Fuel 100 (2012) 110–127

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Fuel
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Combined process schemes for upgrading of heavy petroleum

L.C. Castañeda ⇑, J.A.D. Muñoz, J. Ancheyta
Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas Norte 152, 07730 México, D.F., Mexico

a r t i c l e i n f o a b s t r a c t

Article history: Key refinery technologies for upgrading of heavy oils feasible to be combined to increase yield and quality
Received 7 June 2011 of upgraded oil are reviewed and analyzed. Hydrogen addition and carbon rejection based technologies
Received in revised form 7 February 2012 are described to establish their current situation for heavy oil and residue upgrading. Various integrations
Accepted 9 February 2012
of upgrading processes were identified in the literature and others have been proposed, which include
Available online 23 February 2012
deasphalting, gasification, delayed coking, RFCC, ebullated-bed hydrocracking, slurry-phase hydrocrack-
ing and fixed-bed hydrotreating. The main advantages of the integrated process schemes were high-
Keywords:
lighted in terms of product yields, quality of products, elimination of low-value by-products and
Combined processes
Upgrading
reduction of impurities.
Heavy oil Ó 2012 Elsevier Ltd. All rights reserved.

1. Upgrading today
Heavy oil and bitumen are characterized by high viscosity (i.e.
resistance to flow) and high density (low API gravity) compared
with conventional oil. The World Petroleum Council (WPC, formerly
World Petroleum Congress) implemented the definition of heavy oil
as that whose gas-free viscosity is between 100 cp and 10,000 cp at
original reservoir temperature, with API gravity between 10° and
20°. For its crudes, Venezuela recognizes extra-heavy oil as that
having less than 10°API gravity, but less than 10,000 cp [1].
such a purpose, the main processes are based on carbon rejection,
and hydrogen addition technologies [3].
Reserves are those quantities of petroleum declared to be com-
mercially recoverable by application of development projects to
known accumulations under defined conditions. Fig. 1 shows the
evolution of proved reserves on each region where most of the
world oil reserves are in the Middle East.
1.2. Current commercial situation of upgrading technologies

Table 1 shows a summary of the commercial technologies used

1.1. Heavy oil resources
There are very large heavy oil, extra-heavy oil, and bitumen re-
sources whose extent and locations are well known. The Interna-
tional Energy Agency (IEA) estimates that there are 6 trillion
(6  1012) barrels in place worldwide; with 2.5  1012 bbl in Wes-
tern Canada, 1.5  1012 bbl in Venezuela, 1  1012 bbl in Russia,
and 100–180  109 bbl in the United States. Most of these re-
sources are currently untapped [2].
The main problems that heavy crude oil presents are: low
mobility through the reservoir because of its high viscosity, diffi-
cult and costly transportation from the platform to the ground
and to the refineries, and consequently low processing capacity
in the refineries.
For these reasons, it is mandatory to upgrade the heavy crude
oil, if either upstream or downstream sectors are looking for bigger
benefits during the heavy petroleum production and refining. For
⇑ Corresponding author. Tel./fax: +52 55 9175 8429.
E-mail addresses: lcastane@imp.mx (L.C. Castañeda), jancheyt@imp.mx
(J. Ancheyta).
for heavy oil and residue upgrading and their processing capacity.
Carbon rejection processes represent 56.6% of the total worldwide
processing capacity mainly due to its relative low investment. In
contrast to other countries, Japan refineries prefer the use of
fixed-bed hydrotreating technologies.
The increasing trend of crude prices leads the hydrogen addi-
tion processes to be more attractive in terms of profitability acquir-
ing higher yields and quality. This tendency will probably increase
the capacity of those processes in the world.
2. Technologies for upgrading of heavy oils
Heavy oils have relatively low economic values and are more
difficult to process than conventional crudes, i.e. light crude oils.
Heavy oils, however, can be upgraded with available refining tech-
nologies to improve transportability and increase their value. The
high resid content of heavy oils makes them candidates for upgrad-
ing processes that increase the hydrogen-to-carbon ratio [5].
A number of technologies has been developed over the years for
heavy crude and residue oil upgrading, which include processes

0016-2361/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2012.02.022
 L.C. Castañeda et al. / Fuel 100 (2012) 110–127 111

North America Central & South America Europe

Eurasia Africa Asia & Oceania
Middle East
800

200

Billion Barrels 700

100

0 600

Total, 2003 2004 2005 2006 2007 2008 2009 2010

Billion Bbl 1213 1265 1277 1292 1316 1332 1340 1354

Fig. 1. Evolution of world crude oil proved reserves by region [4].

Table 1
Worldwide commercial residue processing capacity, (Mbbl/d).

Technology United States Europe Canada/Mexico/Venezuela Japan Rest of the world World total % capacity
Carbon rejection
Cracking/visbreaking 44 2260 331 24 1635 4293 25.85
Coking 2245 673 951 66 1169 5104 30.73
Total 2289 2933 1282 90 2804 9397 56.58

Hydrogen addition
Fixed-bed, HDT 499 149 30 591 1042 2312 13.92
Ebullated-bed, HDC 102 79 244 23 49 497 2.99
Slurry-phase, HDC – – 4 – – 4 0.02
Residue FCC 831 681 281 318 1832 3942 23.73
Total 1432 909 559 932 2923 6755 40.66

Others
Deasphalting 283 46 39 16 75 458 2.76
Total 4002 3889 1879 1037 5801 16,609 100.00

HDT: hydrotreating, HDC: hydrocracking.

that are based on the carbon rejection and hydrogen addition
routes [6,7].
Carbon rejection is one of the first type of conversion processes
applied to the oil industry, and has been used since 1913, when dif-
ferent fuels and heavy hydrocarbons were heated under pressure
in large drums until reaching their thermal fracture into lower
molecular size products with a lower boiling point; at the same
time, some of those molecules reacted among themselves to form
others even larger than the original ones, giving origin to the coke.
In general, thermal cracking of residue is carried out at rela-
tively moderate pressures and it is often called coking process.
Coking process transfers hydrogen from the heavy molecules to
the lighter molecules, resulting in the production of coke or carbon.
Visbreaking is a widely-known carbon rejection technology that
consists of a thermal cracking process to produce naphtha and
other distillates, with a residue product that is visco-reduced (less
viscous than the initial feed). Visbreaking, thermal cracking, and
coking technologies can be generally applied to all residues, be-
cause they are not limited to constraints such as metal content
and coke forming tendencies as in the case of catalytic processes
for upgrading.
Fluid-coking and flexicoking are developments of Exxon Mobil
Research & Engineering. Fluid-coking that was commercialized in
the early 1950s, has eight built units with a combined capacity
of 375000 bbl/d and one more under construction with vacuum
residue capacity of 95000 bbl/d in Alberta, Canada. In fluid-coking
about 6% of coke, basis feed, is burned to supply heat for the pro-
cess while the net coke yield is 70–75% of that from delayed
coking.
Flexicoking was commercialized to gasify the coke with steam
and air in a separate gasifier vessel to produce a low-Btu fuel gas
with a heating value of 125–130 Btu/scf. Five units with a total
capacity of 179000 bbl/d were constructed from 1976 to 1986.
Gas and liquid yields are the same as for fluid-coking but up to
97% of the coke can be gasified.
The technology for residue gasification to produce synthesis gas
for hydrogen or chemicals, or for combined cycle power generation
is being applied mainly in Europe where coking of residues is not
extensive.
Hydrogen addition technologies produce high yield of products
and upgraded crude oil with a commercial value higher than that
of the carbon rejection technologies, but require larger investment
and more natural gas availability to produce the required amount
of hydrogen, particularly those working at high reaction severity
conditions, e.g. H-Oil and LC-Fining processes. This family of pro-
cesses upgrades heavy oils by adding hydrogen, thus increasing
the hydrogen-to-carbon ratio of the products (reducing their den-
sity) and increasing their value and usefulness. Hydrogen addition
112 L.C. Castañeda et al. / Fuel 100 (2012) 110–127

