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authors, including:


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Energy Science and Technology

Volume 3

Oil and Natural Gas


Umesh Chandra Sharma Ram Prasad

Sri Sivakumar

Executive Editor

J.N. Govil


Energy Science and Technology Volume 3 Oil and Natural Gas Editors Umesh Chandra Sharma Ram Prasad

Studium Press LLC, U.S.A.

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

Energy Science and Technology

Volume 3

Oil and Natural Gas

© 2015 Publishers

This book contains information obtained from authentic and highly regarded sources. Reprinted material from authentic sources which are acknowledged and indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the editors and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use.

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


Upgrading and Hydrotreating of Heavy Oils and Residua




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

Key words: Heavy oils, Hydroprocessing, Hydrotreating reactions, Hydrotreating catalysts, Hydrotreating technologies, Venezuelan technology

  • 1 Centro de Química, Instituto Venezolano de Investigaciones Científicas, Apartado 20632. Caracas 1020-A, Venezuela.

  • 2 Facultad Experimental de Ciencias y Tecnología. Universidad de Carabobo. Valencia, Venezuela. *Corresponding author: E-mail: ytvillas@gmail.com

Upgrading and Hydrotreating of Heavy Oils and Residua



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


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

Heavy and conventional crude oil residua have similar compositions, as for example, low H/C ratio (1.2–1.4) and high contents of metals (V, Ni), sulphur and nitrogen [2] . Hence, one of the most important objectives of

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

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

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

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

Upgrading and Hydrotreating of Heavy Oils and Residua



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

3.1. Hydrotreating Process

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

The origin of the HDT processes is related to the research of Sabatier and Senderens in 1897, regarding hydrogenation of unsaturated hydrocarbons in vapour phase using a Ni-based catalyst [1315] . In 1904, Ipatieff extended the range of feasible reactions by introducing high pressures of hydrogen. At that time, the progress of the automotive industry was expected to entail a considerable increase in fuel consumption. This led to the experimental work of Bergius, which began in 1910 in Hannover, Germany, seeking to produce gasoline by cracking of heavy oil and oil residua, as well as the conversion of coal to liquid fuels. This researcher found that to overcome the inferior quality of the unsaturated gasoline thus produced, the hydrogen mainly removed as methane by cracking during operation must be replaced by addition of fresh hydrogen. Thus, coke formation was avoided and gasoline produced was of a rather saturated nature. Bergius also noted that the S content in oil was largely eliminated as H 2 S, ferric oxide being used in the process to remove the S. Actually, ferric oxide and Fe sulphide formed in the process acted as catalysts, although the activity was very poor. The first hydrogenation plant of brown coal was custom- built in 1927 in Leuna-Germany. Development of industrial-scale

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

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

3.2. Conventional HDT Catalysts

Nowadays, HDT catalysts are based on Mo supported on ceramic materials, promoted with Ni or Co. These catalysts are active in their sulphide form, being pre-sulphided or sulphided in situ. Therefore, CoMo/Al 2 O 3 is the most widely used for HDS, while catalysts for HDM reaction, generally have large pores and low metal content. Commonly used supports include transitional aluminas with high surface areas (~200 m 2 /g), silica-alumina or zeolites for hydrocracking. Average pore size is 75 to 300 Å, although it is frequent to find wider pore size distributions. Catalytic supports to be used in HDM may also have macropores, namely a bimodal pore structure. Micropores can have a significant incidence on reactants diffusion on active sites, particularly on heavy feed [16] .

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

consist essentially of a monolayer or cluster of slabs of MoS



covering the surface of the Al 2 O 3 [16] . Layer distribution on the support

depends on Mo loading and sulphuring temperature. Under hydroprocessing conditions, it can be easily removed sulphur ions from the corners and edges of MoS 2 crystallites and this phenomenon leads to the formation of coordinatively unsaturated sites and/or vacancies of sulphur ions, which have Lewis acid character [17] and have been reported as responsible of catalytic activity. Promoters such as Co or Ni decorate MoS 2 crystals at the edge of the slabs, modifying the electronic environment of MoS 2 and consequently the way in which reactants are absorbed, as is the case for hydrogen, where homolytic and heterolytic rupture can lead to Mo-H and S-H species that deliver hydrogen to the hydroprocessing reactions [1821] .

Upgrading and Hydrotreating of Heavy Oils and Residua


3.3. HDT of Heavy Crude Oil: General Aspects

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

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

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


Since 1910, with Bergius experiments to produce synthetic gasoline from heavy feeds, residue and coal, many and diverse technologies have been developed in order to perform these processes. In Table 1, a summary of some outstanding technologies is given.

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

Table 1:

Summary of old technologies related to hydroprocessing of heavy feeds

Researcher(s) (Year)

Process name


Beckberger (1956) Hydrocracking

A combination of Fluid Coking (see next item)

Sinclair Refining Co.

of heavy crude

and cracking process to convert crude oil into



with high yields of liquids of low


boiling points. A heavy crude oil is loaded within

a fluidized particle bed of coke in a coking reaction. Large particles of coke formed are selectively removed in order to put them in contact with steam in a separated zone to generate a mixture of water-gas, which is returned as fluidizing medium. The top of the reaction is mixed with activated coke particles that come out from the generator of water-gas mixture to form a fluid suspension and the mixture is cracked in the range of gasoline products [24] .

Pfeiffer et al. (1959) Esso Research and

Fluid coking of This process consists in the coking of heavy heavy hydro- crude oil residue in contact with hot fluidized

Engineering Co.


solids [25] .

Beuther et al. (1959) Visbreaking This process can be applied to AR and VR and Gulf Research and to the remnant of the solvent deasphalting Development Co. process (SDA), where the stream of residue is heated in a furnace (450–500°C) and later, the feed is cracked during a short and specified residence time, to avoid coking reactions. The process is carried out under a soaking zone at moderate temperature and pressure. Cracked products leave the soaking zone after the desired conversion is reached and then this stream is quenched with gasoil to stop the reaction and prevent coke formation [26] .

