chemical industry (in particular, phenols and cresols) from the pyrolysis oil. Finally, it should be remembered that in Brazil, one of the biggest retorting plants is already in operation using gas combustion (Petrosix), through which 3,870 bbl of liquid are produced daily. As far as the in situ conversion process is concerned, in the last fifteen years, several studies and tests have been carried out in the field to optimize the technology. Particularly worthy of note is the work that is being carried out by Shell on the development of the technology referred to as ICP (In situ Conversion Process), which is in an advanced experimentation phase in the Piceance Creek basin in Colorado, while a new project has been announced in Jilin province in North East China.

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Alberto Delbianco
EniTecnologie San Donato Milanese, Milano, Italy

Romolo Montanari
Snamprogetti San Donato Milanese, Milano, Italy

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