technologies are classified depending on the type of reactor used,
e.g. fixed-bed, moving-bed, ebullated-bed and slurry-bed
processes.
More recently a moderate reaction severity process has been
proposed for upgrading of heavy oils and residue, which has as
main advantage low investment and operating costs while produc-
ing high API gravity, low impurity content upgraded oil without
excessive sediments formation problems [8].
Fig. 2 shows a general comparison of various upgrading tech-
nologies taking into account operating temperature and pressure.
The asphaltenes and metals in the feedstock of these technologies
have an important role towards the selection of the type of reactor
[9].
2.1. Solvent deasphalting (SDA)
This is a physical separation process where the vacuum residue
is divided into its components by means of a solvent used as
absorption medium [10–13]. It is a process based on specific grav-
ity as opposed to the boiling point distillation. Its products are
deasphalted oil (DAO), and a residue (pitch) rich in aromatics with
high concentration of impurities such as metals, sulfur, asphalt-
enes and Conradson carbon. DAO can be used as a base for the
preparation of finished lubricants, as well as feed of catalytic crack-
ing or hydrocracking plants, whereas the residue is used to prepare
asphalts and also as feed for thermal cracking processes. SDA pro-
cess offers the additional option of producing a low cost feed for
the gasification process. SDA is an advantageous process because
of its relatively low costs and the implicit possibility of obtaining
a wide variety of deasphalted oils. It also offers a high selectivity
for asphaltenes, a considerable metal rejection, a certain selectivity
to reject carbon and minor selectivity for sulfur and nitrogen. Its
disadvantages are the lack of residue conversion and the high vis-
cosity of the asphalt produced. There are currently more than 50
commercial units, based on the FW–UOP technology. The solvent
extraction processes are classified into two groups, the conven-
tional ones and those operating at super-critical conditions. The
operational philosophy in both cases is the same, and the only dif-
ference is the process conditions, which are set to optimize the sol-
vent handling and the operation efficiency, such as the Demex
conventional and Rose supercritical processes.
2.2. Visbreaking (VB)
Visbreaking is one of the lowest cost conversion process
choices. It reduces heavy fuel oil product by mildly cracking the

350
Hydrogen addition
Fixed Bed
300 4. Hyvahl
5. OCR
6. HYCON
7. IMP
250
Ebullated Bed
Hydrogenaddition
Pressure, kg/cm2

8. H-Oil
9. LC-Fining 11
200 Slurry reactors 8 1312
10. HDH plus
11. VCC 9 16 6
150 12. CANMET 15 4
13. SOC 10
14. MICROCAT 5

100 15. EST 7 Carbonrejection

16. HCAT 1. Delayed coking
2. Fluid coking
3. Flexi coking
50
Deasphalting
Visbreaking
1 2 3 Carbon rejection Gasification
0
0 100 200 300 400 500 600 700 800 900 1000 1100
Temperature, C

40

Slurry

30
Asphaltene (wt %)

Ebullated-bed
20
Moderate
reaction
Fixed-bed
severity fixed-
10 bed

RFCC
0
1 10 100 1000 10000
Metals (ppm)