Kellogg (1960)

Cracking of

This process is a modification of fluid catalytic

Phillips Refinery

heavy crude oils cracking (FCC) and is adapted to heavy

Colyar and Wisdom

crudes [27] . H-Oil process It is an ebullating bed process that can operate

(1960) Hydrocarbon under a wide range of conversion levels and is

Research Institute,

adapted particularly to heavy vacuum residue

Axen with high metal and Conradson carbon content. It also preserves product properties during cycle. Due to the fact that this process is carried

out in a stirring reactor and a fluidized catalyst it can handle exothermic reactions and solid- containing feeds [28] .

Mosby et al.(1973) Residue The feed is pre-heated by exchange and mixed Amoco Oil Co. Ultrafining with recycled hydrogen and heated up in a furnace to the temperature of reactor entrance. Desulphurization occurs in a multi-bed reactor, where an intermediate gas cooler avoids temperature rising and helps maintaining

Table 1: (Contd ...)

Upgrading and Hydrotreating of Heavy Oils and Residua

Table 1: (Contd ...)


Researcher(s) (Year)

Process name


catalytic activity. The products leaving the reactor are separated in several steps to eventually produce fuel gas, naphtha, distillates and desulphured residue. Streams are depurated to produce sulphur free fuel oil [29] .

Bridge et al. (1975) LSFO (Low Vacuum gasoil (VGO) is used and a process of Chevron Research Co. sulphur fuel vacuum residuum desulphurization (VRDS) is and Standard Oil Co. oil) Project applied to obtain products with between 0.1 and 1.2% of sulphur. These products are combined with the diesel feed to produce fuel oil of low sulphur content (only 0.5%). Hydrogen comes from steam reforming [30] .

Chen et al. (1981) Delayed coking Delayed coking process in which part of

Mobil Oil Corporation process

Crowley et al. (1987)


produced coke is heated by partial combustion and mixed with a pre-heated feed to reach coking temperature of the mass present in process drums. This process conducts essentially to the metal and coal removal while providing partial conversion to liquid products (naphtha and diesel) [31] .

Feed is mixed with a light paraffinic solvent

Phillips Petroleum Co. deasphalting (propane, butane, pentane or n-heptane) where

(SDA) crude oil is solubilised. Non-soluble part will precipitate from the mixture as asphaltenic fraction. The separation gives rise to two products: A deasphalted oil (DAO), which is rich in paraffins, and asphaltenes. It is a low cost process and has flexibility to meet a wide range of quality DAO [32] .

Mc. Daniel et al. (1988) LC-fining Fresh feed is mixed with hydrogen and both Amoco process react inside an expanded bed of catalyst which is maintained in turbulence by upflow of liquid to reach an efficient isothermal operation. Product quality is constantly maintained at a high level by occasionally discarding spent and adding fresh catalyst. The reactor products then flow through high and low pressure separators, and finally move to the fractionator. The recycle hydrogen is separated and purified [33] .

Oelderick et al. (1989)

HYCON hydro-

Operating in a fixed bed reactor, but in the case

Shell Research BV processing with of feeds with high metal content additional movable beds reactors for HDM are added. In this process the catalyst and the residue are added in co- current flow, the fresh catalyst enters the top of the reactor, while the spent catalyst is removed from the bottom. The catalyst is replaced at a rate that ensures that the total run of the plant has at least one year duration,

which depends on the contaminant level present in the feed [23] .

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

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


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

thermal and catalytic processes, which are described below.

5.1. Thermal Processes

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

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

Upgrading and Hydrotreating of Heavy Oils and Residua


Regarding these modifications, in 1992 Reynolds et al. [34] published a study in conjunction with Chevron Research and Technology Co. and Stone & Webster Engineering Corp. (S&W), in which they observed that VR could be economically improved using desulphurization process of Chevron (VRDS) and then apply the FCC process of S&W even if all vacuum gasoil is processed by hydrocracking. The combination of a flexible range of products, high yield of clean fuels and a proven technology, made this conversion route an attractive option. During research, they found an improvement in crude oil quality, regarding API gravity, sulphur and metal content and low yield of coke.

In 1993, Del Bianco et al. [35] published a work in which a process of thermal cracking is described. They used crude Belaym VR (Egypt) mixed with 20% of a hydrogen donor solvent (dihydrophenantren, DHP), working in a temperature range of 390–450°C. This process is known as “hydrogen- donor visbreaking” and it was investigated for the first time for direct liquefaction of coal at the end of 1970 by Exxon (Exxon Donor Solvent Process) [36] . Here, researchers found that DHP addition diminishes coke production velocity, while middle distillates production increases. The basis of this process is the thermal cracking of residual crude reaction under visbreaking conditions in the presence of hydrogen donor compounds, which provides new reaction paths, so that higher conversion and better control of condensation reactions are obtained (reduction of coke production). Hydrogen and catalysts presence is not necessary; consequently it is a low cost process. Although some works have described the use of this process, information regarding reaction mechanism and kinetics is limited. Other aromatic and polar solvents were also studied, for example, phenanthrene, 1-methyl-naphtalene, quinoline and naphthol, resulting in different yields in coke, distillates and gas. For example, phenanthrene reduces coke production from 13.5 to 9.8 wt.%, likely due to a solvating control of coke precursors by this solvent avoiding condensation reaction.

In 1994, Chen et al. [37] proposed a process of mild cracking solvent deasphalting (MCSD), which combines these two technologies properly, under supercritical and subcritical conditions, using extraction of solvent as stirring agent. Two solvents were used, pentane and a mixture of C 3 -i-C 5 (mol%: C 3 :

5.7; n-C 4 : 8.3; i-C 4 : 85.4; i-C 5 : 0.6), using Gudao and Shengli (China) VR as feeds. It could be observed when comparing this process with solvent deasphalting that the yield in DAO was superior, also, while increasing cracking temperature leads to an increase in the yield of DAO. Also, demetallization and decarbonization are substantially improved.