Fig. 2. Typical operating ranges for upgrading units. (a) Temperature–pressure and (b) Metals–asphaltenes composition.
 L.C. Castañeda et al. / Fuel 100 (2012) 110–127
resid to reduce its viscosity and produce some distillates. With vac-
uum resid feed, typically about 20% is converted into distillate and
lighter products [14,15].
In 1993, Foster Wheeler and Universal Oil Products made an
agreement to combine their technical experiences, knowledge
and resources in the visco-reduction area. In total, these companies
have developed over 50 visco-reduction plants, 20 after the agree-
ment. The key parameter of VB process is product viscosity. Fol-
lowing a preheating step, the feed is sent to an oven where the
cracking temperature is reached. Although the cracking process
starts in the oven, the major part of it takes place within a reaction
chamber located immediately after the oven. The cracked material
is cooled down to avoid excessive formation of coke, and then is
sent to a fractionation unit for product separation. Similarly to
FW and UOP, Shell and ABB-Lummus have been dedicated to the
development and commercialization of a drum type application
namely Reaction Chamber (Soaker), with over 80 projects based
on this process, many of them already in service [16,17].
2.3. Delayed Coking (DC)
Delayed coking uses thermal cracking to convert petroleum res-
idue into higher value distillate products and coke without the pro-
duction of fuel oil. The general goal of such a technology is to
maximize distillate yield while minimizing coke production. De-
layed coking technology is one of the most cost-effective routes
for converting/upgrading heavy residua. The process can handle a
variety of feedstocks, such as petroleum-derived resids, cracked
materials (pyrolysis tar and cycle oils), and liquid feedstocks de-
rived from coal [18–20].
DC is a mature commercially proven technology which operates
at low pressure without catalyst and no hydrogen is consumed. It
is insensitive to contaminants producing low refinery emissions
(SO2). Disadvantages of this technology can be the abundant pro-
duction of coke, low yield of upgraded oil, and highly aromatic
products which require post-treatment [21,22]. Foster Wheeler of-
fers SYDEC (Selective Yield Delayed Coking) under license with
over 25 revamps designed in the last 10 years, over 20 new units
designed in the last 5 years, and over 2.5 million BPSD have been
installed using such a technology [23].
2.4. Fluid-coking (FCK)
This is a continuous coking process developed by ExxonMobil,
which converts heavy streams, such as residua from atmospheric
or vacuum distillation, bottoms of SDA and catalytic cracking units,
and bitumens of oil sands, into light products. Distillation residue
with an initial boiling point of 1050 °F goes into the scrubbing sec-
tion, where it exchanges heat with the vapors coming out from the
reaction step. The condensing fraction is recycled and blended with
new feed, whereas the vapors are sent to the fractionation tower.
At the reaction section, the feed is thermally cracked into light
products and coke; this is sent to the burner, where air and heat
are provided to burn between 15% and 25% of the total; the balance
is sent back to the reactor to maintain the reaction temperature
[24–26].
Similarly to FCC process, fluids solids are in a continuous circu-
lation. Fluid coke circulates between burner and reactor. The coke
combustion provides heat to the process (around 20% of produced
coke). Fluid coking yields lower coke production and easier han-
dling compared with delayed coking.
The product yield of the process is in the range of 70–75% per
load weight, whereas the balance is coke. Since 1954, seven units
have been put in service worldwide, with an accumulated capacity
of 350,000 BPD. At the beginning it was stated that FCK would re-
place DC in the market, but it has not taken place so far.
113
2.5. Flexi-coking (FXC)
This is a process developed also by Exxon Mobil as a modifica-
tion to FCK, adding a step for coke gasifying to produce flexi-gas, a
coke gas with a low heating power (80–100 BTU/cf), reducing con-
siderably the coke production. It provides higher flexibility yield-
ing two clean products: liquids and flexi-gas. Product yield is
similar to that of FCK, but coke production is reduced from 24%
to 4%, converting it into flexi-gas. Essentially petroleum coke is
eliminated and an economical fuel gas is available for consuming
in refinery. Due to the high initial investment, and mechanical cost,
only five units have been built around the world [25,26].
The first FXC unit was put in service in Japan in 1976 further ex-
panded in 2002. Currently, Hellenic Petroleum is constructing a
21 MBD unit in Elefsis, Greece with an investment higher than
1000 MM Euros, while another unit of 22 MBD is licensed for Petro
Peru [26,27].
2.6. Gasification (GF)
The Texaco Gasification Process (TGP) developed in the late
1940s, was projected to produce hydrogen and carbon monoxide
– syngas – for chemical plant and refinery applications. It was de-
signed to process natural gas. In the 1950s, it was modified for hea-
vy oil feeds, in the 1970s for solid feeds like coal, and in the 1980s
for petroleum coke. Nearly from its origin, the process has been an
attractive means for hydrogen production [28,29].
Among commercially proven technologies, TGP based plants re-
main the most environmentally benign means of generating valu-
able products from sulfur-containing feedstocks. Power plants
with TGP technology emit a fraction of the NOx and SOx pollutants
that are produced from conventional or fluidized bed boiler instal-
lations. Even advanced boiler systems produce solid wastes in
quantities far in excess of those produced in TGP plants. Texaco
gasification converts heavy oils such as vacuum residue and
asphaltenes into synthesis gas (syngas) which is primarily hydro-
gen and carbon monoxide. The use of gasification can help refiners
produce hydrogen, enhance the yield of high-value products, elim-
inate the production of high-sulfur fuel oil, minimize the refinery’s
environmental footprint, and process a wider range of crude oils,
especially those with higher sulfur content [30–32].
2.7. Resid Fluid Catalytic Cracking (RFCC)
RFCC is a refining process to convert residua feedstocks
(CCR > 4 wt.%) with low metal content into lighter, higher value
products. The product includes light olefins such as propylene
and butylenes, gasoline, and distillates, whereas coke is deposited
on the catalyst. RFCC is a commercially proven catalytic cracking
process that can convert a wide range of virgin and pre-processed
residue feedstocks [33,34]. Stone & Webster (S&W), in association
with Institut Français du Petrole (IFP), is the licenser of the S&W–
IFP residual fluid catalytic cracking (R2R) process. The original
S&W–IFP R2R (reactor 2 regenerators) process was developed dur-
ing the early 1980s by Total Petroleum Inc. Today 26 IFP RFCC units
either revamp or grassroots have been licensed worldwide [33].
The RFCC process also works well in combination with other heavy
oil conversion processes such as delayed coking and visbreaking.
2.8. Fixed-bed hydroprocessing/hydrocracking (FBR)
In fixed-bed residue hydroprocessing/hydrocracking, Axens
technology utilizing its Hyvahl process (using the Permutable
Reactor System), has reached an important commercialization le-
vel. The first Hyvahl unit was put on stream in 1995 using Arabian
Light residue (Vacuum or blended with atmospheric residue)
114 L.C. Castañeda et al. / Fuel 100 (2012) 110–127
feedstock, continuing with the start-up in 2002 of the second
50,000 bbl/d unit at the S-Oil Osan refinery in South Korea
[35,36]. In another fixed-bed hydroprocessing commercial
development, Chevron Lummus Global (CLG) licenses a family of
residuum conversion technologies such as On-stream Catalyst
Replacement technology (OCR) for processing high-metal feeds
and the effective revamp alternative, the installation of an Upflow
Reactor (UFR). It is similar in operation to the OCR unit but without
the on-stream catalyst replacement transfer system, which can be
added at a later date. The upflow reactor has now been operated in
vacuum residue desulfurization service at Sinopećs Qilu Shengli
refinery and Kuwait National Petroleum Corporation Selected
CLG for Resid Upgrading Technology for Clean Fuels Project 2020
where the RDS units will utilize CLG’s UFR reactor technology
[37,38].
The third relevant fixed-bed technology (Bunker Reactor Sys-
tem) was developed by Shell as HYCON Process [39]. This process
uses conventional fixed-bed reactors for hydroprocessing of low
metals content feeds. As the metals content of the feed increases,
one or more moving bed ‘‘bunker’’ reactors are added as the lead-
ing reactors for hydrodemetallization. The ‘‘bunker’’ reactors and a
catalyst system are designed for continuous catalyst replacement.
Catalyst is replaced at a rate to insure a total plant run time of at
least a year, typically at a rate of 0.5–2% of catalyst inventory per
day depending on feed metals [40].
Shell started up a HYCON unit with ‘‘bunker’’ reactors at its
Pernis, Netherlands refinery in 1989. After some important modifi-
cations, the plant has been operating since 1998 at a feed rate of
about 27,000 bbl/d of vacuum residue from Arabian and Iranian
crudes. Conversion to distillates is typically 65–70%. The uncon-
verted residue is blended into a 1–2 wt.% sulfur fuel oil.
2.9. Ebullated-bed hydrocracking (EBR)
Ebullated-bed hydrocracking process has been used for desul-
furization, demetallization, Conradson carbon reduction, and
hydroprocessing of atmospheric and vacuum residua. Feedstocks
processed include vacuum residue comprising high sulfur and
heaviest high metals. Commercial designs range from desulfuriza-
tion at minimum conversion for production of high quality fuel
oils, to nearly complete conversion of residue into low sulfur distil-
late products. Residua product can be used as fuel oil, blended into
synthetic crude, or as feedstock to a coker, visbreaker, gasifier, or a
solvent deasphalter [41,42].
In the ebullating bed processes, hydrocarbon feed and H2 are
fed upflow through a catalyst bed, expanding and backmixing the
bed, and minimizing bed plugging. Fresh catalyst is added to the
top of the reactor and spent catalyst is withdrawn from the bottom
of the reactor. There are two ebullating bed processes: the H-Oil
process of Axens/IFP and the LC-Fining process of Chevron Lummus
Global. The two processes are similar in concept but differ in some
mechanical details. The final product contains approximately 25%
of non-converted residual and can be commercialized as upgraded
or reprocessed crude for deep conversion units handling DC, VB or
SDA [43,44].
Three specific H-Oil processes are now promoted:
H-Oil/HCC: This heavy crude conversion process produces syn-
crude. The objective of the unit is to enable just enough conver-
sion to reduce viscosity and increase stability so that the
product can be readily transported to an upgrading center.
H-Oil/DC: Difficult to treat VGOs and VGO mixtures are pro-
cessed in this unit with the objective of moderate conversion.
H-Oil/RC: The classical H-Oil process has been significantly
upgraded to increase conversion levels, increase product stabil-
ity and reduce costs. Among the improvements made to the tra-
ditional technology are the integration of IS2 (inter-stage
separator) between reactors in series and the application of
C2U (cascade catalyst utilization).
Totalizing H-Oil/HCC and H-Oil/RC references, there are cur-
rently seven H-Oil units running around the world with a com-
bined capacity of about 260,000 bbl/d and 5 LC-Fining units with
a capacity of 245,000 bbl/d. Axens also offers the T-Star process,
developed by Texaco for gas oil hydroprocessing, which is a simpli-
fied version of the H-Oil process [45].
The H-Oil unit located at Tula refinery, Mexico was revamped
from residue hydrocracker to FCC feed pretreater since 2009 [46].
2.10. Slurry-Phase Reactor technology (SPR)
The Slurry Phase Reactor processes employ disposable catalysts
whose development aimed at decreasing the cost of the catalyst
inventory, i.e. cost of the fresh hydroprocessing catalysts and that
of the spent catalysts. A number of processes employing a dispos-
able catalyst are in a developmental stage and others are in a near
commercial stage [47,48].
The HDH Plus process is a technology developed in the 80s at
PDVSA-Intevep for the treatment, conversion and valorization of
the Orinoco Belt heavy crudes. It took more than 20 years of re-
search and development, including scaling tests and evaluation
of different crudes, and consists of a high conversion process of
heavy crudes and refinery residua via hydro-conversion, from
90% to 95%, versus the 70% level of the DC case [49,50]. There are
two semi commercial-scale plants under construction at the refin-
eries of El Palito and Puerto La Cruz in Venezuela, projected with a
capacity to convert 25,000 daily barrels of vacuum residua each,
and it has been frequently mentioned by PDVSA authorities that
this technology will be used in the future upgrading complexes
of the Orinoco Belt new projects. This technology generates a con-
siderable yield in liquids (115 vol.%), renders high quality products
and is flexible to process different feeds with high sulfur and metal
contents [51].
The VEBA Combi cracking process (VCC) which derived from the
coal liquefaction experience in Germany is perhaps the best known
slurry phase process [46,52]. The plant was able to achieve 90–94%
conversion of a residue, at about 4000 b/d throughput [53]. Iron
oxide and/or partially gasified lignite char were found to be effec-
tive additives. VEBA operates its unit at Bottrop, Germany for the
conversion of plastic disposals to light fuels.
The CANMET Hydrocracking Process is a high conversion, high
demetallizatlon, residuum hydrocracking process which, using an
additive to inhibit coke formation, achieves conversion of high
boiling point hydrocarbons into lighter products. It was initially
developed to upgrade tar sands bitumen and heavy oils of Cana-
dian origin [54,55].
CANMET usually processes 5,000 BPD of visbreaking residue in
Petro-Canada refinery in Montreal. Petro-Canada reports that the
unit is started-up when operation is economically justified and
suspended when a more attractive option for processing the mix-
ture visbreaking bottom/vacuum residue is available [40].
In the early-2000s UOP evaluated several options focused on
providing a commercially-feasible slurry hydrocracking technol-
ogy offering to the market. They concluded that the most efficient
approach involved Natural Resources Canada’s (NRCan) CANMET
Hydrocracking Process. In 2006 UOP began working with NRCan
to evaluate and improve their CANMET Process technology pack-
age. Pilot plant testing as well as detailed reviews of engineering
design and operations were developed before UOP acquired the
exclusive worldwide rights to license the CANMET Hydrocracking
Process in 2007. Finally this work resulted in the development of
the UOP Uniflex Process, which includes a combination of elements
 L.C. Castañeda et al. / Fuel 100 (2012) 110–127 115

Distillates
Atmospheric Vacuum
Distillation Distillation Distillates

Deasphalting

Heavy Upgraded
crude oil crude
DAO
separator

Atmospheric Extractor
residue

Pitch
Vacuum
stripper
residue
DAO
stripper

DAO
Pitch

Gasification Syngas

Scrubber
Steam
Oxygen BFW
Bleed to SWS

Reactor Boiler
Soot Filtercake Ni/V ash
quench Work up

Filtration

Fig. 3. Deasphalting–gasification upgrading scheme [14].

from the CANMET Process reactor section and UOP’s Unicracking
and Unionfining Process technologies [56,46].
Super oil cracking (SOC) process under development in Japan
has rather unique features, i.e. it uses horizontal furnace tubes as
the reaction zone [48,52]. A finely ground catalyst to promote
cracking of the heavy feed is added to the slurry. The process em-
ploys severe conditions such as H2 pressure above 200 atm, tem-
perature about 480 °C and relatively short residence time. So far,
the process has been demonstrated using a vacuum residue on a
3500 b/d scale.
MICROCAT-RC Process was developed by ExxonMobil for hydro-
conversion of petroleum residue [57,58]. The fundamentals of this
process are to add a small amount of an oil soluble and dispersible
metal compound such as manganese or molybdenum to the reac-
tor feed. At reaction conditions the additive forms a finely dis-
persed powder, less than 1 lm in size, which suppresses coke
formation.
The process was extensively tested in bench units. EMRE used
its experience from the 250 ton/d coal liquefaction plant to develop
a commercial design. This unit is equivalent to about a 2000 bbl/d
residue conversion plant.
Eni Slurry Technology (EST) is a process developed in the early
1990s, after catalyst screening studies in laboratory microreactor
and bench scale autoclave tests [59]. Further a pilot plant with a
capacity of 0.3 bbl/d was started up in 1999. Eni/Snamprogetti
has proposed conceptual designs for the processing of Athabasca
bitumen and Venezuela Zuata heavy crude oil. In 2005 it was com-
pleted and started up a 1200 BPSD of a Commercial Demo Plant
(CDP) at Eni Taranto Refinery [60]. The implementation of the first
EST industrial plant (23,000 BPSD capacity) is in progress at Eni
Sannazzaro de’ Burgondi Refinery (Pavia, Italy) expecting to be in
operation by the end of 2012.
Headwaters Technology Innovations Group (HTIG) developed a
catalytic heavy oil upgrading technology known as HCAT. The
HCAT process converts low quality feedstock such as heavy oil, res-
idue and oil sands bitumen into high quality synthetic crude oil.
The process uses a molecule sized catalyst, chemically generated
within the reactor system through a conditioning process, to
achieve high conversion of oil. HCAT significantly improves the
conversion of heavy oil as well as reduces sediment formation [61].
HCAT technology offers several significant advantages over pro-
cesses using supported catalysts such as non-deactivating molecu-
lar catalyst, constant product quality, feedstock flexibility, flexible
conversion (up to 95%), higher reactor throughput, simple, two-
phase gas–liquid reactor. Recently HTIG has announced that Neste
Oil Corporation’s Porvoo Refinery at South Jordan, Utah, is the first
refinery to commercially implement Headwater’s HCAT heavy oil
upgrading technology. The Neste Oil facility as a commercial refer-
ence would generate interest around the world in adding HCAT to
ebullated bed upgraders. Since more than 500,000 barrels of heavy
oil are processed in these upgraders every day, and at least
200,000 BPD of additional capacity to be added by 2014, top
116 L.C. Castañeda et al. / Fuel 100 (2012) 110–127

Distillates
Vacuum
Distillation Distillates

C3-C4
Delayed coking
Fractionator
Heavy Upgraded
Naphtha
crude oil crude

Light
gas oil
Atmospheric
residue Coke drum Stripper Heavy
gas oil
Heater

Vacuum
residue
Coke

Gasification Syngas

Scrubber
Steam
Oxygen BFW
Bleed to SWS

Reactor Boiler
Soot Filtercake Ni/V ash
quench Work up
Filtration

Fig. 4. Delayed coking–gasification upgrading scheme [28].

authorities of HTIG predict a very substantial market for the HCAT ready reported and tested at commercial scale while others are still
additive technology [62–66]. being proposed and under evaluation.