5.2. Catalytic Processes

This technology involves catalytic cracking and HDT. In the beginning of 1940s, the catalytic cracking mainly consisted in FCC of gas oil and VGO

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

feeds, aiming to maximize gasoline production. Meanwhile, in hydroprocessing VGO is considered a residue, traditionally; residue cracking with low metal content has been referenced as conventional FCC of VGO. The first round of RFCC started when metal-containing feeds, such as heavy VGO and deasphalted residue, were sent to units of conventional FCC of VGO [38] . Feed contamination with metals (V, Ni, Fe and Na) started to play a role in terms of selectivity (coke and gas) and activity (deactivation by coke and high temperatures) of the catalysts. This fact motivated to modify FCC catalysts in order to increase their time on stream. The introduction of substituted zeolites with rare earth metals revolutionized FCC operations due to their high activity and selectivity, enabling to introduce FCC designs with plug flow and lower contact times. Initially, the zeolites were incorporated in gel type amorphous silica-alumina catalysts in the event of any manufacturing processes based on synthetic microspheres, or crystallized in situ as in the classical treatment of the clay-based catalysts. Plank and Rosinski [39] found desirable that the catalysts be dispersed in a relatively inactive matrix to avoid over cracking. Elliot and Ostermaier [40] developed a catalyst with zeolite incorporated in clay-based silica for this purpose. The zeolite catalyst was commercialized with minimal activity of the non- zeolitic matrix pointing in the optimum activity and selectivity for coke.

The activity and selectivity of zeolites may be reasonably correlated to the unit cell size (UCS), which is a measure of the zeolite/alumina ratio in the zeolite structure. Zeolites which have not been fully replaced by rare earth metals, called hydrogen Y (HY) or partially substituted (RE-HY) equilibrate in a lower UCS. These zeolites exhibit a lower tendency toward hydrogen transfer reactions yielding a higher octane gasoline and a smaller volume of coke. However, thermal stability of these zeolites is lower than Y zeolites completely replaced with rare earths (REY). Consequently, zeolites were developed hydrothermally stabilized and they are called ultrastable Y. They maintain their structural stability at temperatures above 1000°C, however, are rapidly deactivated by the poisoning of acid sites due to the metal contaminants such as Ni and V. This protection has become an important field in the development of catalysts for RFCC [41] .

In 1996 Sugioka [42] examined the catalytic activities of noble metals supported on zeolite USY for HDS of thiophene in order to develop a catalyst for this reaction based on a highly active zeolite. It was found that the catalytic activity of the catalysts considerably changed with the noble metal and their activity followed this order: Pt/USY Ã Rh/USY Ã Pd/USY » Ru/ USY. The initial activities of Pt/USY, Rh/USY and Pd/USY were higher than that of the catalyst Co-Mo/Al 2 O 3 . It was also found that Pt/USY exhibited the highest activity and a relatively long life of all the examined catalysts. These results indicate that the Pt/USY hydrogenating catalyst has high capacity and Brønsted acidity, which is necessary for the appropriate thiophene HDS. Furthermore, it was found that the activities of the transition metals supported on USY such as Ni, Co, Fe, Mo and their

Upgrading and Hydrotreating of Heavy Oils and Residua


mixtures in different atomic ratios were lower than Co-Mo/Al 2 O 3 activity. These results indicate that hydrogenating ability of these components and mixtures thereof are insufficient. Moreover, on analysis by X-ray diffraction (XRD) of the reduced catalysts no signals of Pt and Rh were found, but large peaks of Ru and small peaks of Pd were observed. From these results, it can be said that Ru showed the lower dispersion among the noble metal supported on USY and metal dispersion is assumed to be follow this order:

Pt/USY = Rh/USY » Pd/USY » Ru/USY, which is in agreement with that found in the initial activity and stability of the catalysts mentioned above. Therefore, it is very important to prepare catalysts with noble metal/USY with high dispersion of noble metal in order to maintain a high and stable activity for HDS. Additionally, since Pt/USY was the most active for HDS of thiophene but activity gradually decreased over time, tests were made with mixtures of Pt, Pd and Rh in order to enhance catalyst stability. We found that the combination of Pt with Pd/USY was successful and the Pt-Pd/USY catalyst was more active and more stable than Co-Mo/Al 2 O 3 and Pt/USY for this reaction. This fact can be attributed to the increased Pt hydrogenating capacity when combined with Pd. However, it was not clear from the XRD analysis of the reduced catalyst if Pt-Pd/USY form alloys of Pt and Pd on USY.

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

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products (dry gas and coke) decrease with a decrease of the total conversion. Furthermore, it has been found that about 50% of the total hydrocarbons and 20% of the DAO resins can be converted into gasoline. For a given oil content, Lloydminster DAO yields 2–5% more fuel than the DAO from Athabasca. Although poor quality DAO associated to the use of a heavier solvent provides a lower gasoline mileage based on FCC feed, produces substantially more fuel based on VTB due to the higher yield of DAO in the deasphalting process. In summary, under certain assumptions, DAOs produced from VTBs of Athabasca and Lloydminster heavy oils or using propane or n-butane as a solvent can be accepted as feeds for residue cracking. Obtained DAOs using other higher molecular weight solvents must be diluted with cleaner feeds as diesel or have to be hydrotreated to reduce impurity levels and thus produce an acceptable FCC feed.

Notably, over the years the catalytic cracking process has been significantly improved in terms of process and catalyst, enabling to enhance selectivity towards the production of naphtha to be used in the gasoline pool and increase their flexibility to handle feeds with high contents of contaminants [44] . However, some limitations persist regarding carbon and metal contents. In this sense, Rana et al. [45] in 2008 worked on the synthesis of a USY zeolite mixed with an Al 2 O 3 of high surface area, with moderate acidity and meso-and macro-porosity, to support a catalyst based on CoMo for hydroprocessing of Maya heavy crude oil under moderate pressure conditions. The combination of zeolite USY and Al 2 O 3 can produce bimodal type of pore distribution in the catalyst which can contribute to a better combination of HDS and HDM performances and selectivity to asphaltenes cracking on acidic catalyst. According to the catalytic test, the catalysts obtained were more active for the hydrogenolysis (in reactions as HDM, HDS and HDN) than for hydrogenation (in reactions such as Hydrodeasphalting-HDA), which is due to the CoMoS phase. In general, a hydrogenation catalyst is undesirable for the first reactor in a series of HDT reactors, because this type of reactions can increase paraffinic hydrocarbons content, which favours the precipitation of asphaltenes. Furthermore, the direct hydrogenation of asphaltenes has a role on weakening of asphaltenes complex molecules and expose metals (Ni and V) and nitrogen at the catalytic sites [45] .