3. Combined upgrading processes

It is in general accepted that light low-metal content feeds are
better upgraded by RFCC, while heavy high-metal content feeds
by hydrogen addition or carbon rejection type of technologies.
For the case of heavy and extra heavy petroleum the decision of
using coking or hydroprocessing depends on technical and eco-
nomical evaluations, not only based on the production of upgraded
crude oil but also on the impact of the quality of the produced dis-
tillates on the performance of the down-stream refining processes,
for instance distillates from coking base upgraded oil (coker naph-
tha and gas oil) require further hydrotreating, while those from
hydroprocessing may not need post-treatment depending on the
desired specification of final products. In any case, making a deci-
sion on which upgrading technology is more suitable for certain
crude oil is not a simple task and must take into consideration sev-
eral factors, among the most important are: price of crude oil, level
of impurities of the feed, target of upgraded oil quality, and process
scheme of the refinery where the upgraded oil will be sent.
One attractive option to achieve the maximum benefit is by
combining various technologies. That is, using more than one pro-
cess to upgrade heavy petroleum. In such a way the advantages of
each approach are put together in an integrated process scheme
and this synergy may yield higher benefits than the use of single
processes. The most promising combinations would be derived
from solvent deasphalting, visbreaking, delayed coking, gasifica-
tion, hydrocracking and hydrotreating. Some of them have been al-
3.1. Deasphalting/gasification
With the integrated deasphalter–gasification unit, the gasifier
feed is taken directly from the asphalt stripper. The asphalt is
heated to the temperature required for optimal pumping to the
gasifier prior to solvent removal, when its heat transfer character-
istics are more favorable. The result is that viscosity limits on the
asphaltenes are eliminated. Most importantly, high severity deasp-
halting with pentane produces a higher yield of DAO and enhances
the refinery’s production of diesel oil [11,17].
A summary of the feeds and products of integrated deasphalting
and gasification is given in Fig. 3. Integrating solvent deasphalting
with gasification enhances the operation and economics of both
technologies. The following are the main synergies between the
deasphalter and the gasifier:
 Beneficial use of the asphaltenes, internal consumption of low-
level heat.
 Production of hydrogen for DAO treating.
 Recovery of hydrogen from hydrotreating purge gas.
 Increase the throughput or the crude flexibility of the refinery
without creating a new, highly undesirable heavy oil stream.
 Increases a refinery’s production of diesel oil.
 Increase the value of the crude because SDA removes the heavy
components, reduces the metal content, reduces the Conradson
carbon, and increases the API gravity of the crude.
 L.C. Castañeda et al. / Fuel 100 (2012) 110–127 117

Distillates
Atmospheric Vacuum
Distillation Distillation Distillates

Deasphalting
Heavy
crude oil

DAO
separator
Atmospheric
residue Extractor

Vacuum Pitch
stripper Upgraded
residue
DAO crude
stripper

Pitch DAO
DAO

C3-C4
Delayed coking

Naphtha

Light
gas oil

Coke Fractionator
Stripper Heavy
Coke drum
gas oil
Heater

Fig. 5. Deasphalting–delayed coking upgrading scheme [19].

 Sharing of each process’ heat. SDA process requires a significant
amount of heating to recycle the solvent used in the asphaltene
extraction. The heat is used to strip the solvent from the oil and
the asphaltene streams so that it can be recovered and returned
to the process.
 The gasification process produces heat that can be used for the
solvent recovery in the deasphalting unit.
 The energy balance between both units avoids external source
of heat required to separate the solvent from the DAO.
 Minimize stripping and asphalt fired heater duties.
 The products of deasphalting and gasification can also be bene-
ficially integrated.
 The hydrogen required for HDT of DAO is a primary product of
gasification and can be generated from the asphaltene to elim-
inate the need for any external supply.
 The purge gas from HDT may be derived to the gasifier.
 The sulfur in the DAO can be captured internally without
increasing the load on the refinery sulfur facilities.
Some other advantages may be obtained by adding TGP units to
existing solvent deasphalters. The gasification of the bottoms elim-
inates the need to blend the bottoms stream for sale because it
converts the undesirable asphaltene byproduct into clean syngas
in an environmentally manner. Use of this integrated process will
expand the market of each of these processes beyond that which
either could gain on its own.
The main results of the integration of SDA/GF can be:
 Hydrogen recovery on the order of 16,000 SCF/bbl of pitch feed.
 Pitch gasification can be on the order of 20% lower unit capital
cost than petcoke or coal considering elimination of the solids
handling an slurry feed system.
 Pitch gasification is a ‘‘dry’’ system, therefore 20–25% lower
oxygen consumption, higher cold gas efficiency compared with
water-slurry feed.
 In terms of the net realization, the SDA/GF integrated process
shows 1.33 USD/bbl crude versus 1.10 USD/bbl for SDA only,
evaluated for Canadian Cold Lake crude [67].
3.2. Delayed coking/gasification
As in the previous combined scheme (SDA/GF), another pro-
posal is to gasify the petroleum coke aiming at producing electric
power for export to electrical network and to support internal con-
sumption [32]. Fig. 4 shows a delayed coking–gasification scheme.
The main advantages of using a DC–GF combined scheme are:
 Heavy materials are completely exhausted to ashes and high
quality sulfur.
 Since GF can completely destroy the feedstock, the idea of pro-
ducing synthetic crude appears to offer a good opportunity.
 Starting from a crude it is possible to separate the heavy part
and produce electric power while the lighter part (synthetic
crude) can be sold to the crude market.
118 L.C. Castañeda et al. / Fuel 100 (2012) 110–127

Distillates
Atmospheric Vacuum
Distillation Distillation Distillates

Deasphalting C3-C4
Delayed coking
Heavy
crude oil
Fractionator
DAO Naphtha
separator
Atmospheric
residue
Extractor
Light
gas oil
Vacuum Pitch
residue stripper Upgraded
DAO crude
stripper Stripper Heavy
Coke drum gas oil
Pitch
DAO
Coke Heater
DAO

Pitch
Coke

Gasification Syngas

Scrubber
Steam
Oxygen BFW
Bleed to SWS

Reactor Boiler
Soot Filtercake Ni/V ash
quench Work up
Filtration

Fig. 6. Deasphalting–delayed coking–gasification upgrading scheme [28].

100 more asphaltenic hydrocarbons (asphalt) are not dissolved by the

Yield, vol%; API (upgraded crude)

90 Yield, vol% API solvent, and exit from the bottom of the extractor together with
80 a small amount of dissolved solvent.
The DAO mix leaves the top of the extractor and flows to the
70
solvent recovery system where the DAO product and the solvent
60
are separated. The solvent is recycled back to the extractor. Strip-
50 ping of the DAO is done together with the heavy coker gas oil in
40 the coker fractionation section to produce cracking feedstock.
30 The raffinate phase containing the asphalt and some solvent flows
20 at a controlled rate from the bottom of the extractor and is fed di-
10 rectly to the coking section. The asphalt, with recycle and solvent,
flows through the coking heater where it is rapidly heated to the
0
DC-GF SDA-GF DC-SDA-GF desired temperature for coke formation in the coke drums. In some
cases, coker gas oil injection may be desirable for an optimum de-
Fig. 7. Comparison of gasification combination schemes.
sign of the heat transfer equipment.
Advantages that this combination offers include:
3.3. Deasphalting/delayed coking
 Improved recovery of clean liquids and reduced coke produc-
Solvent deasphalting and delayed coking may be combined in tion due to pre-extraction of DAO prior to coking.
technologies such as the Foster Wheeler’s Asphalt Coking Technol-  Heat integration between the coker section and the SDA section
ogy (ASCOT process [14,22]). saves utilities.
Fig. 5 shows the scheme of these integrated technologies. In this  The solvent contained in the unstripped asphalt and deasphalt-
process fresh feed such as vacuum residue is taken to the desired ed oil (DAO) is recovered in the fractionator overhead.
extraction temperature prior to flowing into the extractor. In the  Solvent from the fractionator overhead drum may be used as
extractor, the solvent (normally light naphtha) flows upward, lean oil for C3/C4 recovery in the absorber, eliminating the need
extracting the more paraffinic hydrocarbons from the feed. The for lean oil recirculation from the naphtha stabilizer.
 L.C. Castañeda et al. / Fuel 100 (2012) 110–127 119

Distillates
Atmospheric
Distillation

Heavy
crude oil
Jet fuel

HP HDC
Vacuum Gas Oil Upgraded
Distillation crude
Gas Oil

Gasoline
MHDC
LCO
R2R
Atmospheric Slurry
residue

HYVAHL
HDM HDS
Acid gas
removal
Gas Oil

Hydrogen
Separator

Vacuum
Heater Guard reactors
residue Fractionator

Fig. 8. Hyvahl (VRDS)–RFCC (R2R) integrated scheme.

Table 2
Combined Hyvahl and R2R processes, properties of Hyvahl unit 370 °C + effluent.

Middle East blend properties 100% Vacuum residue 50–50 Blend atmospheric/vacuum residue 65–35 Blend atmospheric/vacuum residue
Sulfur (wt.%) 0.5–0.6 0.5 0.3
CCR (wt.%) 6.5–7.5 6–7 3–4
Ni + V (wppm) 10–15 10–12 8–10
Viscosity at 100 °C (cSt) 60–80 30–50 10–25

 The low asphalt partial pressure results in low coke and high
120
liquid yields in the coking reaction.
Inter-Stage Sep
Capacity per train, MBPD

100 NO Inter-Stage Sep

3.4. Deasphalting/delayed coking/gasification
80
Another option for combination of technologies is the integra-
tion of gasification to the scheme presented in the last section
60
(SDA/DC). Fig. 6 shows a scheme of deasphalting/delayed coking/
gasification integrated technologies [18,32]. The benefits of SDA/
40
DC would be provided and addition of gasification can supply
advantages such as:
20

 Power for site and export.

0
 Hydrogen for further upgrading.
50 60 70 80 90
 Chemicals products (methanol, SNG, etc.).
RV Conversion [%]

Fig. 9. Increasing capacity per train with inter-stage separation [43].
 Solvent introduced in the coker heater and coke drums results
in highly reduced partial pressure of asphalt feed, compared
with a regular delayed coking unit.
Fig. 7 shows a comparison of the three different gasification-
based combinations schemes processing the same feed. The
highest yield was obtained from the SDA/DC/GF combination due
to the higher recovered volume of liquid fractions and because in
this scheme the pitch is fed to the DC process and further the
coke is sent to gasification, while for the other two combinations,
coke and pitch are directly gasified. The API of upgraded crude
120 L.C. Castañeda et al. / Fuel 100 (2012) 110–127

Distillates
Atmospheric Vacuum
Distillation Distillation Distillates

Hydrogen H-Oil

Heavy Heater Acid gas Sour gas

crude oil Separator removal

Sour water
Atmospheric
distillation Naphtha
Atmospheric Mid distillate
residue
Vacuum gasoil
Reactors Separator
Vacuum
residue Vacuum Upgraded
Heater
distillation crude

Vacuum residue

C3-C4
Delayed coking
Fractionator

Naphtha

Light
gas oil
Coke drum
Coke Heavy
Stripper gas oil
Heater

Fig. 10. H-Oil and delayed coking configuration [41].

oil is proportionally affected by the amount of heavy component
entering to gasification.
Similarly to the concept used in FCC to represent the combined
impact of certain change in operation on both gasoline octane and
gasoline yield, that is the octane barrel, for the case of heavy oil
upgrading the ‘‘API barrel’’ can be defined as an index to account
for the increase of the API gravity of the feed and the change in
the volumetric yield during reaction. With the data reported in
Fig. 7, the results of this index are: DC–GF, 2253 API-barrel;
SDA–GF, 1662 API-barrel; DC–SDA–GF, 1953 API-barrel.
From the three gasification combined schemes, the integrated
DC–GF process shows the highest API barrel index. This is sup-
ported by a high yield and higher API than the other combinations.
The SDA–GF integrations shows the lowest API barrel basically due
to the lowest obtained yield, even though the API is similar to the
DC–SDA–GF combination.
3.5. Permutable Reactor System (PRS)/RFCC combination
This approach integrates the Hyvahl and R2R technologies pro-
cessing Arabian Light Vacuum Residue (VR). The vacuum residue
desulfurization unit (VRDS) employs a combination of several cat-
alysts with the objective of either producing ultra-low-sulfur fuel
oil (ULSFO) having a sulfur content of 0.3–0.5 wt.% or pretreating
the R2R feed, producing ‘‘zero’’ fuel oil [36]. This integrated scheme
as shown in Fig. 8 is an example of residue upgrading via the Axens
technology portfolio: high pressure hydrocracking (HP HDC), mild
hydrocracking (MHDC), Permutable Reactor System (Hyvahl) and
fluidized bed residue catalytic cracking (R2R).
The main advantages of this integration are:
 The level of conversion to 565 °C – distillates was varied over a
large range throughout the catalyst cycle: from 25% at the start-
of-run (SOR) to 55% at the end-of-run (EOR).
 The 370–565 °C VGO cut is not separated from the 565 °C + vac-
uum residue and the entire 370 °C + cut is sent to RFCC. The
RFCC therefore processes both hydrotreated VGO from the
MHDC unit and hydrotreated vacuum residue.
 The only product used as fuel is the clarified oil obtained by
filtration of the RFCC slurry. This can be completely con-
sumed as refinery fuel, representing less than 3.5% of the
crude.
 The high flexibility and PRS system enable the refiner to pro-
duce three different kinds of fuel oil which greatly assists in
meeting market needs for a period of at least 11 months of con-
tinuous operation on 100% VR feed. The fuels are produced by
the following HDS operating modes:
(a) 100% vacuum residue, 40,000 BPSD, that produces 0.5–
0.6 wt.% sulfur feedstocks for the RFCC unit at moderate
conversion and efficient removal of metals and Conradson
carbon residue.
(b) 50% vacuum – 50% atmospheric residue to increase the
capacity to 52,000 BPSD, that performs HDS to produce
0.5 wt.% sulfur LSFO.
 L.C. Castañeda et al. / Fuel 100 (2012) 110–127 121

Distillates
Atmospheric Vacuum
Distillation Distillation Distillates

Hydrogen H-Oil

Heavy Heater Acid gas Sour gas

Separator removal
crude oil
Sour water
Atmospheric
distillation Naphtha
Atmospheric Mid distillate
residue
Vacuum gasoil
Reactors Separator
Vacuum
residue Vacuum Upgraded
Heater
distillation crude

Deasphalting

DAO
separator

Extractor

Vacuum
residue

Pitch DAO
stripper stripper
Pitch DAO

Fig. 11. H-Oil and solvent deasphalting configuration [41].