Moreover, other supports have been proved in heavy crude oil processing,

as it was reported by Trejo et al. [46] for the preparation of mixed supports of type MgO-Al 2 O 3 . In this regard, MgO nanocrystals were uniformly distributed in the matrix of the CoMo/MgO-Al 2 O 3 catalyst. This catalyst prepared with chelating agent (1,2-cyclohexanediamine-N, N, N’,N’- tetraacetic acid) showed improved thiophene HDS when using calcinations before activity test. This calcination may contribute to the interaction of the chelating agent with the MgO in the preparation of the catalyst, which facilitates the sulphidation due to the weak interaction between Mo and

support, making them more active. It is also important to note that Raman

Upgrading and Hydrotreating of Heavy Oils and Residua


spectroscopy results confirmed that the chelating agent prevents the formation of Co 3 O 4 and CoMoO 4 ; instead it promotes interaction of Mo with MgO-Al 2 O 3 support leading to the formation of MgMoO 4 species, which are easily converted into MoS 2 . By submitting Maya heavy crude to HDT with Al 2 O 3 supported catalysts with different contents of MgO, it was found that the catalyst containing 10 wt.% MgO is more selective to hydrogenolysis reactions than for hydrogenation, because despite of having larger pores (which would favour the HDA), hydrogenolysis function is further enhanced by the basic nature of the support. Additionally, a higher content of MgO leads to a more stable catalysts and this is associated to a larger pore diameter. It is known that catalysts with wide pores are recommended when large molecules are present, such as porphyrin complexes containing metals, at the expense of reducing the specific surface area and consequently reduce the activity of HDS process [47] . Therefore, preferred catalysts are bimodal catalysts, since the HDS occurs effectively in smaller pores while the HDM is performed in larger pores, as it was discussed in section 3.2. In contrast to this contribution, where HDT of heavy oil with a catalyst support of basic nature was studied, Leyva et al. [48] worked with Al 2 O 3 -SiO 2 acidic supports synthesized by the method of homogeneous precipitation, varying the SiO 2 content (31, 56, 78 wt.%) and therefore varying the acidity of the support. They tested the catalytic activity of NiMo supported on the matrix in the hydroconversion of Maya crude, finding that the catalyst with 31wt.% of SiO 2 on Al 2 O 3 had the highest activity in HDS, HDM and HDN, but the trend is reversed in the case of HDA, which may be due to two effects, the acidity or average pore diameter. However, compromising the two properties favours HDA because the effective diffusion of asphaltenes molecules occurs in the macropores and acidity promotes the cracking of the molecules. In order to elucidate which of the properties affects more the HDT reactions, selectivity plots were used. Those plots permitted to infer that activity variation is due to a combined effect of the two properties. HDM activity showed a roughly similar trend to HDA, while the activity in HDS indicates very different results for the two catalysts. The explanation behind the selectivity towards HDA and HDM reactions is the nature and size of the molecules and the similar role of the acidic sites for both functions. It appears that these results indicate that large pores and optimum dispersion of the active phase so as to complete the processing of heavy loads are needed, but the acidity of the catalysts is a secondary parameter for design of the catalyst and depends on the selectivity towards the desired product, accordingly, it cannot be said that there is an optimum combination of parameters for acidity, dispersion and pore diameter, that provides the best activity in all cases, because it affects the properties of the catalyst of each reaction in a different way. After the study of the catalytic activity was completed, the authors examined the properties and characteristics of the spent catalyst, finding considerable variation in the textural properties with respect to the fresh catalyst, as well as variations in the content of metals and coal deposited in both catalysts, which concluded that the deposition of

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

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

Dejonghe et al. [51] showed that in the presence of V, Ni-Mo-S phase was gradually replaced by V-Mo-S phase which was much less active. In contrast, Takeuchi et al. [52] reported that the V incorporated in phase V-Mo-S could be more active in the HDM and HDA than V sulphides during HDT of heavy oil. Similarly, Sasaki et al. [53] reported that they could have a catalytic activity comparable with CoMo for residue HDM. NiV sulphide catalyst was also suggested by Betancourt et al. [54] , therefore, it is highly likely that a novel active site is formed between the V and Mo that may be responsible for the high activity catalyst in HDM and HDA. In summary, the use of substituted Keggin HPA as precursors, where Mo and V are in the same structure as the starting material seems to be favourable for the preparation of new catalysts of HDM.

Recently, Ti-HMS (Hexagonal Mesoporous Sieves) materials were synthesized and used as catalyst supports for NiPMo (12-molybdophosphoric acid promoted with Ni). The effect of Ti ions in the immobilization of 12- molybdophosphoric acid on mesoporous materials was studied. In this work developed by Boahene et al. [55] double modification of HMS silica surface

was made by combining grafting with H PMo





(HPMo) and modification

of Ti 4+ ion structure. The authors found that the synthesis of NiPMo/Ti - HMS catalyst from the corresponding HPA leads to obtaining better

Upgrading and Hydrotreating of Heavy Oils and Residua


performances in HDS and HDN of a sample of coker light gas oil (CLGO) than their counterparts prepared from ammonium salts of Mo, which are used traditionally. The reason for the high activity of the formulations of NiPMo/Ti- HMS seems to be related to the specific structure of the Keggin type precursor, where small units of Mo oxide form aggregates of defined sizes, since catalysts synthesized with this methodology generate lower metal supports interactions, which helps the formation of NiMoS phase (type II), whose activity has been reported for HDT reactions.

Moreover, Méndez et al. [56] reported the use of Keggin heteropolyacids (H 3 PM 12 O 40 , M=Mo or W) as active phase source for a series of tungsten and molybdenum catalysts supported on MCM-41. These materials were tested for thiophene HDS, which helped to demonstrate the importance of supporting heteropolyacids to increase the catalytic activity, also obtaining a correlation between surface acidity and calcination temperature with the activity and stability of these catalysts in the HDS reaction.

Catalysts acidity impact on activity in HDN, HDS, HDM and HDA residue was recently studied by Marques et al. [57] , where bimodal and multimodal Al 2 O 3 supported catalysts NiMoP were used. Supports were doped with different additives: F, SiO 2 and zeolites. It was found from the results of simulated distillation that the catalysts with acidity improved by F may be selective towards heavy fractions such as asphaltenes, since no additional performance was observed in light fractions (Hydrocracking (HDC) of compounds: 370°C + ~ 5 wt.%) or even in converting residue (HDC of compounds 540°C + ~ 15 wt.%) in comparison to reference catalyst, which confirms that an increase in acidity may increase performance in HDT reactions. The generated Brønsted acid sites increased HDT activity and asphaltenes conversion through a bifunctional type of reaction mechanism, where no additional coke deposition was observed on the catalyst. In order, to explain the effect of acidity on the performances in HDT, authors proposed two hypotheses: • Increased activities in HDT may be an indirect effect of acidity, since acidity increases the adsorption of asphaltenes on the acid sites, thereby increasing their availability to the neighbouring hydrogenation sites; • or it may be a direct effect of acidity due to acid hydrocracking reactions through the breaking of C-C bond by scission of carbenium ions.

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

  • 5.2.1. Technologies based on slurry phase catalysts

HDT technologies with a fluidized bed developed in the 1960s are similar to the slurry type reactor technology [58,59] . The advantages of slurry type reactors include a simple and low-capital construction required, good

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temperature control, high capacity, low pressure loss reducing compression costs considerably, capacity of removal and addition of fresh catalyst in run, less required amount of catalyst compared to the fixed bed reactor because of the greater efficiency of the catalyst in this type of reactor.

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

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

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

Upgrading and Hydrotreating of Heavy Oils and Residua


and sent to a HDT unit, where the unconverted residue (5–10% of the load) can be burned or gasified. Obtained reactor products contain undesirable components such as diolefins, N and S; however, these products are better than the products of a coker. Consequently, a downstream HDT is a prerequisite for some of these fractions which can be achieved in conventional plants with commercially available catalysts [61] .

The Microcat-RC process, which was originally called M-Coke, developed by Exxon during the 1980s and 1990s to the present, is a process that includes the following steps: First, a hydrocracking step in the presence of a catalyst based on Mo of micrometric dimension supported on carbon particles in the dispersed phase. Then, flash distillation and vacuum distillation is applied in order to obtain a distillate with a high yield of the fraction which boils below 560°C and a residue in which are accumulated the metal and catalyst loading. This residue can be burned or gasified. Finally, a HDT reaction for the refinement of the products, which are then divided into naphtha, atmospheric Oil (AGO: Atmospheric gas oil) and VGO. This process can achieve conversions up to 95%, with a typical distribution of 10–15% naphtha products, AGO 45–55% and 30–40% VGO.

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

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

Another slurry process is the so-called slurry HC3 (High conversion, hydrocracking, Homogeneous Catalyst) process developed by the Authority for Research and Technology of the Alberta Tar Sands and the Alberta Research Council (ARC). Here, the upgrading reaction is conducted in the presence of a catalyst defined as colloidal, formed in situ from hydrocarbon soluble precursors such as pentacarbonyl Fe and 2-ethylhexanoate of Mo and if necessary an aromatic diluent is used to prevent asphaltenes precipitation. Conversion products are fractionated in vacuum and the residue may be re-circulated. Also for this process, conversion levels (the fraction that boils above 500°C) in gas, light and heavy distillates can reach 95%. The process was developed on a pilot level 1 bbl/d plant. In 2002, a patented agreement between ARC and Hydrocarbon Research, a company controlled by Headwaters Inc., to develop and commercialize this technology was given [44,63] . In addition to the processes discussed above, there are other industrial initiatives that expand the range of potentially available technologies. These technologies include the cracking process Hydrogen

Transfer, developed by Japan’s Toyo Engineering Corporation in the early 90s, which is based on the use of a catalyst supported on activated carbon Fe acting on the adsorption and desorption of radicals produced by cracking, thereby preventing the formation of coke. The process operates at relatively low pressures (70–100 bar), but, however, makes it possible to achieve good levels of upgrading even with very heavy feeds, such as the Arab oil VGO, Maya heavy crude oil or Carabobo extra heavy crude oil. Reported performances indicate a maximum conversion of 85 to 90%, with good levels of upgrading (HDM and HDS of 95 and 80%, respectively) [44] .

Another process proposed by Nikko Consulting and Engineering Corporation operates in two stages: hydrocracking loads using a slurry- type catalyst based on transition metals for 60–65% conversion and then coking of the non-reacting part in order to achieve a total conversion of 85%. On the other hand, there is a process called CASH (Chevron’s Activated Slurry Hydrocracking) proposed by Chevron Texaco, which is the result of a long period of research, based on the use of a dispersed Mo catalyst promoted with Ni. This formulation appears to be adequate to facilitate the removal of Ni. The process also provides for the recycling of the catalyst from the bottom of the distillation column. Finally, GNO-V technology, proposed by Genoil, involves a hydrogenation process operating with a catalyst in slurry phase at 400°C and 130 bar pressure and upgrading Canadian bitumen enables increasing the specific gravity of 7 to 28° API with volumetric yields above 100% and sulphur reductions from 5 to 0.2%.

Upgrading and Hydrotreating of Heavy Oils and Residua

5.3. Venezuelan Technologies


Petróleos de Venezuela S.A. (PDVSA) [64] is the Venezuelan state company in charge of exploration, production, refining, transportation and marketing of hydrocarbons. PDVSA INTEVEP, Inc. is the technology arm, a subsidiary whose strategic direction of research is to generate comprehensive technological solutions, with special emphasis on the activities of exploration, production, refining and industrialization.

INTEVEP has earned international recognition for the development of the following technology products and services:

  • 5.3.1. ISAL ®

ISAL is a hydroconversion technology to produce gasoline of low sulphur content without loss of octane rating. This process generates gas with <30 wppm of S from FCC gasoline with S 2000–5000 wppm. Further, it has a combination of catalyst and process for HDS, also performing octane recovery via hydrocracking. Since 2003, a unit of 32,500 B/D began operation in CITGO Lemont Refinery [64] .

  • 5.3.2. HDHPLUS ®

HDHPLUS ® is a treatment for conversion and recovery of heavy and extra- heavy Orinoco Belt crude oil. HDHPLUS ® /SHP, residue hydroconversion technology has conversion levels located in the range 85–92 wt.%. It is the result of 20 years of research and development with a high liquid yield (above 90 wt.%). It has a novel catalytic system that allows high conversions with very low metal injection rate. Mo-based catalyst contains incorporated coke, which is used as a support in order to improve the degree of dispersion and to facilitate removal of the residue after the reaction. This technology is also able to treat refractory feeds with high content of contaminants as they have moderate HDS and HDN activities besides HDM of the entire feed. Finally, note that HDHPLUS ® significantly minimizes solid and refinery products and additionally is completely environmentally friendly [64] .