Table 3
Combined H-Oil and SDA processes, yield and properties of crude oil upgrading.
The following benefits of inter-stage separation can be
obtained:
Properties Heavy crude Upgrade crude
Yields (vol.%) 100 85–95  Improve reaction kinetics in the second stage reactor.
API gravity 10.8 23  Single train capacity can be increased.
Sulfur (wt.%) 4.39 1.74
 Improved process performance and product quality.
CCR (wt.%) 13.2 0.5–1.8
Ni + V (wppm) 205 5–6  Alternatively, the second-stage reactor size can be reduced to
Viscosity (cSt) 1447 2.7–3.2 decrease the plant investment.
 Optimization of the treat gas rates to the individual reactors.

(c) 35% vacuum – 65% atmospheric residue desulfurization

Results of inter-stage separation show that single train capacity
unit, 40,000 BPSD, that performs HDS to produce ULSFO at
for a typical residue conversion of 65%, can be increased from
0.3 wt.% sulfur.
about 46,000 BPSD to almost 80,000 BPSD as shown in Fig. 9.

Table 2 reports the results of using Hyvahl technology for pre-

treating FCC feedstock for different residue blends.
3.6. Ebullating bed combinations
Two-stage in-series H-Oil plant configuration is typically a func-
tional combination to assure a high conversion of vacuum residue
and good quality of the liquid products and higher HDS level be-
cause of the benefits of multi-stage reactors [44]. In this configura-
tion, the first stage reactor effluent (mixed phase) is separated into
vapor and liquid products: the inter-stage liquid is fed to the sec-
ond stage reactor and the vapor is routed to the overhead of the
hot high-pressure separator located after the second stage reactor.
3.7. Ebullated bed/delayed coking
The H-Oil process can be used in combination with a delayed
coking unit as shown in Fig. 10. Here a single-stage H-Oil unit is
sufficient, and the unconverted H-Oil bottoms are sent to the DC.
The mixture of distillates from straight run, H-Oil and coking are
refined in fixed-bed hydrotreating units to produce synthetic crude
[68].
Advantages of this process scheme are:
 Economically attractive when there is a market for the coke
product, however, the coker derived liquids must be further
hydrotreated.
122 L.C. Castañeda et al. / Fuel 100 (2012) 110–127

Distillates
Atmospheric
Distillation Hydrogen H-Oil
Heater Acid gas
Sour gas
Separator removal

Sour water
Heavy
Atmospheric
crude oil distillation Naphtha
Upgraded
Mid distillate crude

Reactors Separator Vacuum gasoil

Atmospheric Vacuum
residue Heater distillation

DAO
DAO

Deasphalting

DAO
separator
Extractor
Vacuum
residue

Pitch DAO
stripper stripper
DAO
Pitch

Fig. 12. Deep conversion H-Oil/SDA configuration [41].

Table 4
Combined H-Oil and SDA processes, yield and properties.

Feed CLL AR H-Oil AR DAO from H-Oil Asphalt from H-Oil

Yield (AR-based) (wt.%) 100 56.8 46.8 10.0
API gravity 6.7 13.2 17
Sulfur (wt.%) 4.8 1.4 1.2 2.3
Nitrogen (wppm) 5000 5100 3100 14,500
Nickel (wppm) 84 31 <3 170
Vanadium (wppm) 189 43 <3 240
Conradson carbon residue content (wt.%) 18 10.4 3.5 43
Vacuum residue content (wt.%) 67.5 22.9
Asphalt softening point (°C) 150

CLL AR: cold lake heavy atmospheric residue.

 Even though the ultimate residue is coke it represents only
about 10 wt.% of the feed of the H-Oil unit.
3.8. Ebullated bed/deasphalting
Another processing option is the combination of the H-Oil pro-
cess and solvent deasphalting (SDA) as shown in Fig. 11. In this
scheme the H-Oil unconverted bottoms are sent to the SDA unit
and separated into a deasphalted oil (DAO) stream and a residual
asphalt product. The DAO can either be recycled back to the
H-Oil reactor for further conversion and/or combined with the
H-Oil derived distillates for hydrotreating [68].
The main advantages of this process scheme are:
 Asphalt production is relatively low and can be sold or gasified
to produce hydrogen.
 The asphalt represents the ultimate residue which has a yield
around the same value as with the combination of H-Oil and
Coking.
 In this scheme a softening point of around 150 °C in the asphalt
means that it can be processed in the liquid phase, either sent
via pipeline to a gasification plant or to an asphalt pool.
 As the DAO does not contain asphaltenes, it can be sent as a
mixture with the virgin feed to the H-Oil unit.
The results of upgrading a heavy crude oil when an H-Oil-
deasphalting scheme is applied by IFP are reported in Table 3.
 L.C. Castañeda et al. / Fuel 100 (2012) 110–127 123

Distillates
Atmospheric Vacuum
Distillation Distillation Distillates

Hydrogen H-Oil

Heater
Heavy Acid gas Sour gas
removal Upgraded
crude oil
Sour water crude
Separator
Naphtha
Atmospheric Mid distillate
residue
Vacuum gasoil
Vacuum Separator
Reactors
residue
Atmospheric Vacuum
Heater distillation distillation
Vacuum
residue

Vacuum
residue

Gasification
Syngas

Scrubber
Steam
Oxygen BFW
Bleed to SWS

Reactor Boiler
Soot Filtercake Ni/V ash
quench Work up
Filtration

Fig. 13. H-Oil and gasification configuration [41].

10
70
Heavy Crude oil
Production 60
8 Upgraded crude
Consumption
Composition, Vol %
Hydrogen, wt%

50
6
40

4 30

20
2
10

0
0
50 60 70 80 90 100 LPG Naphtha L Gasoil H Gasoil VR
Conversion, vol.%
Fig. 15. Composition of heavy crude and upgraded crude with H-Oil–gasification
Fig. 14. Hydrogen balance on an H-Oil–gasification scheme [43]. scheme.

Important reductions in impurities contents are observed as well

as increase in API gravity and reduction of viscosity.
An additional ebullated bed/SDA combination is to send
the DAO as a mixture with the virgin AR feed to the H-Oil unit.
The DAO can be deeply hydrocracked in the H-Oil unit because
the DAO does not contain asphaltenes, but it has moderate resins,
aromatics and saturates. Fig. 12 illustrates this scheme.
The metals content of the H-Oil feed is reduced because of the
low asphaltene content of the blend of DAO and virgin AR Typical
DAO conversion levels up to 90% can be obtained. The
post-treatment of the products from H-Oil + SDA is less severe than
that required for products from H-Oil + Coking, particularly for sul-
fur and CCR reduction. Table 4 shows the yield and properties of
the H-Oil bottoms and DAO resulting from this option [68].
3.9. Ebullated bed/gasification
The integration of H-Oil and gasification processes illustrated in
Fig. 13 allows for the optimization of high conversion operations.
124 L.C. Castañeda et al. / Fuel 100 (2012) 110–127

Distillates
Atmospheric Vacuum
Distillation Distillation Distillates

Hydrogen Slurry process

Heavy Heater
crude oil Cold
Hot Separator
Separator
Slurry
Atmospheric Gas Oil
Reactors
residue LVGO
HVGO

Vacuum Fractionator
residue Upgraded
Heater
crude
HCGO Pitch
Naphtha
Vacuum & Gas oil
residue
C3-C4
Delayed coking

Naphtha

Light
gas oil

Fractionator Heavy
Coke
gas oil
Stripper
Coke drum Heater

Fig. 16. Uniflex Process integrated with delayed coking scheme [55].