  • 5.3.3. DHDV TM

It is a technology to produce diesel with ultralow S content (less than 15 ppm) and at the same time to meet cetane number specifications, both American and European (40 and 51, respectively). It can be applied to virgin or cracked feeds operating under moderate pressure (less than 1300 psi) and standard temperature (320–375°C) using 30 to 50% less catalyst volume than conventional technology. This technology has also been evaluated for the HDT of VGO to prepare FCC feeds. DHDV TM can be used in the

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hydroprocessing of streams mixture (petroleum-diesel-VGO), as well as for treating these streams separately [64] .

  • 5.3.4. Aqua Conversion TM

It is a residue upgrading technology where greater decrease in viscosity is achieved without causing any deterioration of the quality of oil; this has some positive effects on transportation making these feedstocks transportable with consequent savings in diluents [64] . This is a process of residue hydrogenation and mild cracking which is achieved through the transfer of hydrogen from water which is activated by a single catalyst to the residual oil being thermally cracked. It is considered a catalytic visbreaking, which operates in the presence of steam. However, an improvement in the stability is obtained in comparison to the products obtained in conventional visbreaking processes, although similar conditions of pressure and temperature are used. The addition of H 2 in this process is much less than that required when a deep hydroconversion process under a high H 2 partial pressure is employed. Still, it is sufficient to saturate the free radicals formed by the thermal process, which normally lead to polymerization reactions forming large asphaltenes and thus causing stability problems. With this H 2 addition, a higher level of conversion can be achieved, thus enabling improvement in the API gravity and viscosity and also helps maintaining product stability [65] .

  • 5.3.5. INT-MECS ®

It is a process for upgrading heavy and extra heavy crude, based on deasphalting through a liquid-liquid extraction with the use of low molecular weight solvents (e.g., C 3 H 6 ) under low severity operation conditions. The benefits provided by this technology embraces the improvement of physico- chemical properties of heavy and extra heavy crude in their API gravity (16–20°API) and reduction in the content of S and metals. Also, upgraded oil can be incorporated into another crude oil production line, such as Merey crude production line. Additionally, the proliferation of new waste pits and the treatment of already existing pits are removed [66] .


Today, as a consequence of the high demand on petroleum derivatives, the near future will be inevitably dominated by heavy oil refining. In this sense, upgrading of this type of feedstock is a major goal in oil producing countries. The upgrading can be achieved through carbon rejection or hydrogen addition technologies. The use of enormous amounts of catalysts during HDT of heavy feeds, have made the carbon rejection route (thermal cracking,

Upgrading and Hydrotreating of Heavy Oils and Residua


hydrocracking and direct coking) the preferred option as it reduces processing costs. However, recent advances in technology for the upgrading of heavy crudes and residues are focused on the production of transport fuels with high quality from crude fractions of low H/C or high boiling point.

The understanding of the role of conventional catalysts during hydroprocessing of heavy feeds has motivated the development of catalysts with high deactivation resistance and selectivity to convert heavier fractions of petroleum. Fluorine, phosphorus, zeolites, SiO 2 among others, have been used to modify the chemical and physical properties of both the supports and the active phase, providing improved selectivity and cracking activity. Moreover, textural properties have also been taken into account since large pores are required to handle large molecules found in these heavy loads, such as asphaltenes and porphyrins which are the precursors of coke and metals deposits on the support. However, a compromise regarding textural properties between HDS and HDM functionalities of the catalysts must be guaranteed by using bimodal and multimodal catalysts. Macroporous catalysts avoid poisoning and/or fouling caused by blocking the active pore mouth either by deposition of metals or coke. In any case, the use of a guard-bed type reactor is highly desirable to retain organometallic compounds that are difficult to process. In addition, high conversions were found when using catalysts in dispersed phase (slurry), but it has an inconvenience in the recovery of the catalyst to be reused from the products and unreacted feed, forcing them to be inexpensive materials with high catalytic activity. Unfortunately, there is no ideal recipe to handle and processing heavy crude oils for all refineries in the world, since these feeds vary as also do the parameters to be achieved in order to meet the needs of the market that is being addressed and the environmental standards. Everything will depend on the configuration of the refinery, the crude oil prices and products, local needs and market trends, which will be defined according to the needs and technical and financial capacity of the refinery.


[1] Speight, J.G. 2006. The chemistry and technology of petroleum. Fourth ed. Boca Raton, Florida: Taylor and Francis Group, LLC. [2] Biasca, F.E., Dickenson, F.E., Chang, R.L., Johnson, H., Bailey, H.E. and Simbeck, D.R. 2003. Upgrading heavy crude oils and residue to transportation fuel: Technology economics and outlook. SAF Pacific Inc. Engineering and Economic Consultants.


Bartholomew CH. 1994. Catalyst Deactivation in Hydrotreating of Residua: A Review. In: Oballa MC y Shih SS, editors. Catalytic hydroprocessing of petroleum and distillates New York: Marcel Dekker.

[4] Wenzel, F.W.S. ed. 1988.Fourth UNITAR/UNDP International Conference on Heavy Crudes and Tar Sand Edmonton, Canada.


Dekkers C and Daane R. 1999. Metal contents in crudes much lower than expected. Oil and Gas Journal, 97(9):44-51.

[6] Speight, J.G. 1998. Asphaltenes and the structure of petroleum. In: Speight, J.G. Ed., Petroleum chemistry and refining. Washington (DC): Taylor and Francis Publ., p. 103.

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


Dickie, J.P. and Yen, T.F. 1967. Macrostructures of the asphaltic fractions by various

instrumental methods. Analytical Chemistry, 39(14): 1847–52. [8] Tynan, E.C. and Yen, T.F. 1967. ESR study of vanadium occurring in petroleum asphaltenes in solution. Preprints, 12(2):A–89–A–101. [9] Villasana, Y., Escalante, Y., Rodríguez Nuñez, J.E., Méndez, F.J., Ramírez, S. and Luis-Luis, M.Á. 2014. Maya crude oil hydrotreating reaction in a batch reactor using alumina-supported NiMo carbide and nitride as catalysts. Catalysis Today, 220–


[10] Rana, M.S., Sámano, V., Ancheyta, J. and Diaz, J.A.I. 2007. A review of recent advances on process technologies for upgrading of heavy oils and residua. Fuel, 86(9): 1216–31. [11] Villasana, Y. 2007. Evaluation of hydrotreatment reaction time of Furrial crude oil for the improvement of the asphalthenes and their fractions in p-nitrophenol [Undergraduate Chemistry Thesis]. Bárbula: University of Carabobo. [12] Jones, P. and Pujadó, P. 2006. Handbook of Petroleum Processing. Netherlands:


[13] Sabatier, P. and Senderens, J. 1905. Nouvelles méthodes générales d’hydrogénation et de dédoublement moléculaire basées sur l’emploi des métaux divisés. Deuxième partie: Dédoublements et condensations moléculaires. Annales de Chimie et de Physique, 4: 433–88. [14] Sabatier, P. and Senderens, J. 1905. Nouvelles méthodes générales d’hydrogénation et de dédoublement moléculaire basées sur l’emploi des métaux divisés. Première

partie: Généralités et réactions d’hydrogénation. Annales de Chimie et de Physique,


[15] Sabatier, P. 2009. The method of direct hydrogenation by catalysis. The Nobel prize in chemistry: Nobel lecture. http://nobelprize.org/nobel_prizes/chemistry/laureates/


[16] Furimsky, E. and Massoth, F.E. 1999. Deactivation of hydroprocessing catalysts.

Catalysis Today, 52(4): 381–495.

[17] Ancheyta, J., Rana, M. and Furimsky, E. 2005. Hydroprocessing of heavy petroleum feeds: Tutorial. Catalysis Today, 109(1–4): 3–15. [18] Rana, M., Srinivas, B., Maity, S., Murali Dhar, G. and Prasada Rao, T. 2000. Origin of cracking functionality of Sulfided (Ni) CoMo/SiO 2 -ZrO 2 Catalysts. Journal of Catalysis, 195(1): 31–7. [19] Trimm, D. 1980. Desing of Industrial Catalysts. Amsterdam: Elsevier. [20] Rana, M., Navarro, R. and Leglise, J. 2004. Competitive effects of nitrogen and sulphur content on activity of hydrotreating CoMo/Al 2 O 3 catalysts: A batch reactor study. Catalysis Today, 98(1–2): 67–74. [21] Furimsky, E. and Massoth, F. 1999. Deactivation of hydroproccessing catalysts. Catalysis Today, 52(4): 381–495. [22] Takur, D. and Thomas, M. 1985. Catalyst deactivation in heavy petroleum and synthetic crude processing: A review. Applied Catalysis, 15(2): 197–225. [23] Oelderik, J., Sie, S. and Bode, D. 1989. Progress in the catalysis of the upgrading of

petroleum residue: A review of 25 years of R and D on Shell’s residue hydroconversion

technology. Applied Catalysis, 47(1): 1–24. [24] Beckberger, L.V.H. 1956. Inventor hydrocracking of heavy oils. US Patents. [25] Pfeiffer, R.W., Borey, D.S. and Jahnig, C.E. 1959. Inventors fluid coking of heavy hydrocarbons. US Patent. [26] Beuther, H. 1959. Inventor visbreaking of reduced crude in the presence of light catalytic cycle stock. US Patents. [27] Qabazard, H., Adarme, R. and Crynes, B.L. 1989. Catalytic processing of heavy residues - An overview. In: Trimm, D.L., Sama, H., D.L. and Bishara, A. Eds. Studies in Surface Science and Catalysis,53: 61–75. [28] Colyar, J.J. and Wisdom, L.I. 1992. Upgrading vacuum Residua from Mexican Crudes for Petroleos Mexicanos Hydrodesulphurization Residue Complex Miguel Hidalgo Refinery. Tokyo: Japan Petroleum Institute.

[29] Mosby, J.F., Hoekstra, G.B., Kleinhenz, T.A. and S, J.M. 1973. Pilot plant proves resid process. Hydrocarbon Processing, 52(5): 93–7.

Upgrading and Hydrotreating of Heavy Oils and Residua


[30] Bridge, A.G. S.J.W. and Reed, E.M. 1975. Ways to hydroprocess resids. Hydrocarbon Processing, 54(5): 75–81. [31] Chen, N.Y. and Walsh, D.E. 1981. Delayed coking process. US Patents. [32] Crowley, R.P. 1978. Solvent deasphalting. US Patents. [33] Daniel, M., Lerman, D.B. and Peck, L.B. 1988. Amocos LC-fining residue hydrocracker yield and performance correlations from a commercial unit. NPRA Refinery and Petrochemical Plant Maintenance Conference. [34] Reynolds, B., Brown, E. and Silverman, M. 1992. Clean gasoline via vacuum residue desulphurization and residue fluid catalytic cracking. Hydrocarbon Processing, 71(4):


[35] Del Bianco, A., Panariti, N., Prandini, B., Beltrame, P. and Carnita, P. 1993. Thermal cracking of petroleum residues: 2. Hydrogen-donor solvent addition. Fuel, 72(1): 81–5. [36] Furlong, L., Effron, E., Vernon, L. and Wilson, E. 1976. The Exxon donor solvent process.Chemical Engineering Progress, 72(8): 69–75. [37] Chen, S., Jia, S., Luo, Y. and Zhao, S. 1994. Mild cracking solvent deasphalting: A new method for upgrading petroleum residue. Fuel, 73(3): 439–42. [38] O´Connor, P., Gevers, A.W., Humphries, A.P., Gerritsen, L.A. and Desai, P.H. eds. 1991. ACS Symposium Series 452, American Chemical Society Washington, D.C. [39] Plank, C.J. and Rosinski, E.J. 1981. Method of making fluid catalysts. US Patents. [40] Elliott, C.H. and Ostermaier, J.J. 1979. Process for preparing a zeolitic hydrocarbon conversion catalyst. US Patents. [41] O’Connor, P., Verlaan, J.P.J. and Yanik, S.J. 1998. Challenges, catalyst technology and catalytic solutions in resid FCC. Catalysis Today, 43(3–4): 305–13. [42] Sugioka, M., Sado, F., Matsumoto, Y. and Maesaki, N. 1996. New hydrodesul- phurization catalysts: Noble metals supported on USY zeolite. Catalysis Today, 29(1–4): 255–9. [43] Ng, S.H. 1997. Nonconventional residuum upgrading by solvent deasphalting and fluid catalytic cracking. Energy and Fuels, 11(6):1127–36. [44] Del Bianco, A. and Montanari, R. 2005. Section 2.5: Emerging technologies for the conversion of residues. In: C.A. Ed., Encyclopaedia of Hidrocarbons. III. Italia: Istituto della Enciclopedia Italiana, pp. 150–60. [45] Rana, M.S., Ancheyta, J., Maity, S.K. and Rayo, P. 2008. Heavy crude oil hydroprocessing: A zeolite-based CoMo catalyst and its spent catalyst characterization. Catalysis Today, 130(2–4): 411–20. [46] Trejo, F., Rana, M.S. and Ancheyta, J. 2008. CoMo/MgO–Al 2 O 3 supported catalysts: An alternative approach to prepare HDS catalysts. Catalysis Today, 130(2–4): 327–36. [47] Rana, M.S., Ancheyta, J., Rayo, P. and Maity, S.K. 2004. Effect of alumina preparation on hydrodemetallization and hydrodesulphurization of Maya crude. Catalysis Today, 98(1–2 SPEC. ISS.): 151–60. [48] Leyva, C., Rana, M.S., Trejo, F. and Ancheyta, J. 2009. NiMo supported acidic catalysts for heavy oil hydroprocessing. Catalysis Today,141(1–2): 168–75. [49] Soogund, D., Lecour, P., Daudin, A., Guichard, B., Legens, C. and Lamonier, C. 2010. New Mo–V based oxidic precursor for the hydrotreatment of residues. Applied Catalysis B: Environmental,98(1–2): 39–48. [50] Loos, M., Ascone, I., Goulon-Ginet, C., Goulon, J., Guillard, C. and Lacroix, M. 1990. X.A.F.S. Study of model vanadium sulphide phases suspected to form on HDM catalyst surfaces. Catalysis Today, 7(4): 515–29. [51] Dejonghe, S., Hubaut, R., Grimblot, J., Bonnelle, J.P., Des Courieres, T. and Faure, D. 1990. Hydrodemetallation of a vanadylporphyrin over sulfided NiMo/ -Al 2 O 3 , Mo/ -Al 2 O 3 and -Al 2 O 3 catalysts - Effect of the vanadium deposit on the toluene hydrogenation. Catalysis Today, 7(4): 569–85. [52] Takeuchi, C., Asaoka, S., Nakata, S. and Hiroto, Y. 1985. Characteristics of residue hydrodemetallization catalysts. American Chemical Society. Division of Petroleum Chemistry Preprints, 30: 96–107. [53] Sasaki, Y., Ojima, Y., Kondo, T., Ukegawa, K., Matsumura, A. and Sakabe, T. 1982. Hydrocracking of heavy oils with fine powder catalysts (Part 5). Activity of nickel- vanadium catalysts. Journal of The Japan Petroleum Institute, 25(1): 27–31.

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

[54] Betancourt, P., Rives, A., Scott, C.E. and Hubaut, R. 2000. Hydrotreating on mixed

vanadium–nickel sulphides: A study of the synergetic effect. Catalysis Today, 57(3– 4): 201–7. [55] Boahene, P.E., Soni, K., Dalai, A.K. and Adjaye, J. 2011. Hydrotreating of coker light gas oil on Ti-modified HMS supports using Ni/HPMo catalysts. Applied Catalysis B:

Environmental, 101(3–4): 294–305. [56] Marques, J., Guillaume, D., Merdrignac, I., Espinat, D. and Brunet, S. 2011. Effect of catalysts acidity on residues hydrotreatment. Applied Catalysis B: Environmental, 101(3–4): 727–37. [56] Méndez, F.J., Llanos, A., Echeverría, M., Jáuregui, R., Villasana, Y., Díaz, Y., Liendo- Polanco, G., Ramos-García, M.A., Zoltan, T. y Brito, J.L. 2013. Mesoporous catalysts based on Keggin-type heteropolyacids supported on MCM-41 and their application in thiophene hydrodesulfurization. Fuel, 110(0): 249–58. [57] Babich, I.V. and Moulijn, J.A. 2003. Science and technology of novel processes for deep desulphurization of oil refinery streams: A review. Fuel, 82(6): 607–31. [58] Furimsky, E. 1998. Selection of catalysts and reactors for hydroprocessing. Applied Catalysis A: General, 171(2): 177–206. [59] Niemann, K. and Wenzel, F. 1993. The veba-combi-cracking-technology - An update. Fuel Processing Technology, 35(1–2): 1–20. [60] Lunin, G., Chambers, L. and Parsons, B. 1985. The commercialization of the CANMET hydrocracking process. Technical Meeting/Petroleum Conference of The South Saskatchewan Section, Society of Petroleum Engineers. [61] Montanari, R., Rose, S., Marchionna, M., Panariti, N. and Del Bianco, A. 2003. Production of ULS fuels from heavy feedstocks. Petroleum technology quarterly (Winter), pp. 61–7. [62] Lott, R.K. ed. 1998. (HC)3 process-A slurry hydrocracking technology designed to convert bottoms and heavy oils. 7th UNITAR International Conference on Heavy Crude and Tar Sand, Beijing, China: Petroleum Industry Press. [63] PDVSA-Intevep, S.A. 2006. Aspectos tecnológicos plan siembra petrolera, refinación 2006-2012. Caracas. [64] Houde, E.J., Thompson, G., Marzin, R., Pereira, P., McGrath, M. and Feintuch, H.

1998. The Aquaconversion™ process: A new approach to residue processing. NPRA Annual Meeting: San Francisco, California. US. [65] Ford, M. 2010. Proyectos tecnológicos que apalancan la explotación y mejoramiento de los crudos pesados de la Faja Petrolífera del Orinoco. II Congreso Internacional de crudos pesados; Maturin, Veneuela.