110
Delayed coking
35°API and 0.8 wt.% of sulfur after the integration of H-Oil and gas-
Uniflex ification units. It is observed that vacuum residue is totally con-
100 verted thus producing more naphtha and light and heavy gasoils.
Liquid Yields [Vol. %]

This route compared with the combination of H-Oil/coking, im-

90
plies that the post-treatment of the products from H-Oil/SDA is less
severe than that required for products from H-Oil/DC, particularly
80
for sulfur and CCR reductions. Table 4 shows the yield and proper-
70 ties of the H-Oil bottoms and DAO produced from this fraction; the
asphalt represents the final residue with a yield of 10 wt.% of the
60 AR, which is around the same value as that obtained with the inte-
gration of H-Oil and coking. The asphalt has a softening point of
50 150 °C and could be blended to be sold as fuel.
DC only 85 90 95
Uniflex Conversion [wt%]
3.10. Slurry phase/delayed coking
Fig. 17. Liquid yields from Uniflex Process residue processed in delayed coking.

Although the Uniflex Process, which is a slurry phase process, is

For high conversion applications, and because the unconverted
residue from H-Oil is not stable for use as a fuel oil blend stock, a
promising alternative is gasification. The main advantage of the
integration of these two processes is the production of hydrogen
for the H-Oil process and any downstream hydrotreating. A bal-
ance conversion point is at about 83% conversion of the feed
because there is no incentive for conversion greater than 90% as
shown in Fig. 14 [45].
Fig. 15 presents the composition of a heavy crude oil with 16.4
°API and 7.3 wt.% of sulfur, and the resulting upgraded crude with
a significantly different process than delayed coking, it can be inte-
grated into a refinery with an existing delayed coking process. This
integration would be via selective routing of each unit’s streams to
the other unit and sharing of infrastructure and light-ends fraction-
ation systems [69].
Fig. 16 shows one possible combination of the Uniflex Process
and delayed coking. In this integration, the vacuum residue is split
with part of it directed to the Uniflex Process and the remainder to
an existing delayed coking process. The Pitch from the Uniflex Pro-
cess is combined with the remaining vacuum residue and directed
to the Delayed Coker. Heavy coker gas oil (HCGO) is now routed to
 L.C. Castañeda et al. / Fuel 100 (2012) 110–127
Heavy
SDA
Crudeoil
SPR
Fig. 18. Other alternatives for upgrading of heavy oils.
the Uniflex Process feed along with the Uniflex HVGO recycle
stream. Both processes products are sent to common fractionation.
The processing of vacuum residue in the Uniflex Process before
the delayed coking process accounts for the following advantages:
 Significant increases in product yields.
 Reductions in net coke yield. The degree to which this occurs
depends on the selected conversion level in the Uniflex Process.
 The relative economic attractiveness of the Uniflex Process ver-
sus delayed coking increases with the level of conversion in the
Uniflex Process.
Fig. 17 shows the results of the integration of Uniflex and DC
processes in terms of the increased liquid yields of an Arab Light
Residue.
The relative economic attractiveness of the Uniflex Process ver-
sus delayed coking increases with the level of conversion in the
Uniflex Process. This economic advantage is maintained at lower
conversion levels in the Uniflex Process, due to the additional pro-
cessing of the Pitch in the DC process resulting in some additional
liquid yields. This then provides the opportunity to optimize the le-
vel of conversion in the Uniflex Process.
3.11. Slurry-phase/fixed-bed hydrotreating
The Uniflex Process also has synergies with a residue hydro-
treating unit. Refiners with existing residue hydrotreating pro-
cesses (RHDT) have an opportunity to add a Uniflex Reactor up
front of the fixed bed reactors. This results in an integrated Uni-
flex-RHDT Process with the benefits of both technologies. Beside
the addition of the Uniflex Process reactor there would be the
requirement for some additional fractionation equipment to sepa-
rate the pitch stream from the other Uniflex products before they
are processed in the main RHDT reactors. The investment for this
approach would be less than the cost of a delayed coking process
[69].
3.12. Slurry-phase/ebullated-bed
As previously discussed, HCAT slurry phase technology is an-
other prospect to be integrated to improve the performance of
existing ebullated bed upgrading units as reported by Neste Oil
[63]. With more than 500,000 BPD of heavy oil processed in their
upgraders and 200,000 BPD of additional estimated capacity to
125
FBR EBR
DC
Upgraded
FBR
oil
GF
FBR
VB
be added by 2014, there would be a considerable market for the
HCAT technology.
3.13. Other combined schemes
Although not totally reported in the literature, the use of fixed-
bed hydrotreating with some other processes, such as delayed cok-
ing, gasification, visbreaking, solvent deasphalting, ebullated-bed
and slurry-bed hydrocracking, represents interesting alternatives
for upgrading of heavy oils. Being sediment formation one of the
main drawbacks of high pressure hydrocracking, e.g. EBR and
SPR, working FBR based technologies at moderate reaction severity
conditions will reduce this problem, thus increasing the possibility
to combine it with other process options, as is schematically repre-
sented in Fig. 18.
Since asphaltenes are the main responsible for catalyst deacti-
vation and strongly contribute to sediment formation, it is highly
desirable that they are either removed (by SDA) or cracked (by
SPR) before the heavy oil enters the FBR hydrotreating, so that
longer life of the catalyst is anticipated with the consequent saving
in catalyst replacement. Not having or having less amount of
asphaltenes in the feed to FBR will allow the hydrotreating for opti-
mizing reaction conditions to make the reaction more selective to-
wards high valuable desired products, e.g. gasoline and diesel. On
the other hand, using another process after FBR HDT has the incen-
tive of total conversion of the residue fraction, which nowadays is
the tendency towards zero fuel oil production refineries.
4. Concluding remarks
The worldwide tendency towards the production of heavy and
extra-heavy crude oils represents a great incentive for exploring
the possibility of combining the currently available technologies
for upgrading of such crudes. Carbon rejection or hydrogen addi-
tion based processes can work alone to reduce impurities content
and increase the API gravity of the feed. The decision of which ap-
proach is the best depends mainly on the properties of petroleum,
the target regarding quality of the upgraded oil, prices of oil, and
products demand.
Refineries like to use coking technologies, particularly delayed
coking, because it is a mature process with well-recognized com-
mercial experience in spite of knowing that product yield is low-
ered and the produced distillates require further treatment to be
incorporated in the fuel pool. This way of thinking is nowadays
126 L.C. Castañeda et al. / Fuel 100 (2012) 110–127